JPS60249145A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a base layer comprised of a layer hardened by the irradiation with electron beam having superior adhesion to a photography constituting layer contg. silver halide and superior film characteristics such as surface smoothness, etc. by allowing an epoxy compd. to coexist with an initiator which discharges a substance for initiating cation polymn. by the irradiation with electron beam. CONSTITUTION:Suitable epoxy compds. are epoxy resins expressed by the formulas, but are not limited to such compds. Although there is no particular restriction for the polymn. initiator, onium salts which liberate Lewis acds capable of initiating polymn. by the irradiation of electron beam are preferred. Further, an inorg. white pigment and a coupling agent as a dispersant are incorporated in the layer of a compsn. formed on the base material, and preferred coupling agent is a silane coupling agent or a titan coupling agent. The base layer comprised of such compsn. can maintain preservation stability of the liquid compsn. for a long period even if the content of the white pigment is elevated to high concentration. Moreover, the workability in the coating stage is superior and can adhere firmly to the photography constituting layer comprised of hydrophilic colloidal silver halide.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a silver halide photographic light-sensitive material. More specifically, the present invention relates to a silver halide photographic material having a support produced by electron beam irradiation and particularly suitable as photographic paper. (prior art). Conventionally, a support having a polyolefin resin coating layer used as a support for photographic paper has a coating layer formed on the surface of the paper base material in a molten state at about 300°C. As a result, the surface of the paper base material is deformed, resulting in poor surface properties and difficulty in forming a mirror surface. Additionally, when applying a thin layer of polyolefin resin, it is necessary to apply the coating at a higher temperature, and the polyolefin tends to thermally decompose, causing yellowing and pinholes. Further, it is preferable that the coating layer contains a white pigment, but when dispersing the white pigment in the molten polyolefin resin, the dispersibility is low and the content of the pigment cannot be increased, resulting in a photographic image. Sharpness is insufficient. In order to overcome these drawbacks, a method has been proposed in which a coating layer that can be cured by m+ ray irradiation is applied onto a paper base material and then cured by irradiating it with electron beams (Japanese Patent Application Laid-Open No. Showa 57
-27257, 57-30830, 57-49
No. 946). According to this method, since the coating and curing are performed at room temperature, the surface of the paper base will not be rough or pinholes will occur, and since the white pigment is dispersed at room temperature, the dispersibility is good, and the pigment-containing The amount can be increased, and the sharpness can also be improved. However, although the dispersibility of the white pigment can certainly be improved by using only the curing method as described above, when the content of the white pigment is increased to a high concentration, the storage stability of the coating composition is not sufficient. Therefore, it is necessary to develop a technology that can maintain white pigment stably for a long time and further improve workability during application. It is also clear that while the photographic paper support produced by electron beam irradiation has the above-mentioned advantages, it also has the following serious drawbacks. has been done. That is, compounds that can be cured by electron beam irradiation, particularly known compounds having ethylenically unsaturated double bonds in their molecular chains, form a cured layer when applied to a support base material and irradiated with electron beams. Since the surface of the cured layer is hydrophobic, it is extremely difficult to firmly adhere a silver halide photographic constituent layer made of a hydrophilic colloid such as gelatin onto the cured layer. Therefore, due to insufficient adhesion between the silver halide photographic constituent layers and the hardened layer, film peeling tends to occur during handling of halide steel photographic materials, especially during the development process, which has become a problem. There is. In order to overcome these difficulties, as a method for improving the adhesion between the hydrophobic support and the silver halide photographic constituent layer,
For example, after surface activation treatment such as corona discharge treatment or ultraviolet irradiation treatment, a photographic constituent layer is directly applied to obtain good adhesion, and a subbing layer is provided. Attempts have been made to obtain strong adhesion by applying a photographic constituent layer on top of the layer, but it has not been possible to obtain sufficient adhesion strength using only the surface activation treatment described above.
Furthermore, regarding the method of forming the subbing layer, it is difficult to expect strong adhesion that will not cause film peeling during the development process. Even when used as a subbing layer, there still remain problems such as insufficient adhesion with the cured layer. (Objective of the Invention) Therefore, the first object of the present invention is to provide a non-rogenated substrate having a support provided with a layer cured by electron beam irradiation, which has excellent dispersibility and filling properties of white pigment, and excellent image sharpness. The second objective is to provide a steel photographic material that can maintain the storage stability of the composition solution for a long time even when the white pigment content is high and the workability during coating is improved. It is an object of the present invention to provide a silver halide photographic material having a support provided with an excellent electron beam irradiation cured layer, and a third object of the present invention is to provide a silver halide photographic material having an excellent adhesive strength with the silver halide photographic constituent layers. Another object of the present invention is to provide a silver halide photographic light-sensitive material having a support provided with a densified layer formed by electron beam irradiation and having excellent film properties such as surface smoothness. (Structure of the Invention) The object of the present invention is to provide at least one surface of the support base material with
A layer of a composition containing a compound having at least two epoxy groups in one molecule, an initiator that releases a substance that initiates cationic polymerization by electron beam, an inorganic white pigment, and a coupling agent is formed, and the layer is cured by electron beam. This can be achieved by using a silver halide photographic light-sensitive material having at least one coating layer consisting of at least one hydrophilic colloid layer on top of the coating layer. The invention will now be described in more detail. In the present invention, the compound having an epoxy group contained in the layer of the composition formed on the support base material is a compound having at least two epoxy groups in one molecule. The above-mentioned compound having at least two epoxy groups in one molecule according to the present invention (hereinafter referred to as the epoxy compound according to the present invention) does not undergo ring-opening polymerization even when irradiated with lightning or consonant beams. It is a compound that causes a polymerization reaction when a substance that initiates cationic polymerization coexists. In the present invention, the epoxy compound according to the present invention and an initiator that releases a substance that initiates cationic polymerization upon electron beam irradiation (hereinafter referred to as the polymerization initiator according to the present invention) are incorporated into a layer of the above composition. Due to the coexistence of K, a polymerization reaction of the epoxy compound according to the present invention occurs by electron beam irradiation. As the epoxy compound according to the present invention, the following epoxy resins can be mentioned. However, the epoxy compound according to the present invention is not limited to dough. (Exemplary compounds) [11 Glycidyl ether type of bisphenol A (1-
1) (n-0~

0) [21 Side chain diglycidyl ether type of bisphenol A (n-2 to 3) (3) Di-(or tri-)glycidyl ether type of glycerin (3-1) (3-2) υ (n= 2 ) 14J Alicyclic diglycidyl ester or alicyclic di-
β-methylglycidyl ester type (diglycidyl or di-β-methylglycidyl containing an alicyclic group derived from tetrahydrophthalic acid, hexahydrophthalic acid, etc. in the molecule)
-Methylglycidyl ester type structure) (4-1 (n=0~1) (4-2) CH. (n-0~1) (5" Cyclo-\xene oxide type (1 in the molecule) (5-1) (5-3) (5-4) (5-5) (5-6) (6) Novolak-type epoxy resin (6'-1) (n-0-2) The epoxy compound according to the present invention as exemplified above is
It can be prepared manually as a commercially available product as shown below. a) Glycidyl ether type to bisphenol, such as Epikot 827 and Epikot 82 from Shell Chemical Co., Ltd.
8. 834. 836. Same 1001゜ Same 100.4.
1007: Ciba Geigy Co., Ltd. trade name Araldite CY252
, CY250, 6y26o, GY280゜6
071, 6084, 6097: Dow Chemical Co., Ltd. trade name DER330. 331. 337. 661. 664: Dainippon Ink & Chemicals Co., Ltd. trade name Epicron 800. Same 101
0, 1000, 3010: b) Bisphenol A side chain type diglycidyl ether type, for example, Adekal Resin EP - manufactured by Kadenka Kogyo Co., Ltd.
4000 C) Di-(or tri-)glycidyl ether type of glycerin For example, Epicoat 12, trade name of Shell Chemical Co., Ltd. d) Alicyclic diglycidyl ester or alicyclic di-β-
Methyl glycidyl ester type, for example, Ciba Geigy Co., Ltd. trade name Araldite CY
-183. CY-182゜Shell Chemical Co., Ltd. trade name Ebiko) E-190゜E
-871° Showa Denko Co., Ltd.'s product name Shokudyne S -500. Same S-508, Same S-509, Same 5-60]
-603X, S-607X, S-609X, S-
729゜S-540, S-550 Trade name of Dainippon Ink and Chemicals Co., Ltd. Epicron 200
．． 400 e) Cyclohexene oxide type For example, UCC product name ERL-4221, ERL-4289
, Ciba-Geigy 4206, Ciba-Geigy 4234, Ciba-Geigy C strain) product names CY-179, Ciba-Geigy CY-178, Ciba-Geigy CY-180. CY-175 Chisso Co., Ltd. product name C
X-221, CX-289. CX-2061 CX-301, CX-313f)
Novolac type epoxy resin (for example, Shell Chemical Co., Ltd., part name Epicor) 15
2. 154: Product name DEN-431 of Dow Ban Chemical Co., Ltd., 43
8, 439: Ciba Geigy Co., Ltd. product name EPN-1138゜ECN
-1235: Dainippon Ink Chemical Co., Ltd. trade name Epicron N-740
, N-680, N-695, N-565. N-577 The epoxy compound according to the present invention preferably has a molecular weight of 10,000 or less, more preferably 100,000 or less.
~3000 range. The polymerization initiator according to the present invention is not particularly limited, but preferably includes onium salts that release a Lewis acid capable of initiating polymerization upon electron beam irradiation. Such onium salts are represented by the following general formula (1). ) can be shown. General formula (1) (Ra' Rb2 Rf, 3 R(1'Z) ' (
MXm+n) where R', R2, R' and R4
represent organic groups which may be the same or different, and a, b
, c and d each represent an integer from O to 3, and a+b+
The sum of C+d is equal to the valence of 2. 2 is N==N, S, Se, Te, P, As, Sb. Bi represents a halogen atom (for example, an atom such as iodine, chlorine, or bromine); M is a metal or metalloid that is the central atom of the halogenide complex; Sb; Fe, Sn, Bi, Al, Ga, In, Ti
, Zn, Sc. Represents V, Cr, Mn, Co, etc. X represents a halogen atom, m represents the net charge in the halide complex ion, and n represents the number of halogen atoms in the rhodanide ion. Examples of complex ions represented by (MXm+n) in the above general formula (1) include BF, -, PF, ,
AsF, . sbF, l-, Fe(J4"-, 5n(J6"-, db
Among the compounds represented by the above general formula (1), diazonium compounds do not necessarily have a good shelf life and have a short pot life, so they are not suitable for two-part formulations. In addition, the nitrogen gas generated by decomposition tends to cause bubbles and pinholes in the coating film, which may cause coloring of the cured layer.Therefore, in the present invention, storage stability is Compounds other than diazonium compounds are preferred because they have excellent properties, are suitable for liquid blending, and are free from the concern of generating nitrogen gas. The onium polymerization initiator represented by the general formula (1) is
Diazonium compounds in which 2 is an NmiN group are known per se; for example, diazonium compounds in which 2 is an NmiN group are described in U.S. Pat. There is. Other onium-based polymerization initiators are Belgian Patent No. 828, 841, Belgian Patent No. 828.669.
and French Patent No. 2,270,269. The polymerization initiator described above is described in U.S. Pat.
No. 6, No. 3,949,143 and the method described in A. L. Mayoock et al., J. Organi.
cChemistry, Volume 35, A 8.2532'
Tf (1970), 1, Goerdeler; M
ethoden der OrganischenCh
em ie + ]IA2 + 591~'640
Page (1958), K. Ba5Se: Id. 12A, pp. 79-112 (1963), M. Drexler et al., J.A.C.S., vol. 75,
2705 (1953) et al. The amount of the polymerization initiator according to the present invention to be used may be determined depending on the curing rate and the applied curing method, and is 0.05 to 1 part by weight per 100 parts by weight of the resin component of the composition layer according to the present invention.
It is preferable to use it in a range of 0 parts by weight. The inorganic white pigment used in the present invention can be one commonly used in the field of photographic paper, such as titanium oxide (anatase type, rutile type), barium sulfate, calcium carbonate, aluminum oxide, magnesium oxide, etc. can also be used, especially titanium oxide, VkWl,
Barium and calcium carbonate are preferred. Further, the surface of the titanium oxide may be partially coated with a metal oxide such as hydrous alumina oxide, hydrous acetate ferrite, etc., on which the hydrated metal oxide legs 11 are removed. However, inorganic white pigments and Satsun 11 are not limited to these. The inorganic white pigment is the electron beam curable compound 1
00 parts by weight, it is preferably in the range of 20 to 200 parts by weight. In addition, the average particle diameter of the pigment is preferably 0.1 to 10 μm. In the present invention, the layer of the composition formed on the support base layer contains a coupling agent as a dispersant, and in particular, Japanese Patent Application Nos. 58-174980 and 5B-1757
It is preferable to include a titanium coupling agent and/or a silane coupling agent described in the specification of No. 385. The coupling agent in the present invention is a compound having two or more different reactive groups in its molecule, and one of these reactive groups is one that chemically bonds with the inorganic white pigment (methoxy group, ethoxy group, silanol group, etc.). The other is a reactive group (eg, epoxy group, methacrylic acid, amino group, vinylene group, etc.) that chemically bonds with a compound that can be cured by electron beams. Such a coupling agent has the function of acting as a bridge between the inorganic white pigment and the compound that can be cured by lightning or coronal radiation, through a strong chemical bond. As a result, the excellent effects described above are produced. In this case, the coupling agent is preferably a silane coupling agent or a titanium coupling agent, which is added to cover the surface of the inorganic white pigment. In other words, the coupling agent is a hydroxyl group of an inorganic white pigment,
It chemically bonds with the hydroxyl groups in the metal oxide layer that partially covers its surface. In other words, since the silane coupling agent has a group that forms a silanol group and a /-1: bamboo silanol group, in the form of a silanol group, the hydroxyl group of the inorganic white pigment and the oxidized It reacts with the hydroxyl groups on the metal surface to form a chemical bond with the inorganic white pigment. Titanium coupling agents also react with the hydroxyl groups of the inorganic white pigment and the oxidized metal surface that partially covers the surface. It reacts strongly with hydroxyl groups and forms chemical bonds with titanium atoms, such as a bond or an ester bond.The following are typical coupling agents used in the present invention. (Silane coupling agent) (17) CI(,=Cl−IC02CT(,C)(,C
H284(QC)1. ). (Titanium coupling agent) (1) (3) CI-1゜(CH3-CH-0→, Ti-[P-(QC8H, □)
2-OH]a(4)(C,I(,,0-),Ti-(P-(QC,3horsey
)2oH3t(6) "OH (8) C)1.-0-C)1.-C)l=c)I. (C3I% CCH2-0-)2T I -CP -(
OC+3Ht7)20H]tCH2-0=CH7-cs
=cH2 (9) CH3 ■ cn, -c-o-Ti+coo-cn=cH,)A(1
0) OH3 [CH2-C-0+2Ti+cOO-C) (=CH,)
As the silane coupling agent used in the present invention, a silane coupling agent having an epoxy group in the molecule is preferable from the viewpoint of adhesive strength with the photographic constituent layer. Among silane coupling agents and titanium coupling agents,
Compounds having -CI (=CH, group) are particularly preferred. In order to include such a coupling agent in the coating layer,
There are methods as below. That is, the first method uses the above-mentioned one type or a mixture of the two types.
This is a method in which an inorganic white pigment and the above-mentioned coupling agent dissolved in a solvent are added at the same time to a compound that can be cured by an electron beam or more, and after being dispersed and mixed, the mixture is coated onto a support base material and cured. . The second method involves dissolving a coupling agent in a suitable solvent, immersing an inorganic white pigment in this solution, subjecting it to surface treatment in advance, drying it, and applying one or more of the above 28 or more electron beams in a mixture. This is a method in which a composition is prepared by dispersing and mixing a composition in a compound that can be cured by a method, and then coating it on a support base material and curing it. The third method involves dissolving one or more of the above-mentioned compounds that can be cured by electron beam entrainment in a suitable organic solvent, and dispersing and mixing the inorganic white pigment that has been surface-treated with a coupling agent and dried. After that, it is applied onto a support base material and cured. Furthermore, a fourth method involves dispersing a coupling agent with an inorganic white pigment in an organic solvent before adding a compound curable by electron beam, and then adding the compound curable by electron beam and dispersingly mixing the coupling agent. In this method, a composition liquid is prepared, and then applied onto a support base material and cured. Among these, a method using an inorganic white pigment that has been previously treated with a coupling agent and dried is preferred. In addition, when an organic solvent is used in these, the viscosity of the composition liquid is lowered, the filling property of the inorganic white pigment is improved, and the surface smoothness of the coating layer is further improved. The amount of these coupling agents to be used is preferably in the range of 0.1 to weighted percentage relative to the inorganic white pigment. The layer of the composition containing the epoxy compound according to the present invention, the polymerization initiator according to the present invention, the inorganic white pigment, and the coupling agent (hereinafter referred to as the composition according to the present invention) is a single constituent layer on the support. It may be applied as a single layer or as a plurality of constituent layers. Various additives can be added to the layer of the composition according to the present invention as long as the adhesion to the photographic layer is not impaired. Specific examples of such additives include thermoplastic resins, coloring agents such as blue-tinted dyes or pigments, other antioxidants, antistatic agents, dispersants, and organic solvents for the purpose of adjusting viscosity. Various additives can be mentioned. Various types of mixers can be used to mix and disperse the composition according to the present invention, and examples of the mixers that can be used include Teha, two-roll mill, three-roll mill, pebble mill, -ball mill,
There are sand grinders, high-speed stone mills, high-speed impact mills, Ni-Goo, homogenizers, etc. Further, as a method for applying the above composition, methods such as air doctor coating, blade coating, squeeze coating, air knife coating, lino-roll coating, and cast coating are used. The coating thickness of the layer of the composition according to the present invention applied by the above coating method can be determined depending on the required performance for various support base materials, and is not particularly limited. Range of 1 to 51″l, preferably 2.0 to 51″l
It is about 30μ. The support substrate used in the present invention can be, for example, paper made of natural pulp, synthetic pulp, or a mixture thereof. Known paper strength agents, sizing agents, inorganic normal phase agents, colorants, fluorescent whitening agents, etc. may be added to these papers as desired. In addition to the above, synthetic papers such as polypropylene, polyethylene, and polystyrene, as well as film bases such as polyethylene terephthalate, etc. can also be used as the support base material according to the present invention, and furthermore, composite materials can be formed by laminating on the surface of the paper base. It is also possible to use a substrate formed with. The coating layer formed by curing the layer of the composition according to the present invention on these support base materials by electron beam irradiation (hereinafter referred to as the coating layer according to the present invention) is smoothed to have a mirror finish. You can also type it if necessary. To achieve a mirror finish, the surface to be treated can be brought into contact with a mirror roll, and an electron beam can be irradiated from the back side of the roll to harden it, thereby giving a trowel finish. In addition, after preliminary irradiation has been performed to partially harden the surface, it is peeled off after contacting the trowel-faced roll.
A method of performing secondary irradiation and completely curing may be used. The trowel-faced rolls include chlorine-plated rolls and stainless steel rolls. In addition, when forming a pattern, instead of using a trowel-faced roll, a roll such as a stainless steel roll or a chrome-plated roll can be used, and surface polishing, vapor deposition, etching, coating, etc. may be used. - It is possible to use a roll having a desired pattern such as a silk texture or a fine grain surface. To finish and mold the trowel surface, if a specific solvent is used, it may be done after applying the composition solution and removing part or all of the organic solvent, or after molding, the organic solvent may be applied. The solvent may be removed. The electron beam accelerator used for electron beam irradiation may be any one of an electrocurtain system, a van de Graaf type scanning system, a double scanning system, and the like. In addition, the electron beam characteristics are 100 to 7 in terms of penetrating power.
Using an electron beam accelerator of 50 KV, preferably 150-'300 KV, the absorption is 1%! lt O, 5-20
It is preferable to treat it so that Mr ad . Note that during electron beam irradiation, N, , He, C
o. However, the present invention does not utilize a radical reaction and therefore does not inhibit polymerization due to oxygen, so an inert gas atmosphere is not particularly required during irradiation. It's not something you do. The N layer according to the present invention exhibits good adhesion to the photographic layer as it is, but even better adhesion can be achieved by subjecting the coating layer to a surface activation treatment such as corona discharge treatment or glow discharge treatment. The same adhesion effect as described above can also be obtained by simple undercoat processing using gelatin or the like. In the present invention, at least one of the coating layers according to the present invention is provided on the surface of the support substrate on which the IC4 (e.g., silver halide emulsion layer, image-receiving layer in the dye diffusion method, etc.) is formed on which the photographic image is formed. exist. Further, in the case where the support base material is a water-absorbing material such as paper, the coating layer according to the present invention is preferably provided on both sides of the support base material from the viewpoint of waterproofing. In addition, if there is no layer on which a photographic image is formed on one side of the support base material, this type of coating layer on this side should be a coating layer having a composition similar to the coating layer according to the present invention except that the saw machine white pigment is removed. You can also do that. In the present invention, at least one hydrophilic colloid layer is provided on the coating layer according to the present invention. The aqueous colloid layer is a layer having a continuous phase of hydrophilic colloid, such as a gelatin-silver halide emulsion layer, an intermediate layer each consisting of a gelatin film, and an image-receiving layer in a dye diffusion method (instant color photography). It is 1-. The hydrophilic colloids include known formats and aqueous colloids used in photographic light-sensitive materials, such as gelatin, hydrolyzed primary cellulose acetate, cellulose derivatives such as carboquine methyl cellulose, hydroxyethyl cellulose, and methyl cellulose, and synthetic cellulose colloids. Binders such as polyvinyl alcohol, partially saponified polyvinyl acetate, polyacrylamide, polyN, N-dimethylacrylamide, polyN-vinylpyrrolidone, U.S. Pat.
, 341°332, 3,615,424, 3,
Water-soluble polymers such as those described in U.S. Patent No. 860,428, etc.; fi14,928, fi2,525
Gelatin conductors such as phenylcarbamylated gelatin, acylated gelatin, and phthalated gelatin as described in U.S. Pat. No. 2,548,520, U.S. Pat.
．． Polymerizable polymers such as acrylic acid (ester), methacrylic acid (ester), and acrylonitrile as described in No. 831,767 etc. include those obtained by graft copolymerizing monomers with ethylene groups to gelatin. , a polymer latex can also be contained in the hydrophilic colloid layer.The photographic light-sensitive material in the present invention is a material that forms visually distinguishable images using energy such as light, radiation, and particle beams. Examples include black and white and color silver halide photographic materials, heat-developable photographic phase materials, diffusion transfer light-sensitive materials, heat-developable color diffusion transfer light-sensitive materials, etc. Among these, the present invention is most advantageously applicable. The photographic materials used in the present invention include black and white and color silver halide photographic materials (silver halide photographic paper). In the case of 2), there is no particular restriction on the composition or layer structure of the photosensitive silver halide emulsion used therein, and it is possible to use a wide range of compositions (including layer structures, etc.) known in the art. %IC The preferred silver halide emulsion layer is a photosensitive silver halide emulsion layer, and examples of the silver halide in the emulsion layer include silver bromide, silver iodobromide, and silver chloride. Silver bromide, silver chloride, silver chlorobromide, etc. can be used as the binder for forming the photosensitive silver halide emulsion layer. Synthetic resins, parent compounds made of natural resins, aqueous colloids, polymer latexes, etc. can also be used in combination.The photosensitive silver halide emulsion used in the present invention is
The first filter is prepared by various well-known methods, such as mixing a nitric acid aqueous solution and a halide aqueous solution in the presence of a water-soluble polymer solution such as gelatin. A silver halide emulsion in which the above-mentioned silver halide grains are dispersed in a binder liquid can be sensitized with a chemical sensitizer. Chemical sensitizers that can be advantageously used in combination in the present invention are roughly classified into four types: noble metal sensitizers, sulfur sensitizers, selenium sensitizers, and reduction sensitizers. As the noble metal sensitizer, gold compounds and compounds such as ruthenium, rhodium, palladium, iridium, and platinum can be used. In addition, when using a gold compound, ammonium thiocyanate and sodium thiocyanate can be further used in combination. As the sulfur sensitizer, a sulfur compound such as activated gelatin can be used. As selenium sensitizers, active and inactive selenium compounds can be used. Examples of reduction sensitizers include monovalent tin salts, polyamines, bisalkylaminosulfides, silane compounds, iminoaminomethanesulfinic acid, hydrazinium salts, and hydrazine derivatives. In the present invention, in addition to the above-mentioned additives, the silver halide photographic light-sensitive material includes stabilizers, development accelerators, hardeners, surfactants, anti-staining agents, lubricants, ultraviolet anchor absorbers, and other photographic additives. Various additives that are unnecessary for phase materials are used. In addition to the silver halide emulsion layer, the above-mentioned light-sensitive material also includes a protective layer, an intermediate layer, a filter layer, a no-ration prevention layer,
An auxiliary layer such as a back layer can be provided as appropriate. Further, in the present invention, when the photographic light-sensitive material is a color silver halide photographic light-sensitive material, a copper halide emulsion adjusted to have blue sensitivity, green sensitivity, and red sensitivity is contained in combination with yellow magenta and cyan couplers, respectively. It is only necessary to apply the most suitable techniques and materials to photosensitive materials for uniform colors, and a non-diffusive coupler having a hydrophobic group called a ballast group in its molecule can be used. The coupler may be either 4-equivalent or 2-equivalent to silver ion. As the yellow coloring coupler, a known open-chain ketomethylene thread coupler can be used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. As the magenta coloring coupler, pyrazolone compounds, indasolone compounds, cyanoacetyl compounds, etc. can be used. As the cyan coloring coupler, phenolic compounds, naphthol compounds, etc. can be used. These couplers can be introduced into the silver halide emulsion layer by known methods such as those described in US Pat. No. 2,322.027. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters such as diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (such as acetyl tributyl citrate)
, benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), etc., or various solvents having a boiling point of about J]°C to 150°C, such as lower alkyl acetates such as ethyl acetate, butyl acetate, etc. After being dissolved in ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyether acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used. Any known method can be used for the photographic processing of the above-mentioned silver halide photographic light-sensitive material, and known processing solutions can be used. Processing temperature is usually 18℃ to 50℃
℃, but lower than 18℃ or 5Q'
The temperature may exceed C. Depending on the purpose, either black-and-white photographic processing to form a silver image or color photographic processing to form a dye image can be applied. In particular, the color developer generally consists of an alkaline aqueous solution containing a color developing agent, and the color developing agent may be a known primary aromatic amine developer 1, such as phenylene diamines. Other alkali metal sulfur salts, carbonates,
pI such as borates and phosphates (buffers, bromides,
Development inhibitors or antifoggants such as iodides and organic antifoggants can be included. In addition, water softeners, preservatives such as hydroxylamine, etc.
It may contain organic solvents such as benzyl alcohol, polyethylene glycol, development accelerators such as quaternary ammonium salts, etc. After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Metal salts of aminopolycarboxylic acids (e.g., ferric salts of ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, etc.) are useful both in stand-alone bleach solutions and in -bath bleach-fixing systems. Sodium thiosulfate, ammonium thiosulfate, and the like are useful as fixing agents. Various additives such as a desilvering accelerator and a pH buffering agent can also be added to the bleaching or bleach-fixing solution. (Examples) The present invention will be further explained below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. A silver halide color photographic emulsion containing gelatin as a binder was coated as a test sample, and after drying, the adhesion between the electron beam hardened layer and the emulsion layer was tested using the following test method. . This test is hereinafter referred to as the wakizuki test, and the test is conducted with the sample in a dry state. The test was carried out for two conditions: immersed in a developing solution and I2. The test method will be described below, and the same test method was used in each of the Examples described below. 1) Use a razor blade to make scratches on the emulsion surface of the test raw film with dry film and the dry film that has been developed at approximately 5-stage intervals in the shape of a base pattern, and apply Shichironon Tape evenly on top of these scratches. The adhesive surface of the cellophane tape was peeled off instantaneously (1), and the peeled portion that stuck to the adhesive surface of the cellophane tape and the portion that remained without being peeled off were measured in area ratio %. Therefore, when the peeling area is 00, the emulsion layer is not peeled off at all, indicating that there is a strong adhesive force between it and the cured layer, and when this value is 100, all the emulsion layers are peeled off, indicating that the hardened layer is not peeled off at all. This indicates that the adhesive force between the two is extremely small. The smaller this value is, the better; however, if it is less than about 20%, there is no problem in practical adhesion. In this method, peeled part h'' - 0 to 10% - 0 to less than 10% to less than 20% is grade 4, 20 to less than 40% is grade B, and 40 to less than 80% is grade 0. 80-100%
is classified as D class. 2) The test sample with the treated film was immersed in the color development solution for 3 minutes at °C, and then scratched in the shape of five square base marks on the emulsion surface with the tip of a sharp iron object in the processing solution. The state of peeling was observed by rubbing it with a finger. The areas where the emulsion layer peeled off were graded into grades AA to D in the same manner as in the end of the drying test. 3) Stability of inorganic white pigment after composition liquid preparation After composition preparation, the composition liquid was weighed for each sample, and the precipitation of the inorganic white pigment after 48 hours was evaluated using the following three-level criteria. . No O precipitate at all △ Some precipitate present × A lot of precipitate, separated from resin 4) Coating layer surface finish The wound sample was sampled and its surface condition was evaluated according to the following three-level criteria. O Smoothness is very good △ Good smoothness × Agglomerates are generated on the entire surface Example 1 Titanium oxide (anatase type, average particle type 0.3〃) 10
After washing and drying 0 g using acetone, 500 ml of methanol in which 3 g of Exemplified Compound (8) as a titanium coupling agent was dissolved was added, and the mixture was stirred for 2 hours at Ma level.
After that, it was left for about 6 hours. After removing the solvent under reduced pressure and air drying the titanium oxide,
Heat treatment was performed at ℃ for 10 minutes. Next, 50 parts by weight of 4-vinylcyclohexene dioxide (3,4-epoxycyclohexyl) methyl-3,4-epoxycyclohexanecarboxylate (50:50 mixture) diphenyliodonium hexafluorophosphate Upper surface treatment of titanium oxide at the top of the sit section 45 was mixed and dispersed in a ball mill using a silk material consisting of bone parts, and then covered with a 160 g/rn'' photographic base paper to a thickness of about K on both sides.
An electron beam was irradiated on each side of this # rice grain layer with an irradiation dose of 8 Mrad at an accelerating voltage of KV. After curing, a silver chlorobromide gelatin emulsion containing a coupler and its retention pI are added to one side of this coating layer.
Layer J was coated and dried to prepare a silver halide color photographic material. Let's call this sample Flat 1. Implementation F911 2 4-Vinyl cyclohexene dioxide bisphenyl A diglycidyl ether (mixture of 40) 54 parts by weight) 9 Phenylsulfonium hexafluorobore) Triple-114 (S titanium oxide (anatase sail 3 nm) 40 parts by weight After mixing and dispersing a composition solution consisting of 3 parts by weight of γ-glycidoxypropyltrimethoxysilane (exemplified compound +3+) in a ball mill,
It will be 2Gp thick on both sides of g/rf photo base paper5
I was honored. Then 8 Mra at 200 KV accelerating voltage
Each side of this coating layer was irradiated with an electron beam at a dose of d. After curing, a silver chlorobromide gelatin emulsion containing a coupler and its protective layer were coated on one side of the coating layer and dried to prepare a silver halide color photographic material. This sample is designated as A2. Comparative Example 1 A composition liquid consisting of 25 parts by weight of polyester acrylate, 2.5 parts by weight of hexanediol diacrylate, 15 parts by weight of trimethylolpropane triacrylate, and 5 parts by weight of titanium oxide (anatase type 0.3μ) was mixed and dispersed in a ball mill. After, scale t16011
One side of photographic base paper 21) was coated to a thickness of ρ. The coating layer was then irradiated with an electron beam on one side at a dose of 6 Mrad at a pressure of 200 KV in an acceleration chamber. After curing, a silver chlorobromide gelatin emulsion containing a coupler and its protective layer were coated on one piece of the coating layer tIi1 and dried to produce a silver halide color photographic material. This sample is designated as Flat 3. Sample A1-Flat 3 was measured for dry film attachment, treated membrane attachment, storage stability of the composition liquid, and surface finish of the coating layer using the above-mentioned method. The results are shown in Table-1. Table 1 From the above results, it is clear that the present invention significantly improves the storage stability of the composition and the adhesion of the silver halide emulsion. (Effects of the Invention) The present invention improves the preservation of coating compositions for coating layers containing inorganic white pigments compared to the prior art (techniques related to coating nets containing inorganic white II 21 cured by electron beam irradiation). The stability and adhesion between the layer and the hydrophilic colloid layer provided thereon are improved. Agent: Juno Bentanuki 1) Father-in-law

Claims (4)

[Claims] (1) A small number of support base materials (compounds having at least two epoxy groups in one molecule on one side, an initiator that releases a substance that initiates cationic polymerization by electron beam, an inorganic whitening agent, and a coupling agent) A halogen characterized by having at least one coating layer formed by forming a layer of a composition containing the compound and curing it with an electron beam, and having at least one hydrophilic colloid layer on the coating layer. Silver chemical photographic material. (2) The silver halide photographic material according to claim 1, wherein the coupling agent is a silane coupling agent. (3) The silver halide photographic material according to claim 2, wherein the silane coupling agent has an epoxy group. (4) The silver halide photographic material according to claim 1, wherein the coupling agent is a titanium coupling agent.