JPH01237539A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the contamination of a processing liquid by outflow of a matting agent by specifying the content of an org. material in the hydrophilic colloidal layers of a photosensitive material after the end of a development processing and constituting the matting agent of the nonphotosensitive protective layers of particles contg. a polymer having a hydrophilic group. CONSTITUTION:The photosensitive material having at least one layer of silver halide emulsion layers and at least one layer of the nonphotosensitive protective layers on a base is so constituted that the content of the org. material existing in the hydrophilic colloidal layers of said photosensitive material after the end of the development processing is >=90wt.% of said content before the development processing and that the matte layer existing in the nonphotosensitive protective layers consist of the particles contg. the polymer having the hydrophilic groups. The higher sensitization in the short-time processing is thereby attained and the contamination of images is prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a photographic light-sensitive material that prevents stains during processing, and in particular prevents image stains caused by matting agents that peel off from the photographic light-sensitive material into a processing solution. The present invention also relates to a silver halide photographic material with reduced haze after processing.

(Prior Art) In recent years, high-temperature, rapid processing has rapidly become popular in the development process of photographic light-sensitive materials, and the processing time of various light-sensitive materials in automatic processing has been greatly shortened.

In order to achieve high-temperature, rapid processing, we need a developer that can achieve sufficient color in a short period of time, a photosensitive material that has good developability and does not leave any residual color even during short processing times, and dries quickly after washing with water. A sensitive material is required. Many automatic processors have a built-in drying zone, and if the drying properties of the photosensitive material are poor, the automatic processor must have a higher drying capacity. I have no choice but to colander. Furthermore, as a result of generating a large amount of heat, there are also problems such as an increase in the temperature of the room in which the automatic processor is installed.

To prevent this from happening, efforts are made to make the drying speed of photosensitive materials as fast as possible. - A commonly used method is to add a sufficient amount of hardening agent in advance during the coating process of the photosensitive material, and to ensure constant development - to reduce the amount of swelling of the emulsion layer and surface protective layer during the water washing process. This is a method of reducing the water content in the photosensitive material before drying begins. In this method, if a large amount of hardening agent is used, the drying speed can be increased accordingly, but by strengthening the hardening agent, development may be delayed and the sensitivity may become low, and the covering power may be reduced and undeveloped halogens may be formed. This method has the drawbacks of causing various problems, such as a delay in the fixing speed of silver particles, worsening of residual color, and an increase in residual hypo in the photosensitive material after processing. On the other hand, the water content in the photosensitive material before drying can also be reduced by reducing the amount of hydrophilic substances coated on the photosensitive material, such as gelatin, synthetic polymers, hydrophilic low-molecular substances, etc. . ! The aqueous low-molecular-weight substance is added to the film for the purpose of preventing drying fog of silver halide grains during the coating process, and if it is removed, capri is produced on the photosensitive material.

On the other hand, if gelatin or a synthetic polymer substance used as a binder for silver halide grains is removed, the amount of binder to the silver halide grains will decrease, resulting in so-called high silver. Decreasing the amount of binder has the drawback of deteriorating graininess in terms of photographic performance, and especially with high aspect ratio tabular grains, sensitivity increases and decreases are more likely to occur due to scratches and bending when handling the photosensitive material before processing. Even if we try to improve drying properties, it is not possible to reduce the amount of binder due to these disadvantages.In this situation, we have achieved sufficient sensitivity in a short processing time, and have excellent fixing properties, water washability, and no residual color. There has been a need for a technology that can dry in a short time without leaving any residue.

In recent years, as a solution to this problem, as described in Japanese Patent Application No. 61-213503, a mechanical material ( For example, gelatin, capping agents, plasticizers, synthetic polymeric substances, and other organic substances) can be deposited during the development, washing, and drying processes by more than 10% of the total weight of the organic substances applied before processing. A technology has been developed to develop the film using an automatic processing machine so that it flows out. According to this method, excellent images with high covering power and a sufficiently fast drying speed were obtained.

However, it has been found that eluting a large amount of organic substances into the processing solution during development processing causes troubles that have not occurred in the past. This is because the matting agent added to photosensitive materials to bond them together and to prevent scratches peels off during the development, washing, and drying process, and precipitates in the processing solution, staining the image. This is the problem.

That is, the matting agent is disclosed in JP-A Nos. 51-6017 and 61-61.
As described in No. 20028, No. 53-7231, etc., this occurs when the surface protective layer of a photographic material comes into contact with another object. Particles with important functions that are used for purposes such as adhesion, preventing starch marks, preventing scratches, and making the surface of photographic materials slippery.
In order to exhibit these functions, it has conventionally been common knowledge to include a matting agent in a photosensitive protective layer (hereinafter referred to as a protective layer). However, in order to perform rapid drying, the mantle agent, which uses a technology to elute organic substances during processing, drops into the processing solution during the development, washing, and drying processes, resulting in an increase in the throughput of photographic light-sensitive materials. It has been found that they remain in the solution as the process progresses, contaminating the processing solution, and also adhering to the surface of the subsequently processed photographic material, staining the image and reducing its commercial value.

The present invention solves the problems of the conventional methods described above, that is, prevents the matting agent contained in the protective layer from leaking into the processing solution and contaminating the processing solution, and also reduces the haze of the photosensitive material after processing. It provides photosensitive materials.

(Objectives of the Present Invention) The first object of the present invention is to provide a photographic material that has a sufficiently fast drying rate and achieves a high degree of demonization in a short processing time. The second object is to provide a photographic material that does not cause image stains caused by the matting agent contained in the protective layer peeling off into the processing solution. The third object is to provide a photographic material with low haze.

In particular, it is an object of the present invention to provide a photographic material for X-ray that has the above-mentioned properties.

(Means for achieving the objects of the present invention) The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer and at least one non-light-sensitive protective layer on a support. , the amount of organic substances present in the colloid layer of the photographic light-sensitive material after development is 90% by weight or less of that before development, and the amount is present in the non-photosensitive protective layer. The cloak agent is 8%
This was achieved by a silver halide photographic light-sensitive material characterized by comprising grains containing a polymer having one group.

In the present invention, the loss of the 8I substance that flows out during the development, washing, and drying processes may be caused by physical elution or by chemical reaction. Specifically, It is preferable to include in the emulsion layer and/or other hydrophilic colloid layers organic substances which are likely to flow out during the development process, such as water-soluble synthetic or natural polymers. When the substance to be washed away is gelatin, it is preferable to use a gelatin type that is not involved in the crosslinking reaction of gelatin with a hardening agent, such as acetylated gelatin, phthalated gelatin, alkyl (e.g., eva, methyl, ethyl, propyl, benzyl) esterified gelatin, etc. falls under this category, and the molecular weight is preferably small, preferably 20,000 or less, more preferably 10,000 or less.

Examples of the water-soluble polymer used in the present invention include synthetic water-soluble polymers and natural water-soluble polymers, both of which can be preferably used in the present invention. Among these, examples of synthetic water-soluble polymers include those having, for example, nonionic groups, anionic groups, and nonionic and anionic groups in their molecular structures. Examples of nonionic groups include ether groups, ethylene oxide groups, hydroxyl groups, etc., and examples of anionic groups include sulfonic acid groups or salts thereof, carboxylic acid groups or salts thereof, phosphoric acid groups or salts thereof, etc. can be given. Furthermore, examples of natural water-soluble polymers include those having a nonionic group, an anionic group, and a nonionic group and an anionic group in the molecule tJILt.

As water-soluble polymers, in both cases of synthetic water-soluble polymers and natural water-soluble polymers, those having anionic groups, nonionic groups, and anionic groups can be preferably used. In the present invention, A water-soluble polymer is o, o per 100g of filtrate at 20°C.
It is sufficient to dissolve s g or more, preferably 0.1 g or more.

Furthermore, it is preferable that the water-soluble polymer of the present invention has a higher solubility in a developer or a fixer, and the solubility is higher than 100 g of a developer or a fixer.
It dissolves 0.05 g or more in 8. Preferably it is 0.5 g or more, particularly preferably 1 g or more.

Examples of synthetic water-soluble polymers include those containing 10 to 100 mol % of repeating units represented by the following general formula CP in one polymer molecule.

General formula (P) R.

+CH-C+ Y (L-)-r-+J-)-tQ In the formula, R3 is a hydrogen atom, an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms (including those with substituents, such as methyl) group, ethyl group, propyl group, butyl group, etc.), halogen atom (e.g. chlorine atom) or -〇 H
t represents COOM, L is 100NH-1-NHCO
-1-COO-1-OCO-1-CO- or -〇-, J is an alkylene group, preferably having 1 to 1 carbon atoms
10 alkylene groups (including those with substituents).

For example, methylene group, ethylene group, propylene group, trimethylene group, butylene group, hexylene group, etc.), arylene group (including those having substituents).

For example, phenylene group), or ÷CHt CHz O+-f-+CHz÷7°÷CHz
CHCHz Oto'→CHt÷0°H (m is an integer of 0 to 40, n is an integer of 0 to 4), and Q is 0M represents a hydrogen atom or a cation, R2
represents an alkyl group having 1 to 4 carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, etc.), Rs,
Ra, Rs, Ra, Rt and R1 are alkyl groups having 1 to 20 carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, hexyl group, decyl group, hexadecyl group, etc.), alkenyl groups (e.g. vinyl group, aryl group, etc.), phenyl group (e.g., phenyl group, methoxyphenyl group, chlorophenyl group, etc.), aralkyl group 7! - (e.g.
t hahenzyl group, etc.), X represents an anion, and p and q each represent O or 1. Particularly preferred are polymers containing acrylamide or methacrylamide.

Next, specific examples of the synthetic water-soluble polymer of general formula (P) will be given.

pt Number average molecular weight M.

÷CH, -CH÷1. .

0H8,000 5 (hK ts,oo.

1,000 CHt -CH++t.

C0OH4,800 9,000 ÷CHt -CH+r・・ 1000H Snow -C H++. .

CONH-CzHyis.

6,000 SO. Na HI ■ 1,000 GHz − C + l @・C O O +
CHzCnCHtO÷s C12 Ward OH 10,000 9, Go.

P-14 ÷CHz CH+*s +CHt -CH+x
CON Ht COOHt2.000 COOCHzCIlzOHC0NI CCIIzS
OJaL 8.000 H2 So, Na 10.500 So, Na (However, fi, : n, -59 mol%: 50 mol%, number average molecular weight (Mn) - about 10,000) CIl
zOCIh 5OJH* CIh0C
Hs (however, nl: n, -75 mol%: 25 mol%, M
n=about 20,000) These synthetic water-soluble polymers can be easily synthesized by various methods such as solution polymerization, bulk polymerization, and suspension polymerization.

For example, in solution polymerization, a mixture of monomers at an appropriate concentration (usually 40% by weight or less, preferably 10 to 25% by weight based on the solvent) in a suitable solvent (e.g., ethanol, methanol, water, etc.) is used. ) as a polymerization initiator (e.g.
benzoyl peroxide, azobisisobutyronitrile, ammonium persulfate, etc.) at an appropriate temperature (e.g. 40°C).
The copolymerization reaction is carried out by heating to 120°C to 120°C, preferably 50 to 100°C. The reaction mixture is then poured into a medium that does not dissolve the water-soluble polymer produced.
The molecular weight of the synthetic water-soluble polymer of the present invention is from t,ooo to 100,000, preferably from 2,000 to 100,000.
000 to 50°000.

°Natural water-soluble polymers are described in detail in the comprehensive technical data collection of water-soluble polymer water-dispersible resins (Management Development Center Publishing Department), but include lignin, starch, pullulan, cellulose, alginic acid, dextran, dextrin,
Guar gum, gum arabic, glycogen, laminaran, lignin, nigeran, etc., and derivatives thereof are preferred.

In addition, fi21 forms of natural water-soluble polymers include sulfonated, carboxylated, phosphorylated, sulfoalkylenated, carboxyalkylenated, and alkyl phosphorylated ones, salts thereof, and polyoxyalkylenes (e.g., ethylene, glycerin, propylene). etc.) and alkylation (methyl, ethyl, benzylation, etc.) are preferred.

In the present invention, two or more natural water-soluble polymers may be used in combination.

Furthermore, among natural water-soluble polymers, glucose polymers and their derivatives are preferable, and among glucose polymers and their derivatives, starch, glycogen, cellulose, lignin, dextran, nigeran, etc. are preferable, and dextran and its derivatives are particularly preferable. Derivatives are preferred.

Dextran is a polymer of α-1,6-linked D-glucose, and is generally obtained by culturing dextran-producing bacteria in the presence of saccharides. The native dextran can be obtained by reacting the separated dextran sucrase with saccharides using a solution, and the native dextran can be lowered to a desired molecular weight by a partial decomposition polymerization method using an acid or alkaline enzyme, and the intrinsic viscosity can be reduced to 0. ．．
03 to 2.5 can also be obtained.

Examples of modified dextran include dextran sulfate, carboxyalkyldextran, and hydroxyalkyldextran. The molecular weight of these natural water-soluble polymers is preferably 1,000 to 100,000, particularly preferably 2,000 to 50,000.

Methods for producing these dextrans and their derivatives are described in Japanese Patent Publication No. 35-11989 and U.S. Patent No. 3,76.
No. 2.924, Special Publication No. 45-12820, No. 45-1
No. 8418, No. 45-40149, No. 46-3119
It is described in detail in No. 2.

The synthetic or natural water-soluble polymer used in the present invention is contained in the photographic material in an amount of 10% or more of the total weight thereof,
The content is preferably 10% or more and 30% or less.

The amount of organic material used in the present invention that flows out during processing is 10% of the total weight of the organic material coated other than silver halide grains.
% or more and 50% or less is effective, preferably 15% or more,
It is preferable that 30% or less flows out.

The layer containing the organic substance washed away in the process of the present invention may be an emulsion layer or a protective layer, but when the total amount of the organic substance coated is the same, the layer containing the organic substance in the protective layer and the emulsion layer is more In a sensitive material with a multi-layered emulsion layer, it is preferable to contain the organic substance in the protective layer, and it is even more preferable to contain it only in the protective layer. It is preferable to contain a large amount.

Next, the matting agent having a hydrophilic group used in the present invention will be described in detail.

The hydrophilic group referred to in the present invention refers to nonionic, betaine,
It may be either cationic or anionic, and may be a combination of two or more species depending on the case.

The preferred hydrophilic group is +B-0%R0 (where B
represents an alkylene group including one having a substituent, such as -CH2-CH2-1-CH2-CH2-CH2-1. R3 represents the average degree of polymerization of the polyoxyalkylene group and is an integer of /-IO. Further, Ro represents a hydrogen atom, an alkyl group including one having a substituent, or an alkyl group including one having a substituent. ), for example, 11
11 [wherein, R12 represents an alkylene group having carbon atoms/-7 (e.g., methylene group, ethylene group, propylene group, butylene group), and R and R1 each represent a substituent having carbon atoms/-r (e.g., methyl group, ethyl group, benzyl group, etc.), and (9) represents an aryl group (e.g., phenyl group, tolyl group, etc.), including those having a substituent. ], for example, it has the same meaning as R1G and R1□, R13 has the same meaning as R2, and Ye represents an anion (
For example, it represents a doxy group, a halogen group, a sulfate group, a carbonate group, a perchlorate group, an organic carboxylic acid group, an organic sulfonic acid group, an organic sulfate group, etc.). ], for example, -8O3M-1-O803M-1-COOM.

-1-0-P-O In the formula, M represents an inorganic or organic cation, preferably a hydrogen atom, an alkali metal,
These include alkaline earth metals, ammonium, and alkylamines having 7 to 3 carbon atoms. ) and the like.

The above-mentioned hydrophilic group is generally introduced into the matting agent having a hydrophilic group by copolymerizing a polymerizable monomer having a hydrophilic group with another polymerizable monomer.

First, as a preferable hydrophilic additive, the following general formula % formula % General formula (sp) is used. In the formula, R14 and R15 are hydrogen atoms, alkyl groups, preferably alkyl groups having 1-hi carbon atoms (some with substituents). (e.g., methyl group, ethyl group, propyl group, butyl group, etc.), a chlorine atom (e.g., chlorine atom), or -CH2600M, and R2 is -CONH-1
-NHCO-1-COO-1-OCO-1-C〇- or -0-, and J2 represents an alkylene group, preferably an alkylene group having carbon atoms/-10 (including those having substituents. For example, methylene group, ethylene group, propylene group, trimethylene group, butylene group, hexylene group, etc.)
, arylene group (including those with substituents, such as phenylene group), or +CH2CH20 piece CH2
(m2 represents an integer of O to ≠O, R2 represents an integer of O-Hiroshi.) -CR2 represents a hydrogen atom or R16,
Of these, -803M is most preferred. M represents a hydrogen atom or a cation, R2 represents an alkyl group having 1 to ≠ carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, etc.) 'Ii-, R16, R17, RRR and R2□ are carbon atoms Represents an alkyl group (e.g., methyl group, ethyl group, propyl group, butyl group, hexyl group, decyl group, hexadecyl group, etc.) having an atom number of 1 to 18% to 19%, X represents an anion, and p and q2 represent Q or 1, respectively.

Specific examples of preferred hydrophilic monomers are described below.

Engineering Engineering J-Q Shiba: A 2
≧M −b, CH-Coo-ecH2CH20+5H
CH-Coo÷CH2CH2〇9H
\M-13, Uh+-2=U UU(JFIM-
/ reference, HOOC-CH-CH-CO
OHM-/7. CH2=CH-COO
HM-2/, CH2=CH-3o 3H 廓 工 PL Ｇａｒｅ ｄ ｄ ｄ）I′1 ′2 2 ΣOther seven monomers for producing a copolymer in combination with the above monomers include, for example, at least 1 Examples include monomers having ethylenic double bonds, which may be used in combination, and specifically include the following.

Examples of acrylic esters include methyl acrylate,
Ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, 5ee-bunal acrylate, tert-butyl acrylate, amyl acrylate, hexyl acrylate, coethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, λ -Chloroethyl acrylate, r-7" lomoedel acrylate, ≠-chlorobutyl acrylate, cyanethyl acrylate, λ-acetoxyethyl acrylate, dimetal ε-noethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, λ
-Chlorocyclohexyl acrylate, cyclohexyl acrylate, fur7lyl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, co-hydroxyethyl acrylate, j-hydroxyintylacrylate, 2-dimethyl-3-hydroxypropyl acrylate, comethoxyethyl acrylate, 3-methoxybutyl acrylate, coethoxyethyl acrylate, λ-1so-propoxy acrylate, cobutoxyethyl acrylate, λ-(comethoxyethoxy)ethyl acrylate, J-(,2-butoxyethoxy)ethyl acrylate, ω-methoxypolyethylene glycol Acrylate (number of moles added n = 2)
, /-bromo-λ-methoxy7 ether acrylate, 1.
Examples include l-dichlorocoethoxyethyl acrylate.

Examples of methacrylic acid products include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 5ec-
Butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, tert-butyl methacrylate,
Cyclohenzyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, sulfopropyl methacrylate, N-ethyl-
N-phenylaminoethyl methacrylate, J-(J-
phenylpropyloxy)ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, talesyl methacrylate, naphthyl methacrylate, co-hydroxyethyl methacrylate, hydroxybutyl methacrylate,
Triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, comethoxyethyl methacrylate, 3-methoxybutyl methacrylate, λ-acetoxyethyl methacrylate, coacehe7
Setoxyethyl methacrylate, coethoxyethyl methacrylate.

Corp., Ropoxyethyl methacrylate, λ-
Butoxyethyl methacrylate, co(2-methoxyethoxy)ethyl methacrylate, -1(coethoxyethoxy)ethyl methacrylate, λ-(2-butoxyethoxy)ethyl methacrylate, ω-methoxypolyethylene glycol methacrylate (number of moles added nex &
), allyl methacrylate, dimethyl methacrylate i
Noethyl methyl chloride salt and the like can be mentioned.

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenylacetate), vinyl acetate, Examples include vinyl salicylate.

Examples of olefin fists include dicyclontadiene,
Ethylene, furopyrene, t-7''tene, l-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, co-, J-dimethylbutazidine and the like can be mentioned.

Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxyethylene, chlorstyrene, dichlorostyrene, bromustyrene, trifluoromethylstere/, Examples include vinylbenzoic acid methyl ester.

Examples of crotonate esters include butyl crotonate, hexyl crotonate, and the like.

Examples of the itaconic acid diester include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

Examples of maleic acid diesters include diethyl maleate, dimethyl maleate, dibutyl maleate, and the like.

Examples of the 7-mer acid diesters include diethyl fumarate, dimethyl fumarate, and dibutyl 7-mer acid.

Acrylamides include acrylamide, methylacrylamide, ethyl acrylamide, propyl acrylamide, butylacrylamide, tert-y' tylacrylamide, cyclohexyl acrylamide, benzylacrylamide, hydroxymethyl acrylamide, methoxyethyl acrylamide, dimethylaminoether acrylamide, phenyl Acrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, N-(coacetoacetoxyethyl)acrylamide, etc.; Methacrylamides, such as methacrylamide, methylmethacrylamide, ethylmethacrylamide, propylmethacrylamide, butylmethacrylamide amide, ter
t-Butylmethacrylamide, cyclohexylmethacrylamide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide, dimethylaminoethylmethacrylamide, phenylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, β-cyanoethylmethacrylamide Allyl compounds, such as allyl acetate, allyl caproate, allyl laurate, allyl benzoate, etc. Vinyl ethers, such as methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxy Ethyl vinyl ether, dimethylaminoethyl vinyl ether, etc.; Vinyl ketones, such as methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, etc.; Vinyl heterocyclic compounds, such as vinyl pyridine, N-vinylimidazole, N-vinyl oxazolidone, N-vinyltriazole, N-vinylpyrrolidone, etc.; Glycidyl esters, such as glycidyl acrylate, glycidyl methacrylate, etc.; Unsaturated nitriles, such as acrylonitrile, methacrylate trile, etc.; Polyfunctional seven-mer-1, such as divinylbenzene, methylene Examples include bisacrylamide and ethylene glycol dimethacrylate.

Matting agents having these hydrophilic groups are described, for example, in US Pat. riPλ, 1st layer Ko, same! , 747° 1st layer issue, Tokukai Sho! ! -723/No. 5r-t6237, No. 60-
/ Described in Colo No. 11.

Also, JP-A No. 62-7 Hiro 6≠7, same 6 Ko 7! For j≠3, a copolymer consisting of a fluorine atom and an alkali solubilizing group is described. Particles composed of these polymers can be preferably used as the matting agent of the present invention, but are not limited thereto.

In the present invention, the polymer forming the matting agent preferably has a monomer having a hydrophilic group in a mole ratio of 2 to 70 moles, and preferably 3 to 70 moles. It is more preferable if it is Q mole rice cake, and what is especially preferable is! ~ It's San〇Morchi.

The coating amount of the matting agent contained in the protective layer is 0.0
0/NO, 3g7m% especially 0.0/~0.11g
7m is preferable, and the average particle size of the matting agent is O0! ~l! It is particularly preferable that it is 1 to t μm. In this case, this effect can be achieved if the matting agent has a hydrophilic group in an amount of 30% by weight or more, preferably 10% by weight or more of the total coating amount. Further, the matting agent having no hydrophilic group used in combination in this case is not particularly limited, and may be, for example, an organic compound such as polymethyl methacrylate or polystyrene, or an inorganic compound such as silicon dioxide. Further, in the present invention, the effect can be sufficiently exhibited even when one or more matting agents having hydrophilic groups are used in combination.

7 of all matting agents used in the photosensitive material in the present invention
171F! % or more, preferably to t %, particularly preferably yo teidobochi or more, is present in the protective layer.

The non-photosensitive protective layer (protective layer) referred to in the present invention is a layer that does not substantially contain silver halide grains for forming an image by being sensitive to radiation, and it The outermost layer is a surface protective layer.

In addition, in the case of a layer on the opposite side of the support, a so-called pack layer, it refers to the entire layer.

The protective layer may be composed of one layer, or may be composed of two or more layers. In the case of two or more layers, the protective layer containing the matting agent may be the outermost layer, or may be a protective layer other than the outermost layer.

The thickness of the protective layer is preferably from 0 to 3 μm, particularly from 0 to 3 μm per layer.

Other constituent factors of the photographic material of the present invention will be described below.

In the present invention, as the binder polymer that remains after processing and forms an image, binders that normally constitute photographic materials can be effectively used. For example, gelatin that participates in crosslinking with an average molecular weight of 70,000 to 100,000 (can be treated with lime or acid), polyacrylamide, polyvinyl alcohol,
Polyvinylpyrrolidone, dextran and their derivatives can be preferably used. Here, the poly(-) other than gelatin may be added separately from the water-soluble polymer of the present invention for the purpose of increasing the covering level of silver halide, or the water-soluble poly(-) used for the purpose of the present invention may be added separately from the water-soluble polymer of the present invention. - has a wide molecular weight distribution, and its high molecular weight components may remain,
It may be composed of components that have not been completely eluted from the low molecular weight components.

The amount of residual binder is preferably in a weight ratio of 173 to 3 times the amount of coated silver, particularly preferably Kl/2 to λ times. Of the binders in photosensitive materials before processing, gelatin is! O weight jIk% or more and 90 weight% or less are preferred, and more preferably 6j weight% or more and 10 weight% or less. The amount of remaining binder is 1. j～4
g/m, preferably 1 to 3 g/m.

The residual binder is generally ensured by curing it with various crosslinking agents. Various crosslinking agents can be used, but curing agents generally known in the art (as described in Research Disclosure, Vol. 776, p. 7) can be used. Gelatin is especially desirable as a residual binder, but as a hardening agent, 2. Hiro-dichloro-4
-Hydroxy-i, 3. Z-triazines or compounds having an active vinyl group or hero-substituted formamidinium salts or carbamoylammonium salts can be preferably used.

Examples of the compound having an active vinyl group include JP-A No. 1 JJ-$/JJ1, JP-A No. 1 J-17217, JP-A No. 1 J/-/Koj/Ko, JP-A No. 1 JJ63,
Tokukai Akira! /-$ reference l≦3, JP-A-Jλ-λ1032, Yoneo Patent 3, Oori No. 11, 3!3211, 3
6kosan t6, Tokuko Sho 10-31107, Tokukai Sho jl
- JOO Coco, Japanese Patent Publication No. 1.3-G4260, Japanese Patent Publication No. 144c-3, Japanese Patent Publication No. 447-17Jt, US Patent No. 3431711, US Patent No. 4c0720, West German Patent No. 17.2/! Compounds described in No. J can be mentioned.

As a compound having a helo-substituted formamidinium group, for example, JP-A-Shoto--λ! l reference RG, JP-A-61-
Examples include metal compounds described in λ4c02J6.

As a compound having a carbamoylammonium group,
For example, Tokko Sho Jls-/aIrJJ issue, Tokko Sho It-
Mention may be made of the compounds described in the Jet Tata issue.

Furthermore, as the gelatin hardener used in the present invention, a polymer hardener can be effectively used.
The polymeric hardener described in No.-417442 provides favorable effects.

The degree of curing of the binder by the curing agent may be sufficient as long as the swelling of the hydrophilic colloid islands comprising the silver halide emulsion layer and the protective layer is 300% or less. (Here, the swelling percentage is determined by a) moistening a sample of a photographic light-sensitive material at J#'C and relative humidity IO% for 3 days, b) measuring the layer thickness, and c) soaking the sample in distilled water at C. Soak for 3 minutes in
) The value determined by measuring the percentage change in layer thickness compared to the layer thickness measured in step b)) The photosensitive silver emulsion used in the present invention includes:
Silver chloride, silver chlorobromide, silver bromide, silver iodobromide, and silver chloroiodobromide can be used, but from the viewpoint of high sensitivity, silver bromide or silver iodobromide is preferable, especially when the legal content is Omo1%. ~j,
jmo1% is preferred.

Among silver iodobromide, grains having a structure having a high iodide phase inside are particularly preferred.

The silver halide grains are preferably tabular.

There are no particular restrictions on various additives, such as antifoggants, sensitizing dyes, dyes, polymer plasticizers, surfactants, anti-seizure agents, and the like.
No. 03, Specification No. 12-320702, etc. can be referred to.

The processing used in the present invention utilizes the dura during fA imaging and the dura during fixing, which is common in rapid automatic processing of X-ray sensitive materials, but the present invention utilizes the dura during development. This is particularly noticeable in automatic processor processing using a combination of a type of developer that does not harden the film and a fixer that does not harden the film during fixing or only slightly hardens the film during fixing.

The developer used in the present invention can contain conventionally known developing chemicals. As developing agents, dihydroxybenzenes (for example, hydroquinone), 3-pyrazolidones (for example, /-phenyl-3-pyrazolidone),
Amine phenols (for example, N-methyl-p-aminophenol) can be used alone or in combination.

The developing solution generally contains other known preservatives, alkaline agents, and
Contains H buffering agents, anti-fogging agents, etc., and further contains solubilizing agents, color toning agents, development accelerators (e.g., grade salts, hydrazine, benzyl alcohol), surfactants, antifoaming agents, water softeners, etc. agents, hardening agents (e.g. glutaraldehyde)
, a viscosity-imparting agent, and the like.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used.

The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

The developing method using an automatic developing machine in the present invention is disclosed in US Pat. Nos. 3,021,772 and 3! /! 111.
It is preferable to use a roller conveyance type automatic converter (*) described in No. 3!73rl≠, No.344<74cj, British Patent No. 1249241, etc.

The developing temperature is it 0c, zo'c, especially 300
It is preferable that C-≠Z a(, and the development time is preferably t seconds to HiroQ seconds, particularly t seconds to Ko! seconds.

It is preferable that the entire development process from the start of development to the end of fixing, water washing, and drying takes 30 seconds to 200 seconds, particularly 100 seconds to 100 seconds.

There are no particular restrictions on the additives, development method, exposure method, etc. of the photosensitive material of the present invention.
You can refer to the descriptions in the same volume item Ir Hiro J/ (/ri 7 r month).

(Example) Next, the present invention will be specifically explained.

Example/1-t Constituent of Emulsion Layer Potato-like grains of silver iodobromide (3 mol % silver iodide) were formed by a double jet method in the presence of ammonia (average grain size o, yrμ), gold sensitized and Chemical sensitization combined with sulfur sensitization was performed.

After chemical sensitization, an antifoggant 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene was added, and sensitizing dye (1) having the following structural formula was added at 200w per mole of silver halide grains. Then, ortho-exacerbation was performed.

(1) C, H.

CJs (CL) and dodecylbenzenesulfonate 0 as a coating aid.
．． 005 g/rd, polypotassium p-vinylbenzenesulfonate 0.03 g/rd as thickener
.

Polymer latex (poly [ethyl acrylate/methacrylic acid-97/3) particles adsorbed with Bolier polymerization degree 10] oxyethylene dodecyl ether [3% by weight of particles], average particle size -0.1 μm) 0.4 g /rd
- Sodium polyacrylate (molecular weight 200,000) O,
1g/rrr, 1. 0.03 g/rd of 2-bis(vinylsulfonylacetamido)ethane was added.

1-2 Configuration of protective layer.

Mu acid treated gelatin 0.4 (g/n?) Sodium polyacrylate 0.05 Mu poly (degree of polymerization 10) Oxyethylene poly (degree of polymerization 3) Glyceryl p-octylphenyl ether 0.03 Mu Fluorine-containing compound C3H? CsF+? 5OtN+CHzCHtO)*(CHi)4
sOsNa0.002 3Hq 0 days o, oos Mu 1,2-bis(vinylsulfonylacetamido)ethane 0.02 Mu p-t-octylphenoxyethoxyethoxyethanesulfonic acid sodium salt 0.02 The above emulsion layer, retention! ! A solution was prepared so that the gelatin concentration for each layer was 4 wt%, and this was used as a basic formulation for each layer.

Gelatin, a water-soluble polymer substance, and a matting agent were added to the emulsion layer and protective layer solutions in the amounts shown in Table 1, and styrene-butadiene latex was added as an undercoat layer. Photographic light materials 101-113 were prepared by simultaneously coating and drying onto a polyethylene terephthalate support on which a gelatin layer was applied.

At this time, the amount of silver coated on one side was 1.9 g/rr+, and the coating was applied on both sides. Further, the layers were arranged so that the emulsion layer and the protective layer were applied from the side closest to the support.

To measure the percentage (by weight) of the organic material applied before processing that has been washed away during the development, washing, and drying processes, use the following method. It can be measured by First 2
The sample was left in the apparatus under conditions of 5°C and relative humidity 1O% until the water content reached equilibrium with the atmosphere, and then the weight of the sample was measured. After the treatment, the specimen was left to stand again at 25° C. and 10% relative humidity, and when the moisture content reached equilibrium, the weight was measured. The weight of the support was measured in advance, and it was confirmed that there was no change in weight due to the treatment of only the support. The amount of developed silver was determined by applying n light uniformly or not at all, and from this value and the specific gravity of the silver halide, the weight loss of the silver halide grains themselves due to development and fixing was calculated. From these values, the weight of the organic material washed away during the treatment was determined. The emulsion also contains inorganic salts, which weigh only 1rjaIl! The amount was negligible compared to the loss of It. Here, the amount of organic substances washed away was determined by weight measurement, but the value can also be found by measuring the film thickness before and after treatment, and the amount of washed out substances can also be quantified by analyzing the treatment liquid.

Air volume: 1 lus ■ [My friend's automatic processor uses Fuji X-ray Processor FPM4000J manufactured by Fuji Photo Film ■.

The developer and fixer had the following compositions.

(Developer) l-phenyl-3-pyrazolidone 1.5g hydroquinone 30g 5-nitroindazole 0.25g potassium bromide
3.0g anhydrous sodium sulfite 5
0g Potassium hydroxide 30g Boron 61
10 g glutaraldehyde Add 5 g water to bring the total volume to 11
(The pH was adjusted to 10.20.) (Fixer) Ammonium thiosulfate 200.0g Sodium sulfite (anhydrous) 20.0g Boric acid
8.0g disodium ethylenediaminetetraacetate 0.1g aluminum sulfate 15.0g sulfuric acid
2.0g glacial acetic acid
Add 22.0g water 1.01
(The pH is adjusted to 4.20.) After the sample was developed using the above developer and fixer at FPM4000 and passed through the water washing process, the film was squeezed and was just before entering the drying zone. I took it out and made the following measurements (at the time of this measurement, FPM4000
(The drying air was stopped), and while blowing hot air onto the taken out film using a commercially available dryer, the time until the temperature of the film surface reached 30°C was measured using a surface temperature needle. Ring 4!1. The temperature was 35°C, and the washing water temperature was 14°C.

1) Processing was carried out using the above-mentioned processing solution and automatic developing machine, with the drying zone also operating normally. Exposure occurred with white light. The sensitivity value was determined as the logarithm of the reciprocal of the exposure amount required to obtain a degree of blackening of fog value +0.5.

E25.4em x 30.5c using the same developing solution and fixing solution as those used to measure drying speed.
Continuous automatic printing of 500 m-sized photosensitive material samples a
After passing through all the processing steps of the machine, the final 10 sheets were subjected to a sensory evaluation of the degree of staining on the surface of the processed sample on a five-point scale.

At this time, the sample used was one whose entire surface had been uniformly exposed in advance so that the density after processing was D-1 or D-2.

A: Almost no dirt is observed.

C: A very small amount of dirt is attached, but it is not a big concern in practical terms.

E: Dirt is attached and is very noticeable.

B and D were each in an intermediate state.

Niko The measuring device used was a turbidity meter manufactured by Nippon Heavy Industries Ltd.

The value automatically measured as haze-scattered light/total transmitted light X100 (%) was used as is. The smaller the haze value, the better the transparency, which is preferable for the photographic material of the present invention.

a) Moisturize a photographic light-sensitive material sample at 38°C and 5% relative humidity for 3 days, b) measure the layer thickness, and C) apply the sample to 2.
The thickness of the layer was measured after being immersed in distilled water at 1° C. for 3 minutes. The swelling ratio was expressed as follows.

The thickness of the layer measured in step b) (The results of the evaluation of 1 or more are shown in Table 1 together with the contents of the sample. The matting agent was poly(methyl methacrylate/methacrylic acid (8/2)), average particle size 4.0 μm poly (methyl methacrylate/methacrylic acid (515)), average particle size 3.8 μm1 poly (methyl methacrylate/ethyl methacrylate/methacrylic acid (4/2/4)
), average particle size 3.9 μm 1 and polymethyl methacrylate average particle size 4. 111m was used, and as water-soluble polymer substances to be eluted, dextran with an average molecular weight of 10,000, dextran with an average molecular weight of 38,000, or polyacrylamide with an average molecular weight of 0,800, was used.

The results in Table 1 will be described.

In contrast to the control (sample 101), in the samples (sample 103 and 104) in which a certain amount of the protective layer was replaced with a water-soluble polymer substance and an alkali-insoluble matting agent was used, the effect of the water-soluble polymer substance, that is, Shortening drying time,
It can be seen that although high sensitivity has been achieved, the staining due to processing has worsened, and the haze of the sample has increased after processing. In contrast, samples using the alkali-soluble matting agent of the present invention (samples 105 to 113)
In this case, the staining caused by the treatment was significantly improved without impairing the effect of the water-soluble polymeric substance, and the haze value of the treated sample was clearly lower than that of the sample using the alkali-insoluble mantle agent. It is clear that these results are due to the effects of the present invention, and it is clear that the present invention is extremely superior to conventional techniques.

Example 2 30 g of gelatin and 6 g of potassium bromide were added to 11 of water, and in a container maintained at 60°C, a potassium bromide aqueous solution containing a silver nitrate aqueous solution (4 g as silver nitrate) and a potassium bromide aqueous solution containing 0.15 g of potassium iodide was poured for 1 minute while stirring. It was added using the double jet method. Furthermore, silver nitrate aqueous solution (145g as silver nitrate) and potassium iodide 4.2
An aqueous potassium bromide solution containing g was added by a double jet method. At this time, the addition flow rate was accelerated so that the flow rate at the end of addition was five times that at the start of addition. After the addition, soluble salts were removed at 35°C by the sedimentation method, the temperature was raised to 40°C, 75g of gelatin was continuously added, and the pH was adjusted to 6.
Adjusted to 7. The resulting emulsion has a projected area diameter of 0.98
The grains were tabular grains with an average thickness of 0.138 μm and a silver iodide content of 3 mol %. Chemical enhancement was applied to this emulsion using a combination of gold and sulfur enhancement. After chemical sensitization, antifoggant 4-hydroxy-6-methyl-1,1,3a,
7-chitrazaindene was added, and sensitizing dye (II) having the following structural formula was added at 500 .mu.m per mole of silver halide grains to effect ortho-sensitization.

(■) II S02eSOJa In the same manner as in Example 1, a coating aid, a thickener, a polymer, and a curing agent were added to this emulsion to prepare an emulsion layer coating solution. The structure of the protective layer was prepared in the same manner as in Example 1, and gelatin, a water-soluble polymer substance, and a matting agent were added in the coating amounts shown in Table 2, and the same support as in Example 1 was prepared. Photographic light materials 201 to 213 were prepared by simultaneously coating the same layer arrangement on the body as in Example 1 and drying. At this time, the amount of silver coated on one side was 2.0 g/rrr and was coated on the screen.

Evaluation was performed in the same manner as in Example 1. The main composition of the sample and the test results are shown in Table 2.

From the test results in Table 2, it can be seen that in the photographic light-sensitive material samples using tabular silver halide grains, as in Example 1, the samples using the matting agent of the present invention (1)
Samples 205-213) are comparative samples (Samples 202-20
4), the staining caused by the treatment was significantly improved without impairing the effect of the water-soluble polymer substance, and the haze value of the sample after treatment was reduced, so it is clear that the present invention has the effect. Therefore, it is clear that the present invention is significantly superior to the conventional technology.

Example 3 3-1 Configuration of polymer layer (lowermost layer).

Mugelatin: 0.2g/n? Polymer A = 0.05g/n? 1 layer (C
Js)z Mu mordant M-Na and K 0.02g/nI poly(1a degree 10) oxyethylene cetyl ether=
0.005g/n? Polymer (thickener):
0.02g/d0J 3-2 Structure of emulsion layer.

30g gelatin, 5g potassium bromide, 0 potassium iodide in 17g water
．． Add 0.5 g of nitrate ttttm aqueous solution (5 g as silver nitrate) and 0.0 g of potassium iodide into a container kept at 75°C with stirring.
An aqueous solution of potassium bromide containing 73 g was added over 1 minute using a double jet method. Furthermore, silver nitrate aqueous solution (nitrate fII
145 g of Iim) and an aqueous potassium bromide solution were added by a double jet method. The addition flow rate at this time was accelerated so that the flow rate at the end of addition was eight times that at the beginning of addition. After this, 0.37 g of an aqueous potassium iodide solution was added.

After the addition, soluble salts were removed at 35°C by the sedimentation method, the temperature was raised to 40°C, 60g of gelatin was continuously added, and p
H was adjusted to 6.5 for I1 layer E. The temperature was raised again to 56°C, and 650 μ of the sensitizing dye anhydro-5,5′-di-chloro-9-ethyl-3,3′-di(3-sulfobrovir)oxacarbocyanine hydroxide sodium salt was added. Later, chemical sensitization using gold and sulfur enhancement was applied. The obtained emulsion had a hexagonal plate shape and a projected area diameter of 0.
The average thickness was 85 μm and 0.158 μm.

This emulsion was added with 4-hydroxy-6-methyl- as a stabilizer.
1, 3, 3a,? -tetrazaindene and 2,6-bis(
hydroxyamino)-4-diethylamino-1,3,5
-) Added riazine.

A coating aid, a thickener, a polymer, and a hardening agent were added to this emulsion in the same manner as in Example 1. However, the amount of 1,2-bis(vinylsulfonylua,cetamido)ethane was tripled.

3-3 Configuration of protective layer.

Real m? The amount of 1,2-bis(vinylsulfonylacetamido)ethane was tripled for the protective layer No. 11.

For the above emulsion layer and protective layer, gelatin, a water-soluble polymer substance, and a matting agent were added in the same manner as in Example 1 in the coating amounts shown in Table 3. Photographic materials 301 to 313 were prepared by simultaneously coating the polymer layer on the support and drying. The layers were arranged so that the polymer layer, emulsion layer, and protective layer were applied from the side closest to the support. At this time, the amount of silver coated on one side was 1.9 g/rd, and the coating was applied on both sides.

Evaluation was performed in the same manner as in Example 1. However, the developer, fixer, and development process were performed as follows.

(Developer) Potassium hydroxide 17g Sodium sulfite 60g Diethylenetriaminepentaacetic acid 2g Potassium carbonate
5g boric acid
3g Hydroquinone 35g
Diethylene glycol 12g 4-hydroxymethyl-4-methyl-1-phenyl-3 monopyrazolidone 1.65g 5-methylhensitriazole 0.6g acetic acid
1.8g potassium bromide
Adjust to 11 with 2g of water (adjust pH to 10.5 at t54) (fixing solution) Ammonium thioljL 140g of sodium sulfite 15g of ethylenediaminetetraacetic acid disodium dihydrate 25■Sodium hydroxide Adjust to 11 with 6g of water (adjust to 11 with acetic acid) The development process (adjusting the pH to 4.95) is as follows.

Processing temperature, time development: 35℃ x 11.5 seconds fixing
35℃ x 12.5 seconds water washing
20°C x 7.5 seconds drying 60°C dry to dry Processing time 60 seconds From the test results in Table 3, it was found that a polymer layer was formed at the bottom layer and hexagonal tabular emulsion grains were used in the emulsion layer to further speed up processing. Similarly to Example 1, in the photographic materials processed through the process, the samples (Samples 305 to 313) using the leather burr ice @Kiken Susa matting agent of the present invention are different from the comparative samples (Sample 302).
~304), the staining caused by the treatment was significantly improved without impairing the effect of the water-soluble polymeric substance, and the haze value of the sample after treatment was reduced, indicating that it has the effects of the present invention. It is clear that the present invention is significantly superior to the prior art.

Example 4 4-1 Preparation of support.

A styrene/butadiene-based latex was coated on both sides of a blue-colored polyethylene terephthalate support, and gelatin (0,085 g/
m), Polymer A (as described in Example 3-1,
0.058 g/rd) Dye with the following structure (0,0
17g/nf), dichlorohydroxytriazine (0
,01g/rrr), poly(degree of polymerization 10) oxyethylene p-nonylphenol ether (0,0015g/rrr)
-) and polymer particles (polymethyl methacrylate/acrylic acid, molar ratio 97:3, particle size 1.8 pm,
0.01 g/rd) was applied to both sides to prepare a support.

dye.

M Exploration Na and K 4-2 Structure of emulsion layer.

Same as Example 3.

4-3 Configuration of protective layer.

Same as Example 3.

For the above emulsion layer and protective layer, gelatin, a water-soluble polymer substance, and a capping agent were added in the same manner as in Example 1 in the coating amounts shown in Table 4, and the support of this example was prepared. Photographic light-sensitive material samples 401 to 413 were prepared by simultaneously coating and drying. At this time, each layer was coated in such a manner that the emulsion layer and the protective layer were arranged from the side closest to the support. In addition, the amount of coated silver was 1.9 g/al on one side.
It was applied to both sides.

Evaluation was performed in the same manner as in Example 1. However, the developer, fixer, and development process were performed in the same manner as in Example 3.

From the test results in Table 4, it can be seen that the photographic light-sensitive material using the support as in this example, the rapid processing solution, and the processing process also had the same effect as in Example 1. Samples using 177 additives (samples 405 to 413)
) compared to the comparative samples (samples 402 to 404), the staining caused by the treatment was significantly improved without impairing the effect of the water-soluble polymeric substance, and the haze value of the samples after treatment was reduced. It is clear that the effects of the invention have been improved, and it is obvious that the present invention is very superior to the conventional technology.

Patent applicant: Fuji Film Co., Ltd.

Claims (1)

[Claims] In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer and at least one light-insensitive protective layer on a support, the hydrophilic colloid present in the hydrophilic colloid layer of the photographic light-sensitive material after development processing is completed. A halogenated product characterized in that the amount of organic substance is 90% by weight or less of that before development, and the matting agent present in the non-photosensitive protective layer is composed of particles containing a polymer having a hydrophilic group. Silver photosensitive material.