JPS61277945A - Preparation of photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce increase of fog during long storage by irradiating electron beams through an electron beam semipermeable film roughened on the surface capable of absorbing the irradiated electron beam energy. CONSTITUTION:The electron beam hardenable resin composition is hardened by irradiating electron beams through an electron beam semipermeable film capable of absorbing the irradiated electron beam energy on the electron beam hardenable resin layer under the conditions of electron beam irradiation intensity lower than the case of irradiating electron beams much enough not to leave any monomer or any low molecular weight oligomer, thus permitting fog to be remarkably decreased, and moreover much move effectively lowered by roughening the surface of said film regularly or irregularly.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a photographic light-sensitive material, and more specifically, the present invention relates to a method for producing a photographic light-sensitive material, and more specifically, a method for producing an electron beam-curable resin composition on a substrate, and irradiating this layer with an electron beam. The present invention relates to a method for producing a photographic material, which is cured to form a support, and a photographic light-sensitive layer is provided on the support.

[Conventional technology and its problems]

Conventionally, this kind of material, for example, a photosensitive material for photographic paper whose support base material is paper, has been made by coating the surface of the paper base material with a polyolefin resin, which is useful for speeding up photographic processing, etc. It has been frequently used in recent years to accommodate.

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

By the way, when forming a polyolefin resin coating, it is necessary to melt the resin at a high temperature of about 280 to 340°C. A large amount of the above-mentioned inorganic white pigment cannot be added to such a high-temperature molten polyolefin resin.
Moreover, under such conditions, the dispersibility is also poor. For this reason, the sharpness of photographic images could not be sufficiently improved.

Under these circumstances, attempts have been made to disperse large amounts of inorganic pigments in polyolefin resins using dispersants.

For example, JP-A-51-6531, JP-A No. 52-35625
No. 55-108658, No. 55-113039, No. 55-113040, etc. disclose techniques for coating the surfaces of titanium oxide particles with various compounds.

However, with these techniques, when polyolefin resin is melted at high temperatures, contamination from these additives occurs at the tie exit end of the extruder, and concave lines are formed on the surface of the molten film, which causes damage to the support. There is a problem in that surface grooves form and uneven coating of the emulsion occurs.

Furthermore, in JP-A-57-151942, it is proposed to use an alkyl titanate instead of the above-mentioned additive (which functions as a type of dispersant), and according to this, the above-mentioned problem can be solved. Improved.

However, in this case, the alkyl titanate-treated pigment enters the molten polyolefin resin at only about 10 to 20 wt%, resulting in insufficient sharpness, and the free alkyl titanate that is not bonded to the pigment This tends to occur, causing problems such as thermal decomposition during melting, emitting smoke in the coating, and sticking to the cooling roll, making it impossible to change the smooth film surface.

As described above, when pigments are incorporated into conventional polyolefin resin coatings, sufficient sharpness has not yet been achieved.

In order to solve the above problems, Japanese Patent Application Laid-Open No. 57-27257,
No. 57-49946 proposes a photographic support having a coating layer formed by coating a paper base material with a composition that can be cured by electron beam irradiation and curing the composition by irradiating it with electron beams. .

Using such a support, the content of inorganic white pigment can be increased to 20-70 wt%, so that the sharpness is significantly improved compared to polyolefin resin coatings.

However, when photographic materials obtained by coating a photosensitive layer on a coating layer that has been cured by electron beam irradiation are subjected to normal storage and development, fog increases, which is not negligible as a product. It has been found that this can lead to.

As an improvement method for this, Japanese Patent Laid-Open No. 59-124336 proposes a technique in which a barrier layer is provided between the paper of the support and the single layer of electron beam curable lacquer. However, this method still does not have a sufficient effect of suppressing fogging, and requires a process to further provide a blocking layer in addition to the conventional manufacturing process, which is disadvantageous in terms of manufacturing cost P.

The cause of fogging is not clear, but the above
99-124336, page 10, lines 4 to 12, it is assumed that one of the causes is a curable or uncured low molecular weight monomer contained in the single layer of lacquer. In order to put into practical use a photographic material using a support having an electron beam curable coating layer, a solution to the above-mentioned fogging is required.

On the other hand, JP-A-57-30830, JP-A-59-1775
No. 43, JP-A No. 59-47845C1, JP-A No. 60-
No. 17446 proposes a technique for manufacturing a photographic support having a coating layer cured by electron beam radiation, which has an uneven surface. A photographic light-sensitive material having a photographic light-sensitive layer provided thereon showed a rapid increase in fog during storage.

[Purpose of the invention]

An object of the present invention is to coat at least one side of a support base material with an electron beam curable composition, cure it with an electron beam, and obtain a photographic support having regular or irregular irregularities on the surface. When a photosensitive layer is coated on the cured coating layer to form a photographic material, there is little increase in fog over storage, and the sharpness of the photographic image is improved, as is the adhesion between the substrate and the coating layer. The object of the present invention is to provide a manufacturing method that allows an excellent photographic material to be obtained.

[Structure of the invention]

In order to achieve the above object, the present inventors have investigated various methods, and have found that, rather than irradiating electron beams sufficiently so that no low-molecular monomer remains when curing the electron beam curable resin composition, Fogging occurs under conditions where the amount of the electron beam curable resin composition is small, that is, when curing the electron beam curable resin composition, the electron beam is irradiated onto the electron beam curable resin composition layer through an electron beam semi-transparent film that absorbs the energy of the electron beam. We have discovered a completely unexpected fact that the amount of water decreases significantly.

In this case, by forming regular or irregular irregularities on the adhesion surface of the electron beam semi-transparent film, the surface has regular or irregular irregularities, and furthermore, it is possible to apply photographic exposure on this film. It was possible to obtain a photographic support that does not have the problems of the prior art even when a layer is formed.

In other words, the problem with the prior art described above is that the electron beam is irradiated from the electron beam curable resin composition layer side, and the electron beam irradiation is performed through an electron beam semi-transparent film that absorbs the energy of the irradiated electron beam. A method characterized in that the surface of the electron beam semi-transparent film has regular or irregular irregularities, and the irregular surface is in close contact with the electron beam curable resin composition layer during electron beam irradiation. It is solved by

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

When a product was manufactured using the method of the present invention, the sharpness of the photographic image, the smoothness of the surface, and the adhesion between the base material and the coating layer were not impaired.

In addition, the method of closely adhering an electron beam transparent film on the electron beam curable resin composition layer during electron beam curing is disclosed in Japanese Patent Application Laid-Open No. 47-30.
No. 730, JP-A-51-77800, JP-A-57-3
No. 0576, JP-A-57-21965, JP-A-57-
No. 22204, Japanese Patent Application Laid-open No. 59-68240, etc., but none of them were expected to have an effect such as a significant reduction in fog when irradiated with an electron beam under the conditions of the present invention. do not have.

The structure of the present invention, materials used, etc. will be further explained below.

In the method for producing a photographic material of the present invention, an electron beam curable resin composition consisting essentially of an electron beam curable compound and a pigment is coated on at least one side of a substrate to obtain an electron beam curable resin composition layer. When this layer is irradiated with an electron beam, the electron beam is irradiated to the electron beam curable resin composition layer through an electron beam semi-transmissive film that absorbs the energy of the irradiated electron beam to cure it. A support is prepared in which the surface of the semi-transparent film has regular or irregular irregularities, and the irregular surface adheres to the electron beam curable composition layer during electron beam irradiation. It consists of providing a photosensitive layer.

Next, materials that can constitute the electron beam curable composition used to obtain the silver halide photographic material of the present invention will be explained.

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 curable by electron beam irradiation.

Compounds that can be cured by electron beams that can be used in the present invention include 1. For example, compounds containing two or more unsaturated double bonds in the molecule 6 can be cured by polymerizing or crosslinking by generating radicals etc. by electron beam irradiation. Compounds can be mentioned. Further, examples include cationic polymerizable compounds (in this case used in combination with an initiator) as shown in JP-A No. 59-147018, Japanese Patent Application No. 59-32237, and the like.

As described above, there are no particular restrictions on the compounds that can be cured by electron beams, but acrylate compounds (including acrylate compounds that have urethane bonds in the molecule and acrylate compounds that also have epoxy bonds), esters (
(including those with similar bonds), etc. can be adopted.

In addition, especially when using a paper base material as a support base material,
If the amount of the inorganic white pigment added is increased, the cured coating layer may become brittle, so it is preferable to select one that does not impair the flexibility peculiar to 织. The following examples can be suitably used.

1) Acrylic compounds such as acrylic polymers 1,)-
1 Aromatic acrylates such as aromatic monoacrylates and aromatic diacrylates (such as those used in Examples) Aliphatic acrylates such as aliphatic monoacrylates, aliphatic diacrylates, and aliphatic triacrylates (such as those used in Examples) etc.) l)-2 Polyester acrylate A.C.G. van Dostachoot &
A, C, J, Van ost
erhout and A, van Neerbos
) Written by Double 1 Liaison Chin Bent (Double
e Liajson-Chiw Pe1nt, )
27 (295), 135 (1980).

1)-3 Acrylate Oligomer 1)-4 Epoxy Acrylate Japanese Patent Publication No. 47-13023, Japanese Patent Publication No. 162713-1987
Compounds disclosed in No.

That is, epoxy acrylates obtained by adding acrylic acid or other α, β unsaturated carboxylic acids to polyfunctional epoxy compounds.

Commercially available products include the product name EA800 and EPM.
800 (Shin Nakamura Chemical Co., Ltd.).

1)-5 Silicon Acrylate A condensate of hydroxyl or methoxy group-containing silicone and hydroxyethyl methacrylate as disclosed in Japanese Patent Publication No. 48-22172 and Japanese Patent Application Laid-open No. 48-39594.

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

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

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

Commercially available products include Uvisan 783 and Uvisan 793 (manufactured by Toshi Thiokol Co., Ltd.).

2) Unsaturated polyester Special Publication No. 48-23654, Special Publication No. 49-23293, Special Publication No. 47103-1972, Special Publication No. 49-44572
No. 54-7473, and the like. As for the commercially available products, the product name is M.
8030 and M806O (both manufactured by Toagosei Chemical Industry Co., Ltd.).

3) Modified unsaturated polyester urethane Modified unsaturated polyester, especially the compound disclosed in Japanese Patent Publication No. 14667/1983.

Acrylic urethane-modified unsaturated polyesters, particularly the compounds disclosed in Japanese Patent Publication No. 14790/1983.

Liquid unsaturated polyester having an acrylic group at the end, especially US Pat. No. 3,455,802 and US Pat. No. 3,485,73
The compound disclosed in No. 2.

4) Ester oligomano acrylates such as oligoester monoacrylate, oligoester diacrylate, oligoester triacrylate, etc. Preferred examples of the compound include the following.

Maronix M-102, M-150, M-152, M
-54'00, M-5500, M-5700, XM-1
01XM-111, XM-113, XM-117, X2
15A (both are trade names, manufactured by Toagosei Chemical Industry Co., Ltd.).

5) Butadiene-based polymer Urethane-ized 1,2-polybutadiene disclosed in JP-A-50-123187, JP-A-54-14809
Modified polybutadiene disclosed in No. 4, which is obtained by adding a monoester compound to epoxidized polybutadiene and further adding an aliphatic lower carboxylic acid, can be mentioned.

Further, the molecular chain may contain hydrogenated or non-additive polybutadiene, and may have an electron beam reactive group (vinyl group, epoxy group, isocyanate group, etc.) or a non-reactive group. Examples of such compounds include Nl5SOPBB series, Gr series, C series, BT series, QI series, Cl series resins, TE resins, maleated P, etc.
B resin, BF resin (Nippon Soda Co., Ltd.) Po1y b
d series.

HTP-4, HTP-9, HTP-5MLD, HT
P-9PA, R-45HT, R-45M,
R-45MA, R-45EPT, R-45EP
Commercially available products such as I, R45ACR (Idemitsu Petrochemical Co., Ltd.) are also available.

6) Electron beam curable polymers containing carbocyclic or heterocyclic bonds in the molecular chain Such polymers have two or more terminal reactive groups in the molecule that can cause a curing reaction by electron beams, and the molecular chain Electron beam curable compounds containing a carbocyclic or heterocyclic bond therein can be used.

Preferable examples of the ring structure of this compound include a phenylene ring, a spiran ring, and a triacylone ring.

Also, a cycloalkylene ring, a bicycloalkylene ring, a naphthalene ring, a furan or fused furan ring, a thiophene or a fused thiophene ring.

Also preferred are pyrrole or fused pyrrole rings, toran or pyrone rings, pyridine rings, quinoline or isoquinoline rings, azole rings and azine rings.

These compounds include, for example, NK ester EA-800, EP
M-800, A-BPE-4, BPE-200 (Shin Nakamura Chemical Co., Ltd.), Photo+mer4028 (Di
amond Shamrock), M210 (Toagosei Kagaku Kogyo Co., Ltd.), R-604 (Nippon Tohoku Co., Ltd.),
M315. Commercially available products such as M325 (Toagosei Kagaku Kogyo Co., Ltd.) are also available.

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

Moreover, the number average molecular weight is preferably 500 to 2000.
about 0, more preferably about 1000 to 10000,
In addition, for the purpose of adjusting the viscosity of the composition, curing characteristics, physical properties of the cured layer, etc., especially for the purpose of imparting flexibility, a monomer having an unsaturated bond may be mixed with the above compound. It is preferable to use it.

The mixing ratio with the monomer is arbitrary, for example, 5/95 to 9.
It can be used in a wide range of weight ratios of 0/10.

Any reactive compound that can be copolymerized may be mixed as these monomers, but acrylate and methacrylate monomers are particularly preferred.

Typical monomers used in combination include the following.

A) Polyester acrylate, polyester methacrylate Toagosei Chemical Industry Co., Ltd., trade name Alonisox M61
00. Alonisox M6200. Aronix M625
0. Aronix M6300. Aronisox M6500
．． Aronifux M7100゜Aronix M8100 San Nopco Co., Ltd., product name Photomer 5007゜Photomer 5018. Photomar 4149゜Northeast Japan (
Co., Ltd., product name Kayamar MANDAi Kayarad HX2
20. Kayarad HX620゜B) Polyurethane acrylate Polyurethane methacrylate Osaka Organic Chemical Co., Ltd., trade name: Bishut 829 Tsukuyasei Kagaku Kogyo Co., Ltd., trade name: Aronix M1200.
Aronix MI100 Shiraki Yubika Co., Ltd., product name A
C3801 Shin Nakamura Chemical Co., Ltd., product name NK Ester U
-108A, NK ester U4HA Toshi Thiokol Co., Ltd., trade name Ebisan 893 San Nobuco Co., Ltd., trade name Photomer 5 Q O7゜Photomer 6008゜C) Epoxy acrylate epoxy methacrylate Osaka Organic Chemical Co., Ltd., trade name Visco- Toro 0 San Nobuko Co., Ltd., product name Photomer 3016° Photomer 3
082 Nippon Yubika Co., Ltd., product name AC3301゜AC370
1, AC3702; EX9004°X9006 D) Silicone acrylate Compounds disclosed in Japanese Patent Publication Nos. 48-22172 and 48-39594, respectively.

E) Monofunctional monomers 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 include the product name Pho.
tomer 4039 (Diamond Shamr
ock company), 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 ,
such as divinylbenzene.

Q) Trimethylolpropane triacrylate or higher functional monomers, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, ethylenediamine acrylamide, etc.

Furthermore, for the purpose of improving flexibility and adhesion of the support base material, thermoplastic resins represented by the following may be mixed and used.

(1) Cellulose derivative nitrocellulose, cellulose acetate butyrate,
Ethyl cellulose, butyl cellulose, etc.

(2) Polyvinyl alcohol resins polyvinyl alcohol, polyvinyl butyral, polyvinyl acetal, etc.

(3) Vinyl chloride copolymers: vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl acetate-maleic acid copolymers, etc.

(4) Polyurethane resins (5) Unsaturated and saturated polyester resins (6) Polyamide resins (7) Low molecular weight polyolefins, low molecular weight polybutadiene, etc. These thermoplastic resins, even if acrylic modified double bonds are introduced, It's okay, and it doesn't have to be.

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

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

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

Solvents that can be suitably used in preparing the composition include methanol, ethanol, isopropanol, alcohols such as buknol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, ethyl butyrate. Examples include esters such as ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, glycol ethers such as dioxane, aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane and 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, etc. can be used, but titanium oxide, barium sulfate, and calcium carbonate are preferably used. . Further, the dispersibility of titanium oxide can be improved by treating the surface of titanium oxide with a metal oxide such as hydrous alumina oxide or ferrite oxide.

The amount of the inorganic white pigment is preferably 25 to 250 parts by weight based on 100 parts by weight of the electron beam curable composition. More preferably, it is 30 to 150 parts by weight. In addition, the average particle diameter of the pigment is preferably 0.05 to 10 μm, more preferably 0.1 to 3 μm.

In addition, a blue pigment, an antistatic agent, a fluorescent whitening agent, etc. 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 wood-free paper, paper bases made of natural pulp, synthetic pulp, or mixtures thereof, and various types of photographic base papers can be used.

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

The thickness of the paper base material is 80 to 250 μm, and the basis weight is 60 to 250 μm.
250 g/rd, more preferably 80-200 g/rd
n? It is preferred that the surface is smooth or rough. The surface may be subjected to various surface treatments, such as corona discharge, if necessary.

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

That is, the above-mentioned components to form a composition are charged into a kneading machine either all at the same time or individually one after another. In this case, various kneading machines can be used for mixing the coating composition, and usable kneading machines include, for example, a two-roll mill, a three-roll mill, a pebble mill, a ball mill, a sand grinder, a high-speed stone mill, and a high-speed stone mill. There are impact mills, Ni-Goo, homogenizers, etc.

Further, as the coating method, for example, air doctor coating, blade coating, squeeze coating, air knife coating, reverse roll coating, transfer roll coating, cast coating, etc. are used.

The coating thickness is 1 to 100 μm, more preferably 5 μm.
It is preferable to set it to 50 micrometers.

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

In addition, the electron beam characteristics are preferably 70 to 750 KV, more preferably 100 to 300 KV in terms of penetrating power.
Using an electron beam accelerator, the absorbed dose is 0.1 to 10 Mrad.
It is preferable to do so.

If the voltage is 70 KV or less, the uniformity of the electron beam in the width direction of the substrate is poor during electron beam irradiation, making it difficult to obtain uniform curing and a coating film.

In the present invention, the electron beam curable resin composition is cured by irradiating the electron beam through an electron beam semi-transparent film. The electron beam semi-transparent film may be of any material as long as it absorbs the energy of the irradiated electron beam. A membrane-like material having the flexibility of a sheet strip can be preferably used. Specifically, copper plates, aluminum plates, metal plates such as copper plates, polyester films, acetic acid fiber films, fluorinated hydrocarbon (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 and shielding properties against electron beams.

In the present invention, the electron beam semi-transparent film is brought into close contact with the electron beam curable resin composition layer. Regular or irregular irregularities are provided in advance on the surface of the electron beam semi-transparent film that is in close contact with the film. Specifically, the surface of the electron beam semi-transparent membrane is made uneven by machining, etching or stamping, or by pressing the electron beam semi-transparent membrane itself into a predetermined unevenness. The unevenness may be provided by any other arbitrary means. There are no particular restrictions on the unevenness, and any type of unevenness may be used. For example, as the unevenness conventionally applied to photographic supports,
No. 5-26507, Special Publication No. 55-5103, Special Publication No. 5
No. 6-4902, Special Publication No. 57-53941, RD18
717, RD19745, etc., can be provided on the electron beam semi-transparent membrane in advance.

The thickness of the electron beam semi-transparent film cannot be unconditionally defined because the applied voltage during electron beam irradiation and the shielding performance of the electron beam semi-transparent film vary greatly depending on the material, but it must be at least the thickness determined according to the formula below. Something is preferable.

H= (V-60)/D However, in the above formula, l (is the thickness of the electron beam semi-transparent membrane, μm)
, V is the electron beam applied voltage (KV), and D is the electron beam semi-transparent film density (g/cat). Most of the irradiated electron beam energy is absorbed by the electron beam semi-transparent film. The amount of electron beam energy absorbed can be confirmed by the method described below.

Commercially available electronic film that changes coloring density depending on the amount of electron beam irradiation energy, such as the FWT Radiochromic Film Detector sold by Toyo Mezoic Co., Ltd.
or), determine the energy amount of electron beam irradiation when the electron beam passes through a semi-transparent membrane using Fuji Photo Film Co., Ltd.'s CAT film, and when it does not pass through the electron beam semi-transparent membrane. It is preferable that the electron beam energy absorption amount of the electron beam semi-transparent film determined in this manner is 50% or more of the irradiation energy.

Note that during electron beam irradiation, an inert gas such as N,
It is desirable to irradiate in a gas atmosphere such as He or GO□.

Further, for the purpose of improving the adhesion with the photographic constituent layers, the coating layer may be subjected to surface treatment such as corona discharge treatment, or an undercoat layer may be separately applied to the surface of the layer to be covered.

It should be noted that the layer structure of the photographic emulsion layer and the photographic light-sensitive material formed on such a coating layer may be arbitrarily selected. As the photographic emulsion layer, monochrome and color emulsion layers can be provided. A color photographic emulsion layer can preferably be provided in the cured coating layer of the light-sensitive material of the present invention.

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

In such a case, the combination of a light-sensitive silver halide emulsion layer and a coupler is usually a cyan coupler in the red-sensitive silver halide emulsion layer, a magenta coupler in the green-sensitive silver halide emulsion layer, and a magenta coupler in the green-sensitive silver halide emulsion layer. A yellow coupler is associated with each blue-sensitive silver halide emulsion layer. There are no particular restrictions on the order in which the emulsion layers are stacked.

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

Preferred yellow couplers include benzoylacetanilide couplers and pivaloylacetanilide couplers. Preferred magenta couplers include 1-phenyl-3-anilino-5-pyrazolone couplers and pyrazoloazole couplers, such as pyrazolotriazole couplers. Preferred cyan couplers include phenolic couplers. Each of these couplers is preferably contained in the silver halide emulsion layer in an amount of about 0.05 to 1 mole per mole of silver halide.

In addition to the above-mentioned silver halide emulsion layer, the color photographic light-sensitive material to which the present invention is applied includes a protective layer, an intermediate layer, one filter layer, one scavenger layer, etc. on the support in an appropriate layer order and number. A photosensitive layer can be provided.

The silver halide contained in the silver halide emulsion layer used may be any of silver iodobromide, silver chlorobromide, silver bromide, silver chloroiodobromide, silver chloride, and silver chloroiodide. There may be,
A mixture of these may be used. These silver halides may be produced by any of the ammonia method, neutral method, acidic method, etc., and may be produced by any of the simultaneous mixing method, forward mixing method, back mixing method, conversion method, etc. Furthermore, silver halide grains with or without boundaries between different halogen compositions can be effectively used.

The binder that can be used in the constituent layers of the color photographic light-sensitive material to which the present invention is applied is most commonly gelatin such as alkali-treated gelatin or acid-treated gelatin. In combination with 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. It can also be used.

The silver halide emulsion used is a salt of a noble metal such as ruthenium, rhodium, palladium, iridium, platinum, or gold (
Noble metal sensitization with active gelatin, sulfur sensitization with unstable sulfur compounds (e.g. sodium thiosulfate, etc.), selenium compounds, etc. Chemical sensitization such as selenium sensitization with stannous salts, polyamines, etc. and reduction sensitization under low PAg conditions can be performed.

Further, these silver halide emulsions can be optically sensitized using various enhancing dyes in order to impart photosensitivity in a desired wavelength range. Preferred sensitizing dyes that can be used at this time include, for example, US Pat.
, 939.201, 2,072.908, 2,
No. 739,149, No. 2,213,995, 2゜49
3.748, 2,519. Oo1, West German patent 92
Cyanine dyes, merocyanine dyes, or composite cyanine dyes described in No. 9,080, British Patent No. 505,979, etc. can be used alone or in combination of two or more. These various optical sensitizers are used for purposes other than their original purpose, such as preventing fogging, preventing deterioration of photographic performance during storage of color photographic materials, and adjusting development (for example, gradation control, etc.). ) can also be used for the purpose of

Furthermore, the constituent layers of the color photographic light-sensitive material to which the present invention is applied may contain various photographic additives, such as ultraviolet absorbers (e.g., benzophenone compounds and benzotriazole compounds), dye image stabilizers (e.g., phenol compounds), etc. , bisphenol compounds, hydroxychroman compounds, bisspirochroman compounds, hydantoin compounds, dialkoxybenzene compounds, etc.),
Stin inhibitors (e.g. hydroquinone derivatives, etc.)
, surfactants (for example, sodium alkylnaphthalate L/7 sulfonate, sodium alkylbenzene sulfonate, sodium alkyl succinate sulfonate and polyalkylene compounds, etc.), water-soluble anti-irradiation dyes (
For example, azo compounds, styryl compounds, oxonol compounds, triphenylmethane compounds, etc.)
, hardeners (for example, halogen-substituted S-) riazine compounds, active vinyl compounds, ethyleneimino compounds,
epoxy compounds, water-soluble aluminum salts, etc.), membrane property improvers (for example, glycerin, polyalkylene glycols, aqueous polymer dispersions [latex], solid or liquid paraffins, etc.) can be added.

In the present invention, various coating methods can be used to coat each constituent layer of the color photographic light-sensitive material on the support of the light-sensitive material, such as dip coating, roller coating,
Methods such as bead coating and curtain flow coating can be employed. After application, drying is performed. In order to obtain a dye image using a color photographic light-sensitive material, after imagewise exposure, a color development process is performed if necessary. The processing steps basically include color development and bleach-fixing steps. In this case, each step may be independent, or two or more of the steps may be performed using processing liquids that have the respective functions, resulting in a single treatment. Further, each step can be divided into two or more times as necessary. In addition, during the treatment process, in addition to the above, a pre-hardening bath,
Various steps such as a neutralization tower, first development (black and white development), image stabilization bath, and water washing are combined. The processing temperature is set within a preferable range depending on the photosensitive material and processing prescription. Generally 20
~60°C, but the above-mentioned color photographic material is particularly
Suitable for processing at temperatures above 0°C.

Color developing agents used in color development include a variety of agents that are widely used in various color photographic processes. Particularly useful color developing agents include N,
It is an N-dialkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted or unsubstituted. 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,
Examples include N,N-diethyl-4-amino-3-(β-methanesulfonamidoethyl)aniline sulfate.

Among these exemplified compounds, those more preferably used include 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-ethyl-3-methylaniline-p-)luenesulfonate, N,N-diethyl-
4-amino-3-(β-methanesulfonamidoethyl)
Aniline sulfate is mentioned.

Various additives can be added to the color developing solution as necessary. For example, alkali metal hydroxides and carbonates, alkaline agents such as tertiary phosphates, buffers such as boric acid and acetic acid, thioethers, 1-aryl-3-pyrazolidones, N-methyl-p-aminophenols, Current accelerators such as polyalkylene glycols, benzyl alcohol, ethylene glycol, diethylene glycol, methanol, acetone, etc. There are solvents, development inhibitors such as potassium bromide and nitropenzimidazole, preservatives such as sulfites, hydroxylamine, glucose, and flukanolamines, and water softeners such as polyphosphoric acid compounds and nitrilo l-IJ acetic acid. .

[Embodiments of the invention]

Hereinafter, the present invention will be explained in more detail with reference to Examples. It should be noted that, as a matter of course, the present invention is not limited to the following examples.

The materials were blended as shown in Composition 1.2 below and kneaded in a ball mill for 20 minutes to uniformly disperse them to obtain two types of compositions. And add composition 1.2 to it (about 16
Apply a 25μ thick film on one side of 0g/m paper using a reverse coater.
An electron beam curable resin composition layer was formed by coating the resin composition in an amount of m.

(Composition 1) Aronix M8060 manufactured by Toagosei Chemical Industry Co., Ltd. 10 parts by weight Nippon Soda (
Polybutadiene TEA 100025 parts by weight Nippon U-Pica Co., Ltd. U-Pica Co., Ltd. AC570 120 parts by weight Titanium dioxide (anatase type, average particle size 0.20 μm) 45 parts by weight Viscodore 0030 parts by Osaka Organic Chemical Co., Ltd. 15 parts by weight of Polybutadiene R45ACR manufactured by Idemitsu Petrochemical Co., Ltd. 15 parts by weight of NK Ester AHD manufactured by Shin-Nakamura Chemical Co., Ltd. Titanium dioxide (rutile type, average particle size 0.25 μm) 40
Part by Weight Then, while conveying the paper at a line speed of L Om /win, a voltage of 280 kV 8 m was applied from the side of the applied composition layer.
A, 200kV10s+A, 200kV1mA (
7) The electron beam curable composition layer was cured by intense electron beam irradiation. The surface of the electron beam curable composition layer was subjected to a matte finish of 30 μm before being irradiated with an electron beam.

Stainless steel plates of 40 μm and 50 μm were brought into close contact and separated after being cured by electron beam irradiation. This cured the composition and formed irregularities in the cured layer. Next, an electron beam curable layer was provided on the opposite side of the paper by the same procedure. For comparison, a comparative sample was prepared in the same manner without attaching the electron beam semi-transparent membrane.

FIG. 1 schematically shows the state in which an electron beam is irradiated from an electron beam irradiation device to an electron beam curable resin composition layer provided on paper in this case. In the figure, 1 is 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 semi-transparent film.

As shown in the enlarged exaggeration, the electron beam semi-transparent film 6
has unevenness, which is in close contact with the resin 1i2.

20 W/m” on one side of each support thus obtained.
A corona discharge treatment was applied at an intensity of Silver halide emulsions are expressed in terms of silver)
.

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

Layer 2: 1.2g gelatin and 0.05g HQ-
A first intermediate layer containing 0.2 g of dioctyl phthalate dissolved in i.

Layer 3: 1.9 g gelatin, 0.040 g green sensitive silver chlorobromide emulsion (11150 mole % chloride) and 0.4 g
2g of the following magenta coupler (M-1), 0.
A green-sensitive emulsion layer containing 0.36 g of dioctyl phthalate in which 0.15 g of HQ-1 was dissolved.

N4: 1.9g gelatin and 0.02g HQ-
A second intermediate layer containing 0.5 g of dioctyl phthalate in which 1 and 0.7 g of an ultraviolet absorber (UV-1) are dissolved.

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

[6: Protective layer containing 1.4 g of gelatin.

C12° HQ-1 l1 Cρ UV-1 cml l Each sample thus obtained was heated at 30°C and relative humidity 60% for 3 hours.
After being stored for several months and subjected to light wedge exposure, it was subjected to color development using the processing steps and processing solution shown below.

A portion of each sample was coated, dried 10 days later, exposed and developed, and was used as data on the same day.

Processing process (33℃) Color development 3 minutes 30 seconds drift fixing,
Wash with water for 1 minute and 30 seconds
Dry for 3 minutes
60-80℃ [Color developer] Pure water 800
ml ethylene glycol 15I11!
Benzyl alcohol 15mJWh
tex B Bcone 1
g (fluorescent bleach manufactured by Sumitomo Chemical Co., Ltd.) Hydroxylamine sulfate 3 g 3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl) aniline sulfate 4
．． 5 g potassium carbonate (anhydrous) 30 g potassium sulfite (anhydrous) 2.0 g potassium bromide 0.65 g l-Hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 2 ml! Add water to make 11 and adjust the pH to 10.1 with sulfuric acid or potassium hydroxide.

[Bleach-fix solution]

Pure water 600
+5ffi Ethylenediaminetetraacetic acid-2-sodium 2 H2O25g Ammonium sulfite (40% aqueous solution) 35mJ Ammonium thiosulfate (70% aqueous solution) 50mf Ethylenediaminetetraacetic acid iron (I [l) ammonium 95g Aqueous ammonia (28
%) Add 25 ml of water to bring the total volume to 11, and adjust the pH to 6.9 with aqueous ammonia or glacial acetic acid.

Next, the following adhesion test and fog density measurement were performed.

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

(Measurement of fog density) The fog density of the developed sample was measured using a Sakura color densitometer model PDA-60 (manufactured by Konishiroku Photo Industry Co., Ltd.).

Figures 2 and 3 show the results of measuring the amount of electron beam irradiation energy in Examples using FWT Radiochromic Film Detectry sold by Toyo Mezoic Co., Ltd. The conditions for the measurement results (■ to ■) are as follows.

■ When irradiating an electron beam at 280 kV, 8 mA, and not passing through an electron beam semi-transparent membrane ■ When irradiating an electron beam at 280 kV, 8 mA,
When passed through a stainless steel plate with a sandblasted surface and a cloaked surface ■ 280 kV, 8 mA't' electron beam irradiated, 40
When passed through a stainless steel plate with a matt surface of μm thickness ■ 280kV, 8mAt' electron beam irradiation, 50μm
When the electron beam is passed through a stainless steel plate with a matte surface of m thickness ■ When the electron beam is irradiated at 220 kV and 10 mA and the electron beam is not passed through a semi-transparent membrane ■ When the electron beam is irradiated at 220 kV and ] mA and the electron beam is semi-transparent When not passing through a permeable membrane■Electronic at 220kV and 10IIA! [tL, 30μm
When passing through a thick stainless steel plate with a matte surface, the electron beam irradiation energy shielding effect of the electron beam semi-transparent film determined from this table was as follows.

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

The photographic materials of Examples 1 to 7 had a clean matte surface.

As is clear from Table 1, Example 1゜2.3 according to the present invention
．． It is clear that in comparison with Comparative Example 1.2, which is outside the scope of the present invention, Sample No. 4 has significantly improved fogging over time, and there is no problem with adhesion. In addition, in Comparative Example 3, it is clear that in order to reduce fog, it is possible to cure by reducing electron beam irradiation*vL and to reduce fog 'fr to some extent, but it is clear that the adhesiveness is poor and the objective cannot be achieved. It is. Examples 5, 6 and 7 according to the present invention also showed a significant improvement in fogging over time compared to Comparative Examples 4 and 5 outside the scope of the present invention, and even if the contents of the electron beam curable composition were changed, the present invention is clearly effective.

〔Effect of the invention〕

As described above, according to the present invention, nine photographic light-sensitive materials are produced which exhibit less increase in fog over storage, excellent sharpness of photographic uniformity, surface smoothness, and excellent adhesion between the base material and the coating layer. can.

[Brief explanation of the drawing]

Figure 1 is a diagram showing the state in which an electron beam irradiation device irradiates an electron beam curable resin composition layer provided on paper. It is a figure which shows several examples of the measurement result of nine electron energy by irradiating a composition layer. 1... Paper, 2... Electron beam curable resin layer, 3...
・Electron beam irradiation device, 4... Accelerator, 5... Electron beam irradiation window, 6... Electron beam semi-transparent membrane Ding Ero k11, Yue's lock 1 #Measurement mouth now Figure 1 Figure 2

Claims (1)

[Claims] 1. An electron beam curable resin composition consisting essentially of an electron beam curable compound and a pigment is coated on at least one side of a substrate to obtain an electron beam curable resin composition layer, and this layer is irradiated with an electron beam. In the method for producing a photographic material, the support is prepared as a cured resin layer, and a photosensitive layer is provided on the support. In this case, 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-transparent film that absorbs the energy of the irradiated electron beam, and the electron beam semi-transparent film is 1. A method for producing a photographic material, characterized in that the surface of the film has regular or irregular unevenness, and the uneven surface is in close contact with an electron beam curable resin composition layer during electron beam irradiation.