JPH01195444A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide color photographic sensitive material permitting rapid processing even if a color developing soln. contg. no benzyl alcohol is used by providing a backing coating layer contg. colloidal silica, polymer latex, and a water-soluble high molecular compd. having carboxyl groups, or sulfone groups, etc. CONSTITUTION:A silver halide color photographic emulsion layer permitting processing at >=30 deg.C and <=90sec with a color developing soln. contg. no benzyl alcohol is formed on one side of the surface of a resin-coated paper type photographic base. Colloidal silica, polymer latex, and either one of a water-soluble high molecular compd. having carboxyl groups and sulfone groups or a salt thereof or hydrophilic colloid, are contained on another side of the surface. The backing coating layer has high film strength even at wet state, and is photographically inactive. Thus, a silver halide color photographic sensitive material generating no unevenness of coating by being transferred to a surface of a resin coated paper type photographic base having a silver halide emulsion layer nor causing fog or desensitization by affecting a silver halide emulsion layer, is obtd.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to an improved silver halide color photographic light-sensitive material, and more specifically, the present invention relates to an improved silver halide color photographic light-sensitive material, and more specifically, the present invention relates to an improved silver halide color photographic light-sensitive material. This invention relates to a silver halide color photographic light-sensitive material that has a back coat layer that does not adversely affect the silver halide color photographic emulsion layer and has excellent antistatic properties and scratch resistance, allowing rapid processing without causing deterioration. be.

<Prior Art and its Problems> Usually, a silver halide color photographic light-sensitive material is composed of a support and a silver halide color photographic constituent layer provided on the support. Such silver halide color photographic constituent layers include a silver halide color photographic emulsion layer, a protective layer,
It is composed of a subbing layer, an intermediate layer or an anti-wrapping layer, an anti-scratch layer or a filter layer, an ultraviolet absorbing layer, etc., and combinations thereof. For example, a single silver halide photographic light-sensitive material has a silver halide emulsion layer and its protective layer provided on a support. In addition, a multilayer silver halide color photographic light-sensitive material has a multilayer arrangement in which a blue-sensitive emulsion layer and an intermediate layer, a green-sensitive emulsion layer and an ultraviolet absorbing layer, a red-sensitive emulsion layer and a protective layer, etc. are sequentially provided on a support. , each color-sensitive emulsion layer contains yellow, magenta, and cyan color-forming couplers, respectively.

By the way, supports for silver halide photographic light-sensitive materials have conventionally been made of films such as polyethylene terephthalate film, cellulose triacetate film, polystyrene film, and polycarbonate film, and paper substrates with resins capable of forming films on both sides, often polyolefin resins. Hydrophobic supports such as resin-coated papers coated with In particular, polyolefin resin-coated paper is increasingly being used as a support for photographic paper in place of the conventionally used baryta paper. The reason for this is that the polyolefin resin-coated paper used as a photographic support is hydrophobic, which makes it difficult for processing liquids to penetrate into the base paper waste during the development and fixing processes of photographic paper, compared to baryta paper. This is because there is an advantage that processing times such as washing with water and drying are shortened.

However, these photographic hydrophobic supports have several drawbacks. The well-known shortcomings are:
Silver halide photographic materials having these hydrophobic supports tend to attract dirt, dust, etc. due to static electricity during handling, and are susceptible to the generation of various spots such as water repellency, desensitization, and capricity. Particularly, as a result of discharging the accumulated static electricity, a partial cover Vt called a static mark, which is extremely unpleasant in terms of photographic characteristics, may be generated in the silver halide photographic emulsion layer.

In addition, silver halide photographic materials having these hydrophobic supports do not have the ability to write on the back surface, particularly the ability to write on them with a pencil.

For this reason, silver halide with a hydrophobic support.

It is known to provide an antistatic and pencil-markable coating layer called a backcoat layer on the back side of a photographic material, that is, on the surface of the support not coated with silver halide photographic constituent layers.

For example, in order to provide antistatic performance,
Colloidal silica described in No. 98, Special Publication No. 52
-18020; loidal alumina,
The use of various carboxyl group-containing compounds described in Japanese Patent Publication No. 58-9408 is known.

In addition, ethylene-maleic anhydride copolymer described in Japanese Patent Publication No. 57-12980, Japanese Patent Publication No. 58-5685
A water-soluble polymer compound or its salt obtained by copolymerizing an ethylenically unsaturated copolymerizable monorod having 4 or more carbon atoms and maleic anhydride as described in No. 9, Japanese Patent Publication No. 1983
It is also known to use organic polymeric antistatic agents such as the water-soluble film-forming polymeric anionic polymer electrolytes described in No. 53940.

In addition, in order to add the ability to write with lead, for example, barium sulfate as described in Japanese Patent Publication No. 57-53940, silicon dioxide, calcium carbonate as described in Japanese Patent Application Publication No. 57-118241, etc. The use of fine particles of magnesium carbonate, titanium oxide, aluminum oxide, barium sulfate, glass powder, etc. is known.

However, these silver halide photographic materials comprising a hydrophobic support with a bank coat layer and a silver halide photographic constituent layer have had one or more serious drawbacks in their use. For example, when used in high-sensitivity silver halide photographic materials, it may not be possible to sufficiently prevent static marks, or the antistatic performance may deteriorate after processing, causing prints to stick to each other, making handling inconvenient. Some of the components may detach and cause undesirable sludge accumulation, or the back coat layer may be weak or have weak adhesion to the hydrophobic support, causing the inside of the printer to back up during exposure of silver halide photographic materials. There have been cases where the coating equipment has been contaminated with powder from the coating layer constituents, or the coating equipment has been contaminated at the stage of dispensing the silver halide photographic constituent layers.

In addition, in a silver halide photographic light-sensitive material having a hydrophobic support provided with a back coat layer containing fine particles, particularly inorganic fine particles, in order to allow addition with a pencil, the surface of the silver halide photographic constituent layer is may be damaged, resulting in unpleasant uneven gloss.

On the other hand, the photographic properties of silver halide color photographic emulsions include low capri and high color development in a short development time, good color reproducibility, and excellent color and image storage stability (less discoloration and fading over time). Being good is important.

In order to satisfy these requirements, so-called oil-soluble disc couplers have been proposed in the past, which are dissolved in a high-boiling point or low-boiling point organic solvent, emulsified and dispersed, and incorporated into an emulsion layer. When using these couplers,
Since the color developing agent has low lipophilicity, it is difficult to penetrate into the coupler-dispersed oil droplets, resulting in a decrease in the density of one color. For this reason, various developing agent penetrating agents have been studied, and in particular, a method of accelerating color development by adding benzyl alcohol to the color developer has been widely used in color photographic materials due to its great color development promotion effect. .

However, when benzyl alcohol is used, diethylene glycol, triethylene glycol i, or the like is required as a solvent because of its low water solubility. However, since these compounds, including benzyl alcohol, have high pollution load values such as BOD and COD, it is preferable to remove benzyl alcohol for the purpose of reducing the pollution load.

Furthermore, even if this solvent is used, it takes time to dissolve benzyl alcohol, so it is better not to use benzyl alcohol in order to reduce the preparation work.

Furthermore, if benzyl alcohol is brought into the bleaching bath or bleach-fixing bath, which is a post-bath, it causes the formation of a leuco dye, which is a cyan dye, and causes a decrease in color density. Furthermore, since the washing-out speed of the developer components is delayed, the image storage stability of the processed photosensitive material may be adversely affected.

Therefore, also for the above reasons, it is preferable not to use benzyl alcohol.

In the past, color development generally took 3 to 4 minutes to process, but with the recent shortening of finishing delivery times and the reduction of laboratory work, it is desirable to shorten the processing time. It had been.

However, when benzyl alcohol, which is a color development accelerator, is removed and the development time is shortened, it is inevitable that the color development density will be significantly reduced.

In order to solve this problem, improvements in photosensitive silver halide, improvements in color-forming couplers, development of combinations of development accelerators, and other auxiliary agents have been made (for example, in JP-A No. 62-1723,
No. 46, No. 62-172350, No. 62-17753
No. 9, No. 62-177550, No. 62-177551
(described in the issue), using a color developing solution that practically does not contain benzyl alcohol,
A silver halide photographic emulsion that can be developed within seconds has been developed.

However, this silver halide photographic emulsion inherently tends to generate capri, and has the disadvantage of being inferior in adhesion to photographic supports compared to conventional photographic emulsions. Even in the constituent elements of the back coat layer, which were thought to have no adverse effect, the surface p of the bank coat layer
When H is high, capri occurs, and when H is low, it affects the surface of the photographic support (front support surface) on which the emulsion is provided, resulting in a problem that the emulsion's coating properties and adhesion deteriorate.

<Objective of the Invention> Therefore, the object of the present invention is to prevent adverse effects on the silver halogenide photographic emulsion layer, which is substantially completed in 30°C or above and within 90 seconds using a color developing solution that does not contain benzyl alcohol. The object of the present invention is to provide a silver halide photographic material having a puncture coat layer having excellent antistatic properties and scratch resistance without causing any adverse effects.

<Means for Solving the Problem> As a result of various studies to achieve the above object, the present inventor has developed a color developing material that does not substantially contain benzyl alcohol on one side of a resin-coated paperback photographic support. It has a silver halide color photographic constituent layer that can be developed using a solution at 30°C or higher and within 90 seconds, and on the opposite side (back side),
(a) colloidal silica, (b) polymer latex,
and (c) a surface containing at least one of a water-soluble polymer compound or a salt thereof having a carboxyl group or a sulfone group, and a hydrophilic organic polymer colloid with a pH of 5.5 to
This was achieved by providing a pack of 7.0.

The back coat layer of the present invention has strong film strength even in a wet state and is inert in terms of photographic properties. It has extremely high commercial value because it transfers to the surface of the body (surface), causing poor adhesion and uneven coating of the photographic emulsion, and acts on the silver halide emulsion layer, causing capri and desensitization.

The colloidal silica preferably used in the practice of the present invention is a colloidal solution in which ultrafine particles of silicic acid anhydride (8102) are dispersed in water mainly using water as a dispersion medium. Further, the dispersion medium is generally water, but methanol or the like may be used in some cases. Further, the colloid solution contains an alkaline component for the purpose of colloid stabilizer and the like. For example, it may contain Na2O, other KNHs, formamide, ethylamine, -1-nylpholine, etc.

The colloidal silica (a) preferably used in the practice of the present invention is preferably colloidal silica with an average particle size of 5fI@μ or 100mμ, and the amount of coating is 0°05f in terms of solid content.
/rtl to 1.0flrd, preferably 0.0flrd.
0.5f/lr from 1 Shiso? Good range. If the particle size of colloidal silica is too small, it will easily gel, and conversely, if the content of the alkali component is increased to stabilize the dispersion, the surface pH of the bank coat layer will increase. Furthermore, if the size is too large, the silica particles will settle and cannot be stably obtained as colloidal silica. If the amount applied is too small, the necessary antistatic performance cannot be obtained, which is the case with the Snowtex series.

The polymer latex (b) used in the practice of the present invention is an aqueous dispersion of a water-insoluble polymer with an average particle size of 20 mμ to 200 mμ, such as acrylic latex, vinyl acetate latex, styrene-butadiene latex, acrylonitrile-based latex, etc. Butadiene latex and the like are useful.

Acrylic latexes include homopolymers of acrylic esters such as methyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, and methacrylic esters such as methacrylic-methyl and butyl methacrylate, or copolymer emulsions thereof. Copolymer emulsion with polyacrylic latex and monomers copolymerizable with acrylic esters and methacrylic esters, such as butadiene, styrene, silicone-modified unsaturated copolymerizable compounds, etc. Examples include carboxy- or amino-modified latex.

Vinyl acetate latex includes polyvinyl acetate latex, vinyl acetate/acrylic ester copolymer latex, vinyl acetate/ethylene copolymer latex, etc. Styrene/butadiene latex includes styrene/butadiene copolymer tex, carboxy-modified Examples include styrene and butadiene latex. In addition, the present invention includes various types of acrylonitrile-butadiene copolymer latex, carboxy-modified acrylonitrile-butadiene copolymer latex, carboxy-modified acrylonitrile-butadiene copolymer latex, polyvinylidene chloride latex, acrylic amphoteric latex, etc. Polymer latex can be used.

In the back coat layer of the present invention, since scratch resistance is particularly required, at least one type of acrylic polymer latex that is highly miscible with colloidal silica, that is, an acrylic polymer latex forming a polymer, is used. It is advantageous to use a polymer latex which is . Specific examples of these polymer latexes include the AE series manufactured by Nippon Synthetic Rubber, the Dicrystal Sumer series manufactured by Nippon Tsumugi, the Siren series manufactured by Hoechst, the 7 vinyl series manufactured by Hoechst Gosei, the HD series manufactured by Toagosei Chemical Co., Ltd., and the Asahi Kasei Chemical Co., Ltd. There are Polytron series manufactured by A ■, Bonlon series manufactured by Mitsui Toatsu ■, etc.

The water-soluble polymer compound or salt thereof and hydrophilic organic polymer colloidal substance having a carboxyl group or sulfone group (c) used in the practice of the present invention include those described below.

As the water-soluble polymer compound or its salt having a carboxyl group, a water-soluble polymer compound or its salt obtained by copolymerization of an ethylenically unsaturated copolymerizable monomer having 4 or more carbon atoms and maleic anhydride; are particularly useful. They are a-olefins having 4 or more carbon atoms,
It is obtained by hydrolyzing a copolymer of an ethylenically unsaturated copolymerizable monomer such as alkyl vinyl ether or styrene with maleic anhydride, optionally with an alkali such as sodium hydroxide or potassium hydroxide. The molecular weight of the ethylenically unsaturated copolymerizable monomer having 4 or more carbon atoms and the maleic anhydride copolymer is preferably 2.000 to 150,000. Specific examples thereof include, for example, a solution obtained by hydrolyzing isobutylene, l-pentene, butyl vinyl ether, or a styrene and maleic anhydride copolymer with an alkali such as sodium hydroxide or potassium hydroxide, and the pH of the solution is 5. Examples include reaction products having a molecular weight of 0 to 9.0. Examples of water-soluble polymer compounds having different types of carboxyl groups or salts thereof include copolymers of styrene and itaconic acid or crotonic acid, copolymers of methyl acrylate and citraconic acid, etc., or salts thereof. .

As the water-soluble polymer compound having a sulfonic group or a salt thereof, polyvinyl aromatic sulfonic acid or a salt thereof is particularly useful. Their molecular weight is
5,000 to 1,000,000 is preferred. Specific examples thereof include 1, for example, polystyrene sulfonic acid, polyvinylbenzyl sulfonic acid, etc., or their sodium, potassium, etc. salts.

Hydrophilic colloid substances having carboxyl groups include:
Carboxyl-modified polyethylene or its salts are particularly useful. Examples of carboxy-modified polyethylene include Zaixen (manufactured by Seitetsu Kagaku Kogyo Co., Ltd.)
Although some of the ethylene residue repeating units are replaced with monomer residues having carboxyl groups such as acrylic acid, maleic acid, etc., polyethylene resins or their alkali metals, ammonia ,
Examples include salts such as amines that are dissolved or decomposed in water.

In addition, the content of the polymer having a carboxyl group or sulfone group used in the implementation of the present invention is 511
I/? If it is less than 150 wq/n1, the inorganic matting effect, the fixing effect of the agent CB component, and the antistatic property of the bank coat layer will be insufficient and undesirable. On the other hand, if it is more than 150 wq/n1, the film strength will be insufficient. Therefore, a range of 5 to 150 arms is preferable. Further, by using a combination of a polymer having a carboxyl group and a polymer having a sulfone group, the effects of the present invention can be exhibited even more advantageously.

The inorganic matting agent used in the practice of the present invention has an average particle size of 0.2μ to 10μ, preferably 0.3μ to 5μ.
Inorganic powders that are μ are useful. Specific examples thereof include fine particles of silicon dioxide, calcium carbonate, magnesium carbonate, titanium oxide, precipitated aluminum hydroxide, barium sulfate, strontium sulfate, and the like. If the particle size of the inorganic matting agent is too small,
If the amount applied is too small, the paper feeding properties will be insufficient, and if the particle size is too large or the amount applied is too large, the texture will be unpleasant and lead to undesirable scratches on the surface. result.

Ninth, the coating amount is preferably in the range of 0.02 f/m' to 0.5 f/d.

In addition, the content of the polymer latex (b) in the back coat layer is expressed as a weight composition with respect to (c) the water-soluble polymer compound or salt thereof having a carboxyl group or sulfone group, or the hydrophilic organic polymer colloid. 3:(c)-
The range of s:g5 to 99:1 is fine, but (b)/(
c) = 5/95 or less, the amount of (c) to the developer during the development process is
) becomes difficult to prevent from flowing out, and the inverse K(b)/(
When c)=99/x or more, the antistatic property deteriorates.

If the amount of (c) is large even if divided, it is better to use an acrylic type for (b). A particularly preferable range is (b)/(c)=1
From 5/85 to 67/33. Similarly, the composition ratio of the polymer latex (b) to the colloidal silica (a) is (a):(b)=25 near 5 to 9 as a weight composition.
A range of 5:5 is preferred. (a)/(b)=25:
If it is less than 75, it is difficult to obtain antistatic properties and it is easy to induce blocking, and conversely (a) / (g)) = 95
If it is 15 or more, the scratch resistance strength will be extremely deteriorated even if a hardening agent, which will be described later, is used in combination. A particularly preferable range is (a)/(
b) = 33/67 to 90/10.

In the back coat layer according to the present invention, activated vinyl-based,
It is advantageous to contain compounds of active halogen type, epoxy type, ethyleneimino type, methanesulfonic acid ester type, active ester type and incyanate type as hardeners.

Hardeners used in the present invention include divinylsulfone, N,N'-ethylenebis(vinylsulfonylacetamide), 1,3-bis(vinylsulfonyl)-2-7''
Lovanol, methylene bismaleito, 5-acetelyl-1,3-diacryloyl-hexahydro-8-triazine, 1,3,5-triacryloyl-hexahydro-8
-) Active vinyl compounds such as riazine, 1,3.5-trivinylsulfonyl-hexahydro-8-triazine.

2.4-dichloro-6-hydroxy-8-) riazine
Sodium salt, 2,4-dichloro-6-medoxy8-
) riazine, 2.4-dichloro-6-(4-sulfoanilino)-8-) riazine sodium salt, 2*4-dichloro-6-(2-sulfoethylamino)-8-) riazine, N, N' - Active halogen compounds such as bis(2-chloroethylcarbamyl)piperazine.

Diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, triglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane diglycidyl ether, Epoxy compounds such as methylolfurohant triglycidyl ether, diglycerol triglycidyl ether, and sorbitol tetraglycidyl ether.

2.4.6-)diethylene-8-)riazine, 1.6-
Ethyleneimino compounds such as hexamethylene-N, N/-bisethyleneurea, and bis-β-ethyleneiminoether thioether.

1.2--/ (methanesulfonoxy)ethane, 1゜4-di(methanesulfonoxy)butane, 1.3-di(
Methanesulfonoxy) pentene-like chimethanesulfonic acid ester compounds.

N-carboethoxy-2-isopropoxy-1゜2-dihydroquinoline, N-(1-morpholinocarboxy)-
Dehydrated condensed peptide reagents such as 4-methylpyridinium chloride; active ester compounds such as N,N/-aziboyldioxydisuccinimide and N,N'-terephthaloyldioxydisuccinimide.

Isocyanate compounds such as toluene-2,4-diisocyanate and 1,6-hexamethylene diisocyanate.

In addition, as for the content of the hardening agent preferably used in carrying out the present invention, the optimum addition amount can be selected according to the performance of the back coat layer, but from the balance between the degree of curing and the antistatic performance, the total polymer weight The range is preferably from 0.2% to 100% by weight, particularly preferably from 2% to 50% by weight.

The hardener can also be used in a suitable solvent, such as water, methanol,
It is advantageous to dissolve it in ethanol, N,N-dimethylformamide, acetone, ethyl acetate, etc. and incorporate it into the back coat layer.

The resin-coated paper type photographic support used in the practice of the present invention is a paper substrate coated on both sides with a film-formable resin.

The resin for coating the base paper used in the present invention is preferably a polyolefin resin or an electron beam curable resin. Examples of the polyolefin resin include homopolymers such as low-density polyethylene, high-density polyethylene, polypropylene, polybutene, and polypentene, or ethylene and propylene. Copolymers consisting of two or more olefins such as polymers, linear low-density polyethylenes that are copolymers of ethylene and α-olefins, and mixtures thereof, with various densities and melt indexes individually. Or they can be used in combination. In particular, in the present invention, it is preferable to use low density polyethylene, medium density polyethylene, high density polyethylene, ethylene-propylene copolymers, etc. alone or in combination of two or more types of resins.

As electron beam curable resins, molecular side chains or molecular terminals,
Examples include resins having a C═C unsaturated bond such as an acryloyl group or a methacryloyl group. Typical examples include ester acrylate, ester methacrylate, epoxy acrylate, epoxy methacrylate,
Examples include urethane acrylate, urethane methacrylate, monofunctional acrylate, monofunctional methacrylate, polyfunctional acrylate, and polyfunctional methacrylate.

In addition, in the resin for coating the base paper in the present invention, white pigments such as titanium oxide, zinc oxide, Merck, calcium carbonate, etc., fatty acid amides such as stearic acid amide and alaxic acid amide, zinc stearate, calcium stearate, etc. , fatty acid metal salts such as aluminum stearate, magnesium stearate, zinc palmitate, zinc myristate, calcium palmitate, hindered phenol, hindered amine, phosphorus-based, sulfur-based, etc. a-breathing inhibitors, cobalt blue, group In fact, various additives such as blue pigments and dyes such as cerulean blue and 7-talocyanine blue, magenta pigments and dyes such as cobalt violet, fast violet, and manganese violet, optical brighteners, and ultraviolet absorbers are appropriately combined. It is preferable to add

The photographic support according to the present invention is manufactured by a so-called extrusion coating method in which heated and molten resin is cast onto a running base paper, and both sides of the support are coated with the resin. Further, in the case of an electron beam curable resin, the resin is applied by a commonly used coater such as a gravure coater or a blade coater, and then the resin is cured by irradiation with an electron beam for coating. Further, before coating the base paper with the resin, it is preferable to subject the base paper to an activation treatment such as a corona discharge treatment or a flame treatment.

The emulsion side surface of the photographic support has a glossy surface, a matte surface, a silky surface, etc. depending on the use, and the back surface is usually a matte surface, and the front surface or the back surface is also treated with corona discharge if necessary. Activation processing such as the following can be performed. Further, although there is no particular restriction on the thickness of the resin layer of the resin-coated paper, it is generally advantageous to coat the paper to a thickness of about 5 microns to 50 microns.

The base paper for the resin-coated paper-type photographic support used in the present invention may be any of ordinary natural pulp paper, synthetic fiber paper, or synthetic resin film bonded, or so-called synthetic paper, but softwood pulp may be used. Natural pulp paper whose main component is wood pulp, hardwood pulp, softwood hardwood mixed pulp, is advantageously used.

There are no particular restrictions on the thickness of the base paper, but paper with good surface smoothness is preferred, and its basis weight is 5 Of/d to 250
f/rrl is preferred. Further, the base paper mainly composed of natural pulp can contain various polymer compounds and additives. For example, starch derivatives, polyacrylamides, polyvinyl alcohol derivatives, dry paper strength agents such as gelatin, fatty acid salts, rosin derivatives, sizing agents such as dialkyl ketene dimer emulsions, melamine resins,
A draft resin, a wet paper strength enhancer such as an epoxidized polyamide resin, a stabilizer, a pigment, a dye, an optical brightener, a latex, an inorganic electrolyte, a pH adjuster, and the like can be contained in appropriate combinations.

The back coat layer according to the present invention can contain various polymer compounds and additives.

Water-soluble polymers include oxidized starch, starch phosphates, polyvinyl alcohol, polyacrylamide, poly-N-vinylpyrrolidone, agar, sodium alginate, etc. Surfactants include alkylbenzene sulfonates, sulfonate, etc. ; Anionic surfactants such as uccinic acid ester salts, nonionic surfactants such as saponin and alkylene oxide compounds, amphoteric surfactants such as amino acids, aminosulfonic acids, and amino alcohol esters;
Fluorine-based surfactants as exemplified in JP-A No. 50-99529, compounds described or exemplified in JP-A-45-24068, JP-A-54-94318, etc. can be included as fluorescent brighteners. can.

In carrying out the present invention, an air knife coater, a roll coater, a bar coater, a blade coater, a slide hopper, and a slide hopper are used to apply the back coat coating liquid onto the surface of the hydrophobic support opposite to the surface on which the silver halide photographic constituent layer is provided. coaters, gravure coaters, 7-lexogravure coaters, combinations thereof, and the like. Prior to coating, it is desirable to activate the surface of the hydrophobic support by corona treatment, flame treatment, or the like.

Various drying devices can be used to dry the applied coating liquid, including hot air dryers such as straight tunnel dryers, arch dryers, air loop dryers, and sine curve air float dryers, infrared heating dryers, and dryers that use metal such as microwaves. I can give it to you.

The silver halide photographic emulsion layer according to the present invention is an emulsion designed so that it can be rapidly developed using a color developing solution that does not substantially contain benzyl alcohol.

The silver halide contained in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer of the present invention has a silver bromide content of 65 mole or less.

In the present invention, the silver bromide content refers to the total silver bromide content of each layer in the total silver halide contained in each of the total green light-sensitive silver halide emulsion layer and the total red light-sensitive silver halide emulsion layer. It refers to the content rate of When the silver bromide content exceeds 65 mol %, processing stability deteriorates, and sufficient photographic performance cannot be obtained when processing is performed with a color developing solution from which benzyl alcohol has been substantially removed.

The preferred silver bromide ownership ratio of the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is 5 to 60 molti, more preferably 20 to 55 molti.

The silver halide contained in the green-sensitive and red-sensitive silver halide emulsion layers may be silver chlorobromide, silver chloroiodobromide, or a mixture thereof, but preferably silver chlorobromide. It is.

When the silver halide contained in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer of the present invention is silver chloroiodobromide, the silver iodide content does not exceed 2 mol%. Preferably.

Silver chloride, silver bromide, etc. may be included within the range that does not impair the effects of the present invention. In the present invention, one or both of the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer may be composed of two or more layers.

The silver halide contained in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer of the present invention is also monodisperse like the silver halide contained in the blue-sensitive silver halide emulsion layer. Preferably.

The composition of the silver halide contained in the grown optical silver halide emulsion layer is not particularly limited, and may be silver bromide, silver chlorobromide, silver chloroiodobromide, or a mixture thereof. silver chloride bromide is preferred, and the silver A content is 5 to 9.
It is of 5 molti. Furthermore, the evening light-sensitive silver halide emulsion layer in the present invention may consist of two or more layers. (9) Silver chloride is also preferably used.

The average grain size of the silver halide contained in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is not particularly limited, but is preferably 0.1 to 2 μm, more preferably 0.2 to 2 μm. 1 μm, particularly preferably 0°25 to 0.8 μm
It is.

In the silver halide color photographic light-sensitive material of the present invention, the amount of silver (bank amount) in the silver halide emulsion layer is preferably 0.3 to 1.5 in the entire photosensitive silver halide emulsion layer. That is, in order to obtain excellent image quality, the amount of silver must be 1.2f.
/1? On the other hand, in order to obtain a high maximum density and high sensitivity, the silver amount is preferably 0.3f/lr or less.
It is preferable that it is greater than or equal to i. In the present invention, the silver amount is particularly preferably 0.4 to 1, Of/I? That is to say.

The crystals of the silver halide grains in the silver halide color photographic emulsion layer of the present invention may be normal crystals, twin crystals, or other crystals, and have a ratio of (1,0,0] planes to (1,1,1:1 planes). Furthermore, even if the crystal structure of these silver halide grains is uniform from the inside to the outside, it may have a layered structure (core-shell type) in which the inside and outside are different. Furthermore, these silver halides may be of the star type, which forms latent images mainly on the surface, or of the type, which forms latent images inside the grains.

On the other hand, tabular silver halide grains (JP-A-58-11393
No. 4, Japanese Patent Application No. 59-170070) is preferably used from the viewpoint of color sensitization efficiency as described above.

Further, the monodisperse silver halide grains preferably used in the present invention may be obtained by any conventionally known preparation method such as an acidic method, a neutral method, or an ammonia method.

Alternatively, for example, a method may be used in which seed particles are produced by an acidic method and further grown by an ammonia method, which has a high growth rate, to grow to a predetermined size. When growing silver halide grains, p)l, pAg, etc. in the reaction vessel are controlled, and an amount commensurate with the growth rate of silver halide grains is controlled, for example, as described in JP-A-54-48521. It is preferable to simultaneously implant and mix silver ions and halide ions.

The silver halide photographic emulsion layer of the present invention can contain a color coupler to provide a multilayer silver halide constituent layer. For example, JP-A-62-172346, JP-A-62-172346;
Oil-soluble couplers, Fischer type couplers, etc. disclosed in Japanese Patent No. 172350 can be used alone or in combination. As the binder for these photographic constituent layers, in addition to ordinary gelatin, hydrophilic polymeric substances such as polyvinylpyrrolidone, polyvinyl alcohol, and polysaccharide sulfate ester compounds can be used. Further, the above-mentioned photographic constituent layer can contain various additives.

For example, as sensitizing dyes, cyanine dyes, merocyanine dyes, etc.; as chemical sensitizers, water-soluble gold compounds, sulfur compounds, etc.; as anti-capri agents or stabilizers, hydroxy-triazolopyrimidine compounds, mercapto-heterocyclic compounds, etc. , as hardeners, active silver halides, vinyl sulfone compounds, aziridine compounds, etc.; as coating aids, benzenesulfonate, sulfosuccinic acid ester salts, etc.; as anti-staining agents, dialkylhydroquinone compounds, etc.; and other optical brighteners. agents, sharpness-enhancing dyes, antistatic agents,
In addition to the pH adjuster, a suitable combination of water-soluble iridium, water-soluble rhodium compounds, etc. can be contained during the production and dispersion of silver halide.

In general, silver halide photographic materials are subjected to processes such as exposure, development, stopping, fixing, bleaching, stabilization, etc., depending on the photographic material. Silver chemical color photographic material is C
D-1[, CD-11/ (the above two compounds are trade names of Kodak Co.), droxychrome (trade name of May and Baker Co.), etc. can be used for processing with any crude drug color developer. Developers containing such herbal medicines further contain various commonly added components, such as IJ hydroxide, sodium carbonate, alkaline earth sulfites, alkali metal hydrogen sulfites, and alkali metal thiocyanates. Salts, alkali metal halides, water softeners, thickeners, and JP-A-62-172346, JP-A-62-172
A development accelerator described in No. 350 or the like may be optionally included.

Examples of additives other than those mentioned above that may be added to the developer of the present invention include bromides such as potassium bromide and ammonium bromide;
In addition to compounds for quick processing solutions such as alkali iodide, nitrobenzimidazole, mercaptobenzimidazole, 5-methyl-benzotriazole, 1-phenyl-5-mercaptotetrazole, anti-stain agents, anti-sludge agents, preservatives, There are multilayer effect promoters, chelating agents, etc.

Further, the color developing solution of the present invention is characterized in that it does not substantially contain benzyl alcohol. "Substantially" means 10,100Os of color developing agent and 2% of benzyl alcohol.
It refers to the following. If it is 2- or less, there is almost no problem in terms of environmental pollution.

Bleaching agents used in bleaching solutions or bleach-fixing solutions in the bleaching process are generally known to be those in which metal ions such as iron, cobalt, and copper are coordinated with aminopolycarboxylic acids or organic acids such as oxalic acid and citric acid. There is. Representative examples of the above aminopolycarboxylic acids include the following.

Ethylenediaminetetraacetic aciddiethylenetriaminepentaacetic acidpropylenediaminetetraacetic acidnitrilotriacetic acidiminodiacetic acid ethyl ether diaminetetraacetic acidethylenediaminetetrapropionic acidethylenediaminetetraacetic acid disodium saltdiethylenetriaminepentaacetic acid pentasodium saltnitrilotriacetic acid sodium saltBleaching solution contains various additives along with the above bleaching agents. It may contain an agent. Step 7: When using a bleach-fix solution in the bleaching process,
A solution containing a silver halide fixing agent in addition to the bleaching agent is applied. Further, the bleach-fix solution may further contain a halogen compound such as potassium bromide. As with the bleach solution mentioned above, various other additives such as pH buffers, optical brighteners, antifoaming agents, surfactants, preservatives, chelating agents, stabilizers, organic solvents, etc. are added. addition,
It may be included.

As the silver halide fixing agent, for example, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, thio original, thioether, etc., which react with silver halide and become water-soluble, are used. Compounds that form silver salts can be mentioned.

The processing temperatures of the silver halide color photographic light-sensitive material of the present invention in various processing steps such as development with the developer of the present invention, bleach-fixing (or bleaching, fixing), and further washing with water, stabilization, drying, etc. as necessary are as follows. From the viewpoint of rapid processing, it is preferable to carry out the treatment at a temperature of 30° C. or higher.

The silver halide color photographic light-sensitive material of the present invention is disclosed in Japanese Unexamined Patent Publication No. 58
-14834, 58-105145, 58-1
No. 34634 and No. 58-18631 and patent application 1973
A stabilization treatment as an alternative to washing may be performed as shown in Japanese Patent No. 8-2709 and No. 59-89288.

The method for processing the photographic element of the present invention is not particularly limited, except that the substantially benzyl alcohol-free color developing solution of the present invention is used, and various processing methods can be applied. for example,
Typical methods include a method in which bleach-fixing is performed after color development, followed by further washing and/or stabilization treatment if necessary, and a method in which bleaching and fixing are performed separately after color development, and further washing and/or stabilization is performed if necessary. Or a method of stabilizing; or prehardening, neutralization, color development, stopping, fixing, washing, bleaching, fixing,
A method in which the order of washing with water, post-hardening, and washing with water is carried out, a method of carrying out in the order of color development, washing with water, supplementary color development, stopping, bleaching, fixing, washing with water, and stabilization. After that, any method may be used for processing, such as a development method in which color development is carried out again to increase the amount of produced dye.

Next, examples will be described in order to explain the present invention more specifically.

Example 1 Paper with a basis weight of 160 f/d was run at a speed of 80 m/min, and the first
After corona discharge treatment on the back side in the zone, 50 parts of low density polyethylene (density 0.918.MI5) and 50 parts of high density polyethylene (density 0.965° MI7) were processed using melt extrusion method.
A resin composition consisting of 30% of the resin composition was melt-extruded and coated to a resin thickness of 30 μm to form a resin layer with a matte surface.

After corona discharge treatment on the cover surface in the second zone, melt extrusion @gold layer, low density polyethylene (density 0.918° MI8.
5), 30 parts of a masterbatch kneaded with 30% by weight of titanium oxide, and low-density polyethylene (density 0.9
18. A resin composition consisting of 45 parts of MI 5.0) and 25 parts of high-density polyethylene (density 0.965.MI 7.0) was melt-extruded to a resin thickness of 30 μm to form a glossy resin layer. In the third zone, after corona discharge treatment is applied to the back resin surface, the coating solution described in Table 1 is applied to the first
A gravure roll with a size of 40 mesh was immersed, the excess coating solution was scraped off with a blade to make the coating solution constant, and the coating solution was transferred to the back resin surface and dried to produce a photographic support having antistatic properties. Is the amount of water-based coating liquid applied 3 f/rr? (moisture).

After corona discharge treatment was applied to the surface of the polyethylene-coated paper coated with cholera backcoat gold (i.e., the side of the support opposite to the side on which the backcoat layer was applied), JP-A-62-1998-1 was applied adjacent to the support. A blue-sensitive silver chlorobromide gelatin emulsion layer containing a yellow coupler and an intermediate layer prepared according to the recipe disclosed in Example 1 of No. 172350, a green-sensitive silver chlorobromide gelatin emulsion layer containing a magenta coupler and an ultraviolet absorber. An ultraviolet absorbing layer containing cyan coupler, a red-sensitive silver chlorobromide gelatin emulsion layer containing cyan coupler, and its protective layer were coated using an extrusion method and dried to create a multilayer silver halide color photographic paper (photosensitive). The average grain size and silver bromide content in the silver chlorobromide emulsion are listed in Table 2).

Each sample obtained as above in Table 2 t-50℃, 60%R
After being stored in a constant temperature and humidity bath for 1 day, the samples were evaluated by the method described below. At that time, the antistatic performance and film strength of the back coat layer are numerically evaluated, and the evaluation criteria for photographic (fogging) properties, pencil retouchability of the back coat, and haze on the surface of the photographic paper are: O mark (good), Indicated by Δ mark (slightly good) and × (unsatisfactory).

1 Development processing and photographic (fog) property evaluation: 50°C, 801
An unexposed sample in the form of a roll after being stored under RH conditions for 7 days was processed in the following steps, and fog on the emulsion surface was visually determined.

Processing steps (38°C) Color development 90 seconds Bleach-fixing 60 seconds Washing with water 60 seconds Drying 60-80°C 60 seconds The composition of the processing solution used in each processing step is as follows.

[Color developer]

Pure water 800- Hydroxyamine sulfate 2. O2 Potassium Bromide 1.5F Sodium Chloride 1. Of potassium sulfite 2. Of triethanolamine 2.0fN-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.521-hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 1.5
m Potassium carbonate 321 Add pure water to make 1 t, and adjust the pH to 10.1 with 20% potassium hydroxide or 10% diluted sulfuric acid.

[Bleach-fix solution]

Pure water 55o- Ethylenediaminetetraacetate iron (III) ammonium 6
59 Ammonium thiosulfate 85F Sodium hydrogen sulfite 1 (1 Sodium metabisulfite 2F Ethylenediaminetetraacetic acid 121 Sodium 20F Sodium bromide
10? Add pure water to make 1 t, and adjust the pH to 7.0 with aqueous ammonia or dilute sulfuric acid.

Evaluation of Emulsion Adhesion The coated support was rolled at 50°C.
It was stored for 7 days under 80% RH, and then the silver halide photographic emulsion of Example was coated and dried to prepare silver halide photographic paper.

The above-mentioned bactericidal development process was carried out in a bright room, and the emulsion side was scratched with four nails vertically and horizontally at intervals of 2 and 3 to create scratches in the shape of base grains, and then the surface was scratched with a fingertip under running water. was rubbed for 2 minutes, and the peeled area of the emulsion layer was determined using an image analyzer, and the area was determined as a percentage.

-Evaluation of antistatic property of skin 1. For samples before color development and samples subjected to the above color development treatment, 20
The surface resistivity of the sample back coat layer was measured at ℃ and 40% RH. :,.

Evaluation of the film strength of the bank coat layer 1 After immersing the film at 20°C for 3 minutes before color development, a ball point needle with a sphere diameter of 1-mm was set perpendicular to the film surface of the bank coat layer, and the sample surface was immersed at a rate of 2 cm/sec. The load of the ball point needle that caused damage to the back coat film (hereinafter referred to as film strength) when the back coat film was moved in parallel at high speed was measured.

Evaluation of edge writing properties of the back coat layer Writing was performed using a pencil HB knife and the recording state on the surface was observed to determine effectiveness.

Evaluation of haze on the surface of photographic paper 1 Sample t-8, cut into a size of 25m x 8.25m,
Ten layers are stacked so that the puncture coat layer and the silver halide photographic constituent layer are in contact with each other. This is t-40℃, 80% R, H
The device is placed under a 4.5 kg load and left for 24 hours. Thereafter, it was taken out, the sample was peeled off, and the degree of cloudiness on the surface of the photographic paper was visually determined.

The results obtained are shown in Table 3.

(Left below) As can be seen from Table 3, the back coat layer without colloidal silica (A14) has inferior antistatic properties and film strength compared to the back coat layer containing colloidal silica (A3). This is a problem. The same can be said for the case (A 15 ) in which sodium silicate is used as the silica source. In addition, this system (A15) has a surface pH of the back coat layer.
was high, and fog occurred in the photographic emulsion according to the present invention.

When polyvinyl alcohol is used instead of polymer latex as a binder for the back coat layer (A16
: The solid content of the binder is the same as that of A3), and the film strength when dry is strong, but the film peels off during development, which not only significantly reduces the antistatic property after development but also contaminates the developer, which is a problem.

On the other hand, the one having a back coat layer in the present invention (A
It can be seen that the materials X to 10) are excellent silver halide photographic materials that can satisfy photographic properties and other properties in a well-balanced manner. In particular, the value of medium)/(c) is 1
Back coat ranging from 5/85 to 66.7733.3 [
-For those with (Jf62-6.8-10),
Particularly good antistatic properties and film strength properties can be satisfied. Also, the value of (a)/(b) is 33/67
The same can be said for those having backcoat layers in the range of ~90/10 (Y3~6.8~10).

Example 2 The same procedure as in Example 1 was carried out except that the colloidal silica shown in Table 4 was used in place of the colloidal silica used in coating liquid A3 shown in Table 1 of Example 1. In addition, the same procedure as in Example 1 was carried out except that a N/10HCt or N/1ONaOH solution was added to the adjustment stage to make the solid content the same as in Coating Solution Boiling 3 to change the surface pH of the finished bank coat layer. carried out.

The results obtained are shown in Table 4.

As can be seen from Table 4, the surface pn of the bank coat layer mainly affects photographic properties (capri) and emulsion adhesion, and the surface pn
When H is low (418, 20, 21), emulsion adhesion deteriorates, and when surface pn is high (Y 17, 23, 24), fog occurs and photographic properties deteriorate. From these, if the surface pn of the bank coat layer of the present invention is 5.5 to 7.0, all the properties including photographic properties and emulsion adhesion can be satisfied.

Example 3 The same procedure as in Example 1 was carried out except that the coating liquid shown in Table 5 was used instead of the coating liquid shown in Table 1 of Example 1. still,
In the coating liquid listed in Table 5, [Yes])/(c) = 3
It is a constant value of 0.3/69.7.

The results obtained are shown in Table 6.

(The following is a blank space) Table 6 As can be seen from Table 6, the silver halide color photographic light-sensitive material having a back coat layer according to the present invention not only exhibits good photographic properties but also satisfies other properties in a well-balanced manner. It's an excellent thing to do. In particular, the amount of 2 da(c) is 5 my/lr? ~150 tng/? It can be seen that for those in the range of (A# to 30), the film strength of the back coat layer was also good, and the silver halide color photographic light-sensitive material had an excellent - layer.

Example 4 In place of the latex (a) used in coating liquid J163 and boiling liquid 4 of Example 1, the following latexes (a) to (g) were used at the same solid content, respectively.

(a) Styrene/acrylic latex 45% liquid (product name Bonron 5X-224, manufactured by Mitsui Toatsu ■) (b) Styrene/butadiene latex 48.3%g (product name
JSR-0642, manufactured by Japan Synthetic Rubber ■) Acrylic latex 45% liquid (Product name Movinyl 748)
(Made by Hoechst Synthesis) (1) Acrylic latex 5
0% liquid (Product name: Prifle TR-520, Rohm & Haas Japan Wheel) (E) Vinyl acetate latex 55% liquid (Product name: Cevian A-512, manufactured by Daicel ■) (Strength) Vinyl acetate latex 46 .5%g (Product name Cevian A-52
2. Manufactured by Daicel ■) (ki) Acrylic/silicone latex 42% liquid (product name: Siren ARJ-12L,
As a result, an excellent silver halide photographic material was obtained which satisfies the characteristics of good photographic properties, emulsion adhesion, and antistatic properties no matter what type of latex is used.

Example 5 The following polymer was used in place of the styrene-maleic anhydride copolymer Na salt used in coating liquids M3 and A4 of Example 1. At that time, the pI of the polymer solution was adjusted to 6.5 to 8.0 with an alkali or acid by heating as necessary.

(ri) Styrene-maleic anhydride 1:1 copolymerization (molecular weight 3000) (ke) Hexyl vinyl ether-maleic anhydride 1:1
Co-heavy metals (molecular weight approx. 10,000) (co) Isobutylene-maleic anhydride 1:1 copolymer (molecular weight approx. 60,000) (su) Inbutylene-maleic anhydride 1:1 copolymer (molecular weight approx. 160,000) (C) 1-hexene-maleic anhydride 1:1 copolymer (molecular weight approximately 10,000) (molecular weight 5 ooo) (C) 1-octene-maleic anhydride 1:1 copolymer (molecular weight approximately 10,000) ( (g) 1-decene-maleic anhydride 1:1 copolymer (
(molecular weight approximately 10,000) (ri) l-dodecene-maleic anhydride 1:1 copolymer (molecular weight approximately 10,000) (h) Higher α-olefin (carbon number 20 to 28)-maleic anhydride 1:1 copolymer Sodium salt (molecular weight: 10,000) Carboxy-modified polyethylene (trade name: Seiksenhe, manufactured by Steel Chemical Co., Ltd.) (Te) Sodium polyacrylate (trade name: Aron T-
40. Manufactured by Toagosei ■→ As a result, we have created an eroded silver halide photographic material that can satisfy the characteristics of good photographic properties, emulsion adhesion, and antistatic properties even when using any of the above-mentioned types of polymers. Obtained.

In place of the matting agent used in Example 1, silicon dioxide fine particles (trade name Thyroid 308゜ manufactured by Fuji Davison ■) were used, and a case with an average particle size of 4μ produced and dispersed by a double jet method was used. The same procedure as in Example 1 was carried out except for the case where barium sulfate particles were used.

As a result, exactly the same results as in Example 1 were obtained.

Example 7 Instead of the hardening agent used in coating solutions A3 and A4 of Example 1, N,N'-ethylenebis(vinylsulfonylacetamide), 1,3.5-)rivinylsulfonyl-hexahydro -8-) riazine, 2,4-dichloro-6-
The same procedure as in Example 1 was carried out except that hydroxy-8-triazine sodium salt and 1,6-hexamethylene isocyanate were used. As a result, exactly the same results as in Example 1 were obtained.

<Effects of the Invention> In summary, according to this invention, benzylal: d! I
Fortunately, the tin salts and halogens have no adverse effect on the skin, and have antistatic properties and scratch resistance.

Claims (1)

[Claims] 1) Using a color developing solution that does not substantially contain benzyl alcohol on one side of a resin-coated paper-type photographic support,
It has a silver halide color photographic emulsion layer that can be developed within 90 seconds above 30°C, and on the opposite side (back side), (a) colloidal silica, (b) polymer latex, and (c) carboxyl. surface pH 5.5 to 7.0, containing at least one of a water-soluble polymer compound or a salt thereof having a group or a sulfone group, and a hydrophilic polymer colloid.
A silver halide color photographic material comprising a back coat layer. 2) The silver halide color photographic material according to claim 1, wherein the back coat layer further contains a matting agent. 3) The silver halide color photograph according to claim 1 or 2, wherein the polymer latex is an acrylic polymer latex, and the composition ratio thereof is (b):(c) = 5:95 to 99:1 in terms of weight composition. photosensitive material. 4) Claim 1, wherein the composition ratio of the colloidal silica is (a):(b)=25:75 to 95:5 in terms of weight composition.
The silver halide color photographic light-sensitive material according to , 2 or 3. 5) Content of (c) is 5mg/m^2 to 150mg/m
The silver halide color photographic light-sensitive material according to claim 1, 2, 3 or 4, which is ^2. 6) Claim 1, wherein the back coat layer further contains a hardening agent selected from the group consisting of activated vinyl type, active halogen type, epoxy type, ethyleneimino type, methanesulfonic acid ester type, active ester type, and isocyanate type. ,
Silver halide color photographic light-sensitive material according to 2, 3, 4 or 5.