JPS61270750A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To give flexibility to a coating layer, to alleviate fogging, and to prevent yellow staining after a processing step by coating at least one side of a support with a prescribed electron beam-hardenable compsn. and forming the hardened coating layer by irradiation of electron beams. CONSTITUTION:At least one side of the support of a silver halide photographic sensitive material is coated with the compsn. to be hardened by the irradiation of electron beams, and the hardened coating layer is formed by said beams. This compsn. contains at least one of the following compds. (a) the electron beam-hardenable compd. having at least 2 terminal electron beam-hardenable groups, such as phenylene or cycloalkylene, in the molecule, and da carbon or hetero ring bond in the molecular chain; (b) that having polybutadiene in the molecular chain; and (c) that capable of reacting with said 2 compounds.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material in which a cured coating layer is formed by electron beam irradiation.

This type of material is used, for example, as a light-sensitive material for photographic paper.

[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. 55-11304.0, 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. It becomes a surface groove,
There is a problem that 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 only about 10 to 20 wt% in the molten polyolefin resin, 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.

This') 5 臥 Conventional (7) #! Jttz7+7 resin coating 91
When pigments are included, 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, the above technology still has problems in terms of flexibility.

In other words, it has been found that photographic materials using a support having a coating layer cured by electron beams exhibit a significant increase in fog over storage over time, and are also susceptible to breakage, significantly reducing their commercial value. Furthermore, it was found that yellowing appeared on the image surface when the image was subjected to a development process.

As an improvement method for these, Japanese Patent Application Laid-open No. 124336/1983 proposes a technique for providing a blocking layer between the paper of the support base and a single layer of electron beam curable rough carpet, but this method has not yet succeeded in suppressing overburden. The effect is not sufficient, and a process for providing an additional barrier layer is required in addition to the conventional product process, which is also disadvantageous in terms of cost.

Furthermore, for the purpose of improving flexibility, especially against bending,
Although it has been proposed to mix monomers or polymers with flexibility, the effect may not always be sufficient.

Moreover, there is a problem in that improving flexibility increases fogging, especially fogging over time.

There is also the problem that yellowing tends to occur after the treatment process, resulting in a decrease in commercial value.

In order to put into practical use a support having an electron beam cured coating layer,
There is a need for a solution to the above-mentioned flexibility and the problems of fogging and yellowing which are difficult to achieve at the same time.

[Purpose of the invention]

The purpose of the present invention is to impart excellent flexibility to a coating layer formed on a support, to significantly reduce the occurrence of fogging (particularly fogging over time), and to prevent yellowing after processing steps. The object of the present invention is to provide a silver halide photographic material having an excellent electron beam cured coating layer and having excellent photographic performance.

[Structure and operation of the invention]

As a result of intensive research, the present inventors have found that at least one side of the support base material of a silver halide photographic light-sensitive material is coated with an electron beam curable composition, and the composition is cured by irradiation with an electron beam. The above object has been achieved by forming a layer and by making the electron beam curable composition contain at least one of each of the following compounds fat, (bl, and tel).

fat An electron beam curable compound that has two or more terminal reactive groups capable of causing a curing reaction with electron beams in its molecule and contains a carbocyclic or heterocyclic bond in its molecular chain.

Mt.) An electron beam curable compound containing polybutadiene in its molecular chain.

(C1 Electron beam curable compound capable of reacting with the above two compounds.

Further, the above compound (the electron beam curable compound which is al has two or more terminal reactive groups capable of causing a curing reaction by electron beam in the molecule, and in the molecular chain) a unicine ring, a spiran ring, In the case of a substance having a structure containing a triazolone ring, the intended purpose can be more suitably achieved.

The reason why the terminal reactive group is used here is that although reactive groups in the molecular chain may occasionally participate in the curing reaction by electron beam irradiation, they do not participate in the curing reaction in most cases.

The electron beam curable composition is composed of the above electron beam curable compound and, if necessary, an inorganic white pigment and other additives.

In the electron beam curable composition used in the present invention, the elastic modulus of the coating layer obtained by electron beam irradiation is preferably 180 kg/m" or less, particularly preferably 120 kg/m" or less.

Preferred ring structures contained in the compound (al) of the present invention are, for example, the structures listed below.

■ Phenylene ■ Cycloalkylene ■ Bicycloalkylene ■ Naphthalene ■ Spiran ■ Thiophene and fused thiophene ■ Virole and condensed pyrrole ■ Triazolone 0 Pyran and pyrone @ quinoline and isoquinoline ◎ Azole [phase] Azine Next, the compound of the present invention (preferably used as al Specific examples of compounds that can be used are shown below.However, compound +a) is not limited to these.

(al Compound example: * -0-CH2-CH-Cut-00C-CH=CH
zR ” -(CH1CH*O) 5-OQC-C1=CHz
No. C1h-C1h-COO-CH=CHz These compounds are, for example, NK ester EA-800, EPM-800, A
-BPE-4, BPE-200 (Shin Nakamura Chemical Co., Ltd.)
, Photomer 4028 (Diamond S
hamrock)% M210 (Toagosei Chemical Industry Co., Ltd.), R-604 (Nippon Kayaku Co., Ltd.), M315
．． Commercial products such as 'M325 (Toagosei Kagaku Kogyo Co., Ltd.) are also available.

Preferred structural formulas of those used in combination with the compound tb of the present invention are as follows, for example.

(1) (A + - + ) is 70% or more hydrogenated polybutadiene, (X) is an electron beam non-reactive group, (Y) is an electron beam curable functional group, and n is an integer of 1 or more. Any compound that falls under this category can be preferably used.

Furthermore, the average molecular weight of (A) (A') is 300 to 4000
Preferably, it falls within this range. Preferable electron beam curable functional groups include vinyl groups, epoxy groups, and isocyanate groups. The X bonded to the polybutadiene in (A) includes a hydroxyl group, an alkyl group, a carboxyl 74 group, a -COOR group (R: an alkyl group), and the like.

Moreover, the polybutadiene (A) may have an added structure,
For example, maleic acid is added to (A).

Next, specific examples of compounds that can be preferably used as the compound (bl) of the present invention will be shown. However, the compound list is not limited to these.

(bl　Compound example: 毫-00-) 10 snow OH.

CH2 *-C1h-CH-CTo-CHg-OHCH CI(2 αυ CH2 *-Cut-CH-C)Iz-CHz-OHCH CI+.

These compounds of a are, for example, Nl5SOPB TE series TEA-1000, TE-2000 (Nippon Soda)
Commercial products such as Poly bd series R45ACR (Idemitsu Petrochemical) are also available.

Next, specific examples of compounds that can be preferably used as the compound (C1) of the present invention will be shown. However, of course, the compounds are not limited thereto.

(Example of C1 compound: Any electron beam curable compound that can react with the above compounds (a) and (b) can be used. Unsaturated polyesters having the following, modified unsaturated polyesters, allyl polymers, monomers having unsaturated bonds (septumer), and the like can be used.

Particularly preferred among these monomers are acrylate and methacrylate monomers.

Typical tel compounds are illustrated below.

A) Polyester acrylate, polyester methacrylate Toagosei Chemical Industry Co., Ltd., trade name Aronix M61
00. Aronix M6200. Aronix M625
0. Alonisox M6300. Aroninox M6500
．． Aronixx M7100゜Aronix M8100 San Nobuco Co., Ltd., product name Photomer 5007゜Photomer 5018. Photomer 4149 Japan Tohoku Co., Ltd., product name Kayamar MANDA; Kaya Lad HX22
0. Kayarad HX620B) Polyurethane acrylate, polyurethane methacrylate Osaka Organic Chemical Co., Ltd., trade name Bishut 823 Tsukuyasei Kagaku Kogyo Co., Ltd., trade name Aronix M1200.
Aronix MI100 Japan U-Pica 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 Nobuko Co., Ltd., trade name Photomer 5007'.

Photomer 6008 C) Epoxy acrylate, epoxy methacrylate Osaka Organic Chemical Co., Ltd., product name Visco-Toro 00 San Nobuco Co., Ltd., product name Photomer 3016 Photomer 3
082 Nippon Yubika Co., Ltd., product name AC3301, AC370
1, AC3702, EX9004. EXD) Silicone acrylate Compound 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.

For commercially available products, the product name is ph□
j□l1er4 Q 39 (Diamond 5ha
s+rock), 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.

G) 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 acecool, etc.

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

(4) Polyurethane resin (5) Unsaturated, saturated polyester resin (6) The (al compound) of the present invention such as polyamide resin is preferably contained in an amount of 15 times or more, particularly 25 times or more, in the total electron beam curing component. is preferable.If the placement is less than 15 times, the fog reduction effect is not significant.

In addition, the compound (b) is 5 to 65% by weight of the total electron beam curing components.
The content is preferably from 10 to 60% by weight. If it is less than 5% by weight, sufficient flexibility may not be obtained, and if it exceeds 65% by weight, it will harden and become stiff.
It requires a large amount of energy to form, which is disadvantageous in practice, and causes high fogging (which may be undesirable).

Further, the content of the compound (C) is preferably 5% by weight or more, particularly preferably 15% by weight or more. If it is less than 5% by weight, the viscosity may be too high, resulting in poor coating workability, or the curing reactivity may not improve.

In addition to the above-mentioned compounds, thermoplastic resins represented by the following may be mixed and used for the purpose of improving flexibility and adhesion of the support base material.

(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 (4) Polyurethane resin (5) Unsaturated, saturated polyester resin (6) Polyamide resin These thermoplastic resins may or may not have an acrylic modified double bond introduced therein.

These thermoplastic resins can be used in an amount of 20 parts by weight or less when the total amount of the electron beam curable resin composition of the present invention is 100 parts by weight.

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 alcohols such as methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, butyrate Examples include esters such as ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, glycol ethers such as dioxane, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane and heptane, and mixtures thereof.

Note that the support according to the present invention uses a white pigment in order to increase the reflectance since it is used as a reflective support, and the following inorganic white pigments are typically mentioned. That is, titanium oxide (anatase type, rutile type), barium sulfate, calcium carbonate, aluminum oxide, magnesium oxide, etc. can all be used. Preferred are titanium oxide, barium sulfate, and calcium carbonate. 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.

By irradiating the composition obtained by mixing the monomers etc. mentioned above with an electron beam, the elastic modulus of the coating layer becomes 180 k.
It is possible to obtain a photosensitive material with an elasticity of 120 kg/mm1 or less, which has sufficient flexibility and exhibits good performance as a photographic material.
When a covering layer having an elastic modulus as below is obtained, −i good flexibility can be obtained.

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 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.

In addition, the basis weight of the paper base material is 60 to 250 g/rd.

More preferably 80 to 200 g/n? It is preferred that the surface is smooth or rough.

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

That is, the above-mentioned 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 types of kneading machines can be used to mix and disperse 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, kneaders, 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 coating layer of the present invention can be smoothed to have a mirror finish, and can also be patterned 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 is irradiated from the back side of the roll to harden it, thereby giving the surface a mirror finish. In addition, after preliminary irradiation is performed to partially harden the surface, it comes into contact with a mirror roll and peels off.
A method of performing secondary irradiation and completely curing may be used.

Further, when applying the pattern, a desired pattern such as a silky texture or a fine grain surface can be formed by using a patterning roll instead of a mirror-finished roll.

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 50 to 750 KV, more preferably 1°O to 300 KV in terms of penetrating power.
Using an electron beam accelerator, the absorbed dose is 0.1 to 20 Mrad.
It is preferable to do so.

Note that during electron beam irradiation, N z , Her r
Irradiation is preferably performed in an inert gas atmosphere such as +CO□.

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 coating layer.

Incidentally, 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 pyrazolotriazole couplers. Preferred cyan couplers include phenolic couplers. Each of these couplers is present in the silver halide emulsion layer in an amount of 0.0 per mole of silver halide.
It is preferably contained in an amount of about 5 to 1 mole.

In addition to the above-mentioned silver halide emulsion layer, the color photographic light-sensitive material to which the present invention is applied includes, on the support, a non-photosensitive layer such as a protective layer, an intermediate layer, one filter layer, one scavenger layer, etc. in an appropriate layer order and number of layers. A sexual 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, observation 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 used in the present invention is most commonly gelatin such as alkali-treated gelatin or acid-treated gelatin. Derivatives such as gelatin, albumin, agar, gum arabic, alginic acid, partially hydrolyzed cellulose derivatives, partially hydrolyzed polyvinyl acetate, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone,
It can also be used in combination with a copolymer of these vinyl compounds.

The silver halide emulsion used is ruthenium, rhodium, palladium, iridium, platinum, gold, etc. ), activated gelatin, sulfur sensitization with unstable sulfur compounds (e.g., sodium thiosulfate, etc.), selenium sensitization with selenium compounds, or reduction with stannous salts, polyamines, etc. and under low PAg conditions. Chemical exacerbations such as exacerbations can be administered.

Further, these silver halide emulsions can be optically sensitized using various sensitizing dyes in order to impart photosensitivity in a desired wavelength range. Preferred exacerbating dyes that can be used at this time include, for example, US Pat.
, No. 939,201, No. 2,07-2.908, No. 2.739.149, No. 2.213.
No. 995, No. 2゜493, No. 748, No. 2,519.0
No. 01, West German Patent No. 929,080, British Patent No. 505.
Cyanine dyes, merocyanine dyes, or composite cyanine dyes described in No. 979 and the like 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 controlling development (for example, controlling gradation). etc.) It is also possible to use it for the purpose of

Furthermore, various photographic additives such as ultraviolet absorbers (e.g., benzophenone compounds and benzotriazole compounds), dye image stabilizers (e.g., phenol compounds, bisphenol-based compounds, hydroxychroman-based compounds, bisspirochroman-based compounds, hydantoin-based compounds, dialkoxybenzene-based compounds, etc.), stain inhibitors (e.g., hydroquinone derivatives, etc.),
Surfactants (e.g., sodium alkylnaphthalene sulfonate, sorta alkylbenzene sulfonate, sodium alkylsuccinate sulfonate, polyalkylene compounds, etc.), water-soluble anti-irradiation dyes (e.g., azo compounds, styryl compounds, oxonol) hardeners (e.g., halogen-substituted 5-1-riazine compounds, active vinyl compounds, ethyleneimino compounds, epoxy compounds, water-soluble aluminum salts, etc.), membranes Physical property modifiers (eg, glycerin, polyalkylene glycols, aqueous polymer dispersions [Latte 7x], solid or liquid paraffin, etc.) can be added.

In order to coat each constituent layer of the color photographic light-sensitive material on the support of the light-sensitive material of the present invention, a commonly known coating method is used.
For example, the coating is applied by dip coating, roller coating, bead coating, curtain flow coating, etc., and then dried.

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, even if each process is independent,
In some cases, two or more of these processes can be completed in one process using processing liquids having those functions. Further, each step can be divided into two or more times as necessary. In addition to the above, during the treatment process,
If necessary, various steps such as a pre-hardening bath, a neutralization bath, first development (black and white development), an 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, the temperature is 20 to 60°C, but the above-mentioned color photographic light-sensitive materials are particularly suitable for processing at 30°C or higher.

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-hydroxyethylaminoaniline 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-
Examples include ethyl-3-methylaniline-p-toluenesulfonate, N,N-diethyl-4-amino-3-(β-methanesulfonamidoethyl)aniline sulfate, and the like.

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)-1N-ethyl-3-methylaniline-p-)luenesulfonate and N,N-diethyl-4-amino-3-(β-methanesulfonamidoethyl)aniline sulfate.

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, Development accelerators such as polyalkylene glycol, organic solvents such as benzyl alcohol, ethylene glycol, diethylene glycol, methanol, and acetone, development inhibitors such as potassium bromide and nitropenzimidazole, sulfites, hydroxylamine, glucose, and alkanolamines. water softeners such as polyphosphoric acid compounds and nitrilotriacetic acid.

[Embodiments of the invention]

Examples of the present invention will be described below. It should be noted that, as a matter of course, the present invention is not limited to the following examples.

First, the formation of the coating layer in each example will be explained, and the results of various tests (folding durability test and fog measurement) on the obtained photosensitive materials will be summarized later.

Example 1 30 g/rd of the following mixture was coated on one side of a photo base paper weighing about 160 g/rd, and then energy beam 571
Cured using a Mrad electron beam. The composition of the mixture is as follows.

Exemplary compound (2) 25 parts by weight Exemplary compound (7) 60 parts by weight Propylene glycol diacrylate 15 parts by weight Titanium dioxide (rutile type, average particle size 0.2 μm) 40 parts by weight Example 2 A mixture consisting of the following composition was used. The same operation as in Example 1 was carried out to prepare a support.

Exemplary compound (2) 30 parts by weight Exemplary compound (7) 30 ffi 1 part Propylene glycol diacrylate 40 parts by weight Titanium dioxide (rutile type average particle size 0.2 μm) 40 parts by weight Example 3 Conducted using a mixture consisting of the following composition A support was prepared in the same manner as in Example 1.

Exemplary compound (2) 50 parts by weight Exemplary compound (7) 10 parts by weight Propylene glycol diacrylate 40 parts by weight Titanium dioxide (rutile type average particle size 0.2 μm) 40 parts by weight Example 4 Using a mixture consisting of the following composition A support was prepared in the same manner as in Example 1.

Exemplary Compound (1) 30 parts by weight Exemplary Compound (7) 30 parts by weight Kayamer HDDA manufactured by Nippon Ka Tohoku Co., Ltd. 40 parts by weight Titanium dioxide (rutile type average particle size 0.2 μm) 40 parts by weight Example 5 Consists of the following composition A support was prepared using the mixture in the same manner as in Example 1.

Exemplary compound (5) 30 parts by weight Exemplary compound (7) 30 parts by weight Photomer 4149 manufactured by Sannopco 40 parts by weight Titanium dioxide (rutile type average particle size 0.2 μm) 40 parts by weight Example 6 A mixture consisting of the following composition was used. A support was prepared in the same manner as in Example 1.

Exemplary compound (5) 30 parts by weight Exemplary compound (9) 30 parts by weight M240 manufactured by Tokanesei Chemical Industry Co., Ltd. 40 parts by weight Titanium dioxide (rutile type average particle size 0.2 μm)
140 parts by weight Comparative Example 1 A support was prepared in the same manner as in Example 1 using a metal alloy having the following composition.

Exemplary Compound (2) 10 parts by weight Exemplary Compound (7) 80 parts by weight Propylene glycol diacrylate 10 parts by weight Titanium dioxide (rutile type average particle size 0.2 μm) 40 parts by weight Comparative Example 2 A mixture having the following composition was used as an example. A support was prepared in the same manner as in 1.

Exemplary compound (2) 76 parts by weight Exemplary compound (7) 4 parts by weight Propylene glycol diacrylate 20 parts by weight Titanium dioxide (rutile type average particle size 0.2 μm) 40 parts by weight Comparative example 3 A mixture consisting of the following composition was used as an example. A support was prepared in the same manner as in 1.

40 parts by weight of aliphatic polyurethane acrylate 30 parts by weight of trimethylolpropane triacrylate 30 parts by weight of diethylene glycol diacrylate 40 parts by weight of titanium dioxide (rutile type average particle size 0.2 μm) Comparative Example 4 40 parts by weight of aliphatic polyurethane acrylate Exemplary compound (2 ) 30 parts by weight Diethylene glycol diacrylate 30 parts by weight Titanium dioxide (rutile type average particle size 0.2 μm) 40 parts by weight Comparative Example 5 Exemplary compound (7) 40 parts by weight Trimethylolpropane triacrylate 30 parts by weight Diethylene glycol diacrylate 30 parts by weight 40 parts by weight of titanium dioxide (rutile type average particle size 0.2 μm) (Folding durability test M of support) Each sample was
Humidify at 3℃ and 55% relative humidity for 10 minutes, and increase the sample length to 15X.
200 (111111”), and using an MIT folding durability tester (manufactured by Unishima), a load of 1.0 kg was applied.
It was measured with The results are shown in Table-1.

Table 1 Measurement results of folding durability (fogging test of photographic layer) In order to measure the effect on fog of each obtained support, the following layers were sequentially coated on the cured coating layer, and five different colors were coated. A photographic paper sample was prepared (the amount added is shown per 1 d unless otherwise specified, and the silver halide emulsion is shown in terms of silver).

Jffl 12 g gelatin, 0.042 g blue-sensitive silver chlorobromide emulsion (silver chloride 10 mole %), and 0.83 g
The following yellow coupler (Y-1), 0.01g
1 (blue-sensitive emulsion layer containing 0.6 g of dioctyl phthalate in which Q-1 was dissolved).

N2: 1.2g gelatin and 0.05g HQ-
A first intermediate layer containing 0.2 g of dioctyl phthalate dissolved in 1.

Layer 3: 1.9 g gelatin, 0.040 g green sensitive silver chlorobromide emulsion (50 mole % silver chloride) and 0.42 g
The following magenta coupler (M −1), 0.015
A green-sensitive silver chlorobromide emulsion layer containing 0.36 g of dioctyl phthalate dissolved in 2 g of HQ-1.

Layer 4: 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.

@5: 1.5 g of gelatin, 0.027 g of red-sensitive silver chlorobromide emulsion (silver chloride 50 mol%), 0.4 g of the following cyan coupler (C-L), 0.01 g of ■ (
Q-1 and 0.3g (7) 0,3 in which UV-1 was dissolved
Red-sensitive emulsion layer containing 5 g of dioctyl phthalate.

Layer 6: Protective layer containing 1.4 g of gelatin.

CI! Q-1 0H H rI.

(J V-1 Cs8 mouths (t) l Each sample thus obtained was incubated at 30°C and 60% relative humidity for 3 hours.
After being stored for several months and exposed to light, 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
n+j! H ethylene glycol 15111 benzyl alcohol
15m1Whitex B Bcon
c 1 g (fluorescent bleach manufactured by Sumitomo Chemical Co., Ltd.) Hydroxylamine sulfate
3g3-Methyl-4-amino-N-ethyl-
N-(β-methanesulfonamidoethyl)aniline sulfate 4; 5g potassium carbonate (anhydrous) 30g potassium sulfite (anhydrous)
2.0 g potassium bromide
0.65 g1~hydroxyethylidene-1,
1-diphosphonic acid (60% aqueous solution) 2I111 Add water to make 11, and add sulfuric acid or potassium hydroxide to p
J adjustment is made to H=10.1.

(Bleach-fix solution) Pure water 600m
j! Ethylenediaminetetraacetic acid-2-sodium・2Hz0 25g ammonium sulfite (40% aqueous solution) 35mj! Ammonium thiosulfate (70% aqueous solution) 50m4 Ethylenediamine iron tetraacetate (I [[) ammonium 95g aqueous ammonia (28
%) 25mm! Add water to make 11,
Adjust pH to 6.9 with aqueous ammonia or glacial acetic acid.

The fog density of the developed sample was measured using a Sakura color densitometer model PDA-60 (manufactured by Konishiroku Photo Industry Co., Ltd.). The results are shown in Table-2.

Furthermore, as is clear from the Sun Table 1 after the development treatment, yellowing of the support itself was observed in the samples (Samples Nal-6) of the supports (Examples 1-6) constituting the light-sensitive material of the present invention. Compared to the support samples of Examples 1 to 5 (sample cases 7 to 11), the performance against folding is significantly improved.

In addition, as is clear from Table 2, compared to the comparative example, the folding durability and fogging, which were difficult to achieve in the past, were improved while improving the folding durability without deteriorating the fogging over time. It can be significantly reduced. It is also effective against yellowing of the support itself after development.

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

〔Effect of the invention〕

As mentioned above, in the silver halide photographic light-sensitive material of the present invention, the coating layer of the support has excellent flexibility, and furthermore, fog, which has conventionally been difficult to achieve at the same time as flexibility, especially fog over time, deteriorates flexibility. It has good photographic performance, such as being able to reduce the amount of photosensitive material while improving it, and also prevent yellowing after the processing step, and solve the problems of conventional photosensitive materials having an electron beam-cured coating layer.

Claims (1)

[Scope of Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer provided on a support, wherein the support has electron beam curable on at least one side of the support base material. A cured coating layer is formed by coating a composition and curing the composition by irradiating it with an electron beam, and the electron beam curable composition is composed of the following compounds (a), (b) (
A silver halide photographic material containing at least one of each of c). (a) An electron beam curable compound that has two or more terminal reactive groups capable of causing a curing reaction with electron beams in its molecule and contains a carbocyclic or heterocyclic bond in its molecular chain. (b) An electron beam curable compound containing polybutadiene in its molecular chain. (c) An electron beam curable compound capable of reacting with the above two compounds. 2. The electron beam curable compound which is the above compound (a) has two or more terminal reactive groups capable of causing a curing reaction by electron beam in the molecule, and has a phenylene ring, a spiran ring, or a triazolone ring in the molecular chain. The silver halide photographic material according to claim 1, which contains the following.