JPS5940637A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To suppress deterioration of image quality accompanied by addition of a sensitizing dye, by incorporating a specified heterocyclic compd. in a silver halide photosensitive material contg. a sensitizing dye. CONSTITUTION:Hydrophilic colloidal layers contg. a silver halide emulsion layer are formed on a support, and a sensitizing dye having formula I or II is added to said emulsion layer. The intended silver halide photosensitive material is obtained by incorporating in an least one of said colloidal layers, a compd. represented by formula III in an amt. of 0.001-2mg per 1g of the total binder of the hydrophilic colloidal layers on the side of the support on which the emulsion layer is formed. In the formula, Z1, Z2, Z3 are each a thiazole ring or the like; Z4 is a 2-thiohydantoin ring or the like; R1-R5 are each lower alkyl or the like; n1, n2, n4 are each 0 or 1; n3 is 0, 1, or 2; (m) is 1 or 2; X<->1, X<->2 are each anion; A is S or Se; and B1, B2 are each a hetero ring.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic photosensitive material that exhibits little deterioration in image quality and can provide stable photographic properties.

More specifically, even if a sensitizing dye that has extremely effective properties for silver halide photographic materials is used in necessary and sufficient quantities, deterioration in the quality of photographic images can be suppressed. / Concerning Kagin Shasei photosensitive materials.

In recent years, there have been increasingly complex and wide-ranging demands regarding the performance of feather materials. Photosensitive materials are required.

In particular, in the case of X-ray photosensitive materials, in order to reduce the amount of X-rays that the human body is exposed to, we need to make them highly sensitive so that more information can be obtained with a smaller amount of X-rays, as well as to reduce the occurrence of fog. There is a demand for high-quality photographic materials.

Conventionally, one method of increasing the sensitivity of p-silver oxide photographic light-sensitive materials is to add a sensitizing dye to a p-granide photographic emulsion during the production of a p-granide photographic emulsion.・10
Silver germide is known to increase the sensitivity of photographic materials.

In general, sensitizing dyes are compounds that give very effective properties to silver norogenide photographic light-sensitive materials.
There are major restrictions on its use. That is, if the sensitivity of the /%P-gen illusion photosensitive material is increased by using violet exceeding a certain limit, it has the property of deteriorating the image quality of the photographic image, and the photographic characteristics will be seriously deteriorated. That's true. Among them, the compounds represented by the general formula (+-a) or (t-b) shown below have excellent sensitizing effects, but have problems such as deterioration of image quality and increase in fog. have.

In particular, for X-ray photosensitive materials, etc., under *ILO of rapid processing,
In image forming processing, development processing is performed for a short time of 20 to 30 seconds at a high temperature of 30 to 40° C., which has resulted in increasingly poor image quality of photographic images.

In this regard, many reports have been made regarding methods that can withstand harsh conditions such as high-temperature rapid MS processing for image formation of silver halide photographic materials. A typical method for obtaining a high-quality halogen-recording photographic material that can withstand such high-temperature and rapid development processing is to use a hardening agent that hardens the gelatin (binder) of the photographic material. known how to use. For example, inorganic compounds such as chromium alum, aldehyde compounds such as formaldehyde and glutaraltehyde, and US patent tJX3.
, 288,755, etc., and compounds having active halogens such as those described in U.S. Patent No. 3,635,7.
Compounds having reactive ethylenically unsaturated bonds such as those described in US Pat. No. 3,091,
Epoxy compounds as described in No. 537,
Organic compounds such as carboxaldehydes such as mucocuric acid are known.

However, when such hardeners are added to a sufficient amount to withstand the high-temperature rapid development processing of silver halide photographic materials, they adversely affect the properties of the photographic materials. For example, increase in fog, decrease in sensitivity, change in 1val,
It has drawbacks such as a decrease in the maximum concentration, etc.) and a long-term change in the hardening effect called "posterior dura".

Another known method is to increase the amount of gelatin (binder) used to record the original material, but this method causes a decrease in sensitivity. It also has the disadvantage that processing properties such as development, fixing, and washing with water are degraded.

Therefore, in order to obtain a high-quality silver Hagunide photographic photosensitive material that can withstand high-temperature rapid development processing even if the sensitizing dye represented by the general formula (1-a) or [g-b] shown below is used in a necessary and sufficient amount, The current situation is that the advent of technology is highly desired.

The first object of the present invention is to suppress the deterioration of the image quality of arrogant images even if a specific sensitizing dye that gives extremely effective properties to silver halide photographic light-sensitive materials is necessary and sufficient. (It is possible to provide a silver genide photographic photosensitive material).

The second object of the present invention is to carry out halogenation using a silver halide photographic emulsion containing a dye represented by the general formula (1-a) or (+-b) described later, which has a particularly high sensitizing effect. An object of the present invention is to provide a silver halide photosensitive material containing an additive for suppressing the deterioration of the image quality of a photographic image in the composition of the photosensitive material.

The third object of the present invention is to provide a high-quality silver halide photographic sensitizer that is capable of suppressing deterioration of the image quality of photographic images even when subjected to rapid development processing at a high temperature under the requirements of rapid processing. The goal is to provide materials.

The above object of the present invention is to coat a hydrophilic colloid layer containing at least one silver halide emulsion layer on one or both sides of a support, and at least one of the silver halide emulsion layers is as described below. In a silver halide photographic light-sensitive material containing at least one compound represented by formula [a] or (r-b) (hereinafter referred to as compound [, 1-a] or (y-b)), hydrophilic At least one of the colloid layers has a hydrophilic colloid layer on the side of the support coated with the silver halide emulsion (0.00 per 1f of total binder).
1 to 2 compounds represented by the following general formula [grave] (hereinafter referred to as
This is achieved by an I-ρ silver-genide photographic light-sensitive material, which is characterized by containing at least one of the following compounds.

General formula [Summer-a] In the formula, s zI and z2 are unsubstituted or each /Sq
Gen atom, lower furkyl group, lower alkoxy group or tophenyl group 1d-substituted birulin disintegration, thiacillin monkey,
Thiazo-/k at, Miss Benzothiazole.

Show the nonmetallic atomic groups necessary to form a naphthothiazole ring, a selenazole ring, a benzoselenazole ring, a naphthoselenazole ring, an oxazole term, a benzoxazole ring, a naphthoxazole ring, an imidazole ring, a benzimidazole ring, or a pyridine ring. , ``l and bird represent a lower alkyl group, hydroxyfurkyl group, carboxyalkyl group, or sulfoalkyl group, and when n3 is 1, ``l'' is a lower alkyl group or a hydrogen atom, and
When 3, 0 or 2, s nl and n2 represent 0 or l, and nBljO, 1 or 2
Represents X? represents an anion, m is 1 or 2 (
When the compound represented by the general formula (1-a) forms an inner salt, nl represents ψ which is 1.

General formula (r-b) 1 1 too.

4 In the formula, Z3 is unsubstituted or each substituted with a halogen atom, lower alkyl group, lower alkoxy group or phenyl group, forming a thiazole, benzothiazole, benzoselenazole, benzoinoxazole ring or pyridine ring. represents a nonmetallic atom group necessary for
, 4'-dione ring or a nonmetallic atom group necessary to form a ρ-menine ring, Ill, l represents a lower γ-rugyl group, a carboxyalkyl group, or a sulfoalkyl group, and R45 is a lower furkyl group or hydrogen represents an atom,
``4 represents 0 or 1.

General formula C11) In the formula, ATi represents a sulfur atom or a selenium atom, and B
1 and B2 each represent a group of nonmetallic atoms necessary to form a heterozygote, and X? represents an anion.

The present invention provides a composition of a photosensitive material containing the above compound (1-a) or [+-b] and the above compound (U).
Although the combination of these two types of compounds is contained in the layer Even if at least one of these compounds is separately contained in independent component layers, the aforementioned object of the present invention can be achieved. A preferred embodiment of the present invention is the above compound (
1-a) or (1-b) is added to a silver halide emulsion layer, and the above compound (If) is contained in an emulsion layer and/or a non-photosensitive layer, and the contained violet is the above compound. (ff) at least 11- of the hydrophilic colloid layer,
The total amount h of the hydrophilic colloid layer on the side of the support coated with the hydrophilic colloid layer [o, ooi ~ per 1 volt of binder]
2 Make it a lie.

At this point, if the distance is less than 0.001 my, the addition effect will not be enhanced, and 2
If the additive amount exceeds that level, the purpose of the present invention cannot be achieved because it will lead to deterioration of image quality.

The present invention will be explained in detail below.

First, to explain compound (1-a) or (1-b), the nonmetallic atom groups of z1 and Z2 in the general formulas (la) and [1-b] are the same or different. As long as it can complete the above-mentioned benzothiazole ring etc., examples of the benzothiazole ring include benzothiazole, 5-pμ benzothiazole,
5-Methylbenzothiazole, 5-methoxybenzot7zole, 5-human ρoxype/zoti7zole, 5-hydroxy-6-methylbenzothiazole, 5,6-methylbenzothiazole, 5-ethoxy -6-methylbenzothiazole, 5-henylbenzothiazole, 5-
Carboxybenzothiazole, 5-ethoxycarbonylbenzothiapour, 5,6-dimethylaminobenzothiazole, 5-7cetylaminopenzole, etc. are mentioned. Examples of the benzoselenazole ring include beyanzoselenazole, 5-riμlobenzoselenazole, 5-methylbenzoselenazole, 5-methoxybenzoselenazole, 5-human-oxybenzoselenazole, 5.6- dimethylbenzoselenazole, 5.6
-dimethoxypenzonanazole, 5-ethoxy-
6-methylbenzoselenazole, 5-human-oxy-6
-Methylpe/Zoselenazole 5-Henylbenzoselenazole, t', and further 7-thiapyl term and 1-teke, such as β-naphthothiazole, β, β-
Examples of naphthothiazole include naphthoselenazole, such as β-naphthoselenazole.

Specific examples of the above R1 and islands include alkyl groups such as methyl group, ethyl group, n-propyl group, β-carboxyethyl group, r-carbogypyl group, r-sulfopropyl group, r-sulfobutyl group, δ -Substituted alkyl groups such as a sulfobutyl group and a sulfoethoxyethyl group can be mentioned. Further, specific examples of the above-mentioned 4 include a hydrogen atom, a methyl group, an ethyl group, and a propyl group.

Specific examples of the 7-ion represented by X include halogen ion, perchlorate ion, thiocyanate ion, benzenesulfonate ion, p-toluenesulfonate ion, methylsulfate ion, and the like.

General formula (1-b) In the general formula (+-b), z3 is a
Represents a group of nonmetallic atoms necessary to form a thiazole group, a benzothiazole ring, a benzoselenazole group, a penzoisoogizazole term, or a pyridine ring substituted with a gun atom, a lower furkyl group, a lower alkoxy group, or a phenyl group. , 24 represents a group of nonmetallic atoms necessary to form 2-thiohydantoin, 2-thioxazolidine-2,4'-dione, or monodanine, and Rq's lower furkyl group, carboxyalkyl group, or sulfonate group. It represents an alkyl group, R5 is a lower alkyl group or a hydrogen atom, and 4 represents 0 or 1.

Preferably, each substituent in the above general formula (+-b) is specifically shown below. That is, Z3 is oxazole, 4
-Methyloxazole, 5-methyloxazole, 4.
5-dimethyloxazole, 4·-p-)lyloxazole, benzoxazole, 5-fluorobenzoxazole, 5-dimethyloxazole, 5-p-mobenzoxazole, 5-)! I Fluo ρ methylbenzoxazole, 5-methylbenzoxazole, 5-methyl-6-phenylbenzoxazole, 5.6-dimethylbenzoxazole, 5-methoxybenzoxazole, 5.6-cymethoxybenzoxazole, 5-7 enylpenzogisazole, 5-carboxybenzoxazole, 5-methoxycarbonylbenzoxazole,
5-7 Cetylpenzuoxazole・・・・・・・・・
Selenazole, 4-methylselenazole, 4-7enylselenazole, 4,5-dimethylselenazole, benzoselenazole, 5-chlorobenzoselenazole, 5-bromobenzoselenazole, 5-methylbenzoselenazole, 5- Methoxybenzoselenazole, 5,6-dimethylbenzoselenazole, thiazole, 4-methylthiazole, 4-phenylthiazole, 4
．． 5-dimethylthiazole, 4-methyl-5-phenylthiazole, benzothiazo-/, 5-cu-benzothiazole, 5-bromobenzothiazole, 5-methylbenzothiazole, 5-methylbenzothiazole, 5-ethoginebenzo Thiazole, 6-methylbenzothiazole, 6-benzothiapur, 5-carboxybenzothiazole, 5-7 cetylbenzotheazole, 5-methoxybenzothiazole, 5-human p-xybenzotebuzole, 5-)!j Fluo ρ Methylbenzote γ
sol, 5-cy7nobenzothi7pool, 5,6-methylbenzothi7zole, 5-7cetylaminopenzonaazole, 6-medogishipenzonazole, 5,6-cymethoxybenzothi7zole, 5,6-dikup Examples include rubenzote7zole, nando(1,2-a)thiazole, and the like.

In addition, z4 in the general formula (+-b) represents a nonmetallic atomic group necessary to form 2-thiohydatoin, 2-thioxazolidine-2,4'-dione, or ρ-danin, It may have the substituents shown below. That is, a furkyl group (for example, a methyl group, an ethyl group, a propyl group), a carboxyalkyl group, a hydrogynealkyl group, a sulfoalkyl group, an alcogincarbonylfurkyl group, an alkoxyfurkyl group, an acyloxyfurkyl group, an allyl group, Furthermore, substituted alkoxyalkyl groups [e.g., hydroxymethoginemethyl group, 2-hydroxyethoxymethyl group, 2-(2-hydrogynethoxy)ethyl group, 2-(2
-7cetogyethoxy)ethyl group, acetoxymethoxymethyl group], dialkyl7minoargyl group [e.g., 2-dimethylaminoethyl group, 2-dimethylaminoethyl group, 3-dimethylaminonoropyl group, 2-piperidinoethyl group, 2- morpholioether group, etc.), N-(N
, N-dialkyl7minoargyl)-rubamoylargyl group (e.g.
N-dimethylamino)ethyl]carbamoylmethyl group,
N-(3-morpholino)bupyl]carbamoylmethyl group, N-(3-(piperidi)bupyl]carbamoylmethyl group, etc.), N-(N,N,N-)realkylammoniumalkyl)carbamoylfulgyl group (For example, N
-(3-(N,N,N-1trimethylammonium)propyl]carbamoylmethyl group, N-(3-(N,N,N
-)ethylammonium)ppyl]carbamoylmethyl group, N-(3-(N-methylmorphojJ=o)pp
[Pyl]carbamoylmethyl group, N-(3-(N-methylpiperidinio)propyl]carbamoylmethyl group, etc.)
, N,N,N-trialkylammoniofurkyl group (e.g., N,N-diethyl-N-methylammonioethyl group, N,N,N-)rietherammonioether group, etc.)
, cyanoargyl group (e.g., 2-cyanoethyl group, 3
- sialaburyl group, etc.), carbamoyl alkyl group (
For example, 2-car/cumoylethyl group, 3-carbamoylpurpyl group, etc.), multi*mmm alkyl group (for example,
Tetrahydrofurfurylmethyl group, furfurylmethyl group), aryl group (e.g., phenyl group s l'
-Cup phenyl g, p-tolyl group, p-methoxyphenyl group, p-carboxifS nyl &% p-methoxycarbonylphenyl group, m-7 cetyl aminophenyl group, p-7 cetyl amino phenyl group, m -dialkylaminophenyl group (e.g. In-dimethylaminophenyl &) % p-dialkylaminophenyl & (H e.g.
p-dimethyl7minophenyl group), etc.

It also represents an alkyl group (for example, a methyl group, an ethyl group, a propyl group), a carboxyalkyl group, a hydroxyalkyl group, a sulfoalkyl group, a 2-human-oxy-3-sulfobopyl group, and a vinylmethyl group. and R5
is a hydrogen atom, a methyl group, an ethyl group, a propyl group, a ii-substituted furkyl group (e.g. 2-carboxyethyl, etc.)
, phenyl group, Wt-substituted phenyl group (for example, 0-carboxyphenyl group, etc.).

Next, typical examples of compounds (+-a) and (+-b) that can be effectively used in the present invention will be given, but the dyes that can be used in the present invention are not limited to these.

(ra-a-2) (1-a3) (+-a-4) (1-a-5) (1-a-6) (1-a-7) (1-a8) (+-a- 9) (1-a-FO) (1-a-11) (1-a-12) (1-a-13) (OH2)3803Na (+-a-14) (+-a-15) (+ -a-16) (l -a-17) (1-a-18) (1-a-19) (l-a-20) CI-a-213 (1-a-22) (1-a- 23) (1-a-24) 0□H5 (+-a-25) (+-b-t) (1-b-2) (1-b-3) (+-b-4) (+- b-s) (+-b-6) (1-b-7) OH□-011=OH□ (1-b-8) (1-b-9) (+-b-1o) (+-b -11) (+-b-12) (1-b-x3) (L2115 Compound (1-a) or (+-b) used in the present invention
can be easily synthesized, for example, by the method published in Japanese Patent Publication No. 47-23573, etc., or according to these methods. These compounds are added to the silver halide emulsion layer of the light-sensitive material according to the present invention. Then add it.

The stiff compound may be added at any time during the emulsion manufacturing process, but it is generally preferable to add it at or after the start of the second ripening, during the second ripening, or before or after the end of the second ripening. Yes. The content of the core compound varies depending on the type of silver halide emulsion, etc., but it can usually be used in the range of 119 to 500 species per mole of silver halide, but preferably 30 to 200 gy. It is best to use within a range. Nucleated substances (1-a3 or (
I-b) may be used alone or in combination of two or more.

Next, to explain compound (It), the nonmetallic atom #B1 necessary to form the hetep ring of this compound and/or the removed Hirodo 2 are (CH3'm' (however, R6 is water
L6 elementary atom or low acid glukyl group, m' represents 2 or 3;

] is preferred. Representative examples of compound C11) include the compounds shown below.

(Compound (exemplary compound of IIJ) [II-1] CI+-2) (II-3:) Lll-4) (ns) (i-6) tt-r3 CI+-8) ll-9) C =0 Cover 0 mouth 3 (ll-1o,) Compound (II) exemplified in Queen can be synthesized by the following method.

Synthesis Example 1 (Synthesis Example of Exemplified Compound [1]) 2-Methylthiobenzothiazole 50f and Ethylene Pr+j Doro 02
was reacted by heating at 160°C for 5 hours, cooled (k), the precipitated crystals were collected by filtration, and recrystallized using ethanol to give a
A desired product 502 in the form of needle-like crystals at 0.degree. C. was obtained.

Synthesis Example 2 (Synthesis example of exemplified compound ([-2)) 2-Methylthiobenzothiazole 509 and 1,3-dibulomopane 80 fQl were reacted by heating at 60°C for 5 hours,
After cooling, the precipitated crystals were collected by filtration and recrystallized using ethanol to obtain the desired product 22f in the form of needle-shaped crystals with a melting point of 261°C.

Also, for example, C11-73, (II-8:l and [■-
9] The chemical 4s product is chemical
mjcal Abstracts) Volume 72, 316
It can be synthesized using the method described on page 6 (1970).

Compound (1) of the present invention is usually dissolved in a solution of water or methanol to a concentration of 01 to 1%, and then added to the necessary solution. Also, it may be added at any stage during the emulsion w4M process, but it is generally preferable to add it after chemical ripening. Total binder of colloid layer 12 equivalents IJ O,001~2 m9
f) There is a % range, and special KO, 01-189 is desirable.

The compound of the present invention [salmon] has conventionally been used in
No. 95, No. 48-39169, and No. 49-48172, the compound is known as a compound used in a protein curing method, a gelatin hardening image creation method, or a vinyl polymer hardening method. No suggestion regarding the present invention is made at all. That is, the present invention does not utilize the hardening effect of a binder such as gelatin,
In this respect, the present invention clearly differs from the prior art. A feature of this invention is that it is possible to maintain stable photo-X performance that cannot be obtained by methods that utilize the hardening action of a binder such as gelatin.

To further discuss this point, the compound (If) of the present invention
The amount of violet used is 2 mg or less per 1V of binder such as gelatin contained in the ordinary silver halide photosensitive material to be processed, and this violet does not harden the binder. With this addition lid, the melting point of the photosensitive material to which the compound (n) of the present invention is added does not increase, and the object of the present invention can be achieved without causing the effect of causing (d[).

The silver halide photographic emulsion used in the present invention can be prepared by a conventional method known in the art, for example, as described in "The Theory Op.
It can be made according to the descriptions of ``The Photographic Books'', published by Macmillan Publishing, or ``Photographic Book Gummistry'' by Mr. Graffikides, published by Fantemples. The silver halide used may be silver chloride, silver bromide, silver chlorobromide, silver chlorobromide, or silver iodobromide, and may be used regardless of grain size or crystal shape. I can do it.

Silver halide photographic emulsions can be produced by applying various sensitization methods such as commonly used chemical sensitization, such as gold sensitization, sulfur sensitization, reduction sensitization, and combinations of these, such as spectral sensitizing dyes other than those of the present invention. Good too.

4 more! It is also possible to include r types of stock additives, such as stabilizers, anti-capri agents, hardeners and various coating aids. Gelatin is commonly used as a binder, and in addition, natural or synthetic hydrophilic polymer compounds such as I4 gelatin such as acylated gelatin, casein, Cell ρ-Z #Ij conductor, polyvinyl alcohol, and polyvinylbiridone are used. Can be used in combination. In addition, in order to further improve the physical properties, plasticizers, latex polymers, matting agents, and the like can be incorporated into the silver halide photographic emulsion as a thickening agent.

The silver halide photographic light-sensitive material according to the present invention is produced by applying a silver halide photographic emulsion to baryta paper, polyethylene-covered paper, polypylene synthetic paper, glass paper, It is constructed by coating on a support such as Cel 1-suacetate, Cel 1-sunitrate, polyvinyl acetal, polypropylene, polynisdel film of polyethylene terephthalate, polystyrene, etc. by a known method.

Compound (1-a) or (t-b) of the present invention and compound (
The /%R silver genre photographic light-sensitive material using a combination of It) is as follows:
It shows the following excellent effects. In other words, the drawbacks of these dyes, such as deterioration in image quality, increase in capri, and deterioration in granularity, are improved without reducing the photosensitivity of the sensitivity-sensitizing crystalline compounds (1-a) and (+-b). It also has very good stability, with no loss of texture or other deterioration during storage.

There are various types of silver halide photographic sensitivity according to the present invention. In other words, in addition to those used generally as black and white photographic materials, there are also photosensitive materials for X-ray photography, photosensitive materials for radiation use, photosensitive materials for direct positive use, photosensitive materials for diffusion transfer, photosensitive materials for microphones, and high M images. These include photosensitive materials for photosensitive applications and photosensitive feather materials for printing. Further, various multi-J-color η^ photosensitive materials containing couplers, direct positive color photosensitive materials, color X-ray photosensitive materials, color diffusion transfer photosensitive materials, etc. may be used.

The silver halide photographic light-sensitive material according to the present invention may be exposed to light for a short time or to flash light in addition to normal exposure, and can be photographically processed by a normal method. The basic processing steps are an image carrying step and a fixing step, and these two steps may be performed simultaneously.

The present invention will be illustrated below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 Emulsion I High-sensitivity iodobromide emulsion for X-rays containing 50t1 gelatin 452 with an average grain size of 1.3μ and 2.3 mol% of silver iodide in KQ After a second ripening using gold sensitizer and sulfur sensitizer, the emulsion was divided into equal parts and compound (+-a) or (1-b) was added to each part as shown in Table 1. After subsequent addition of stabilizers, hardeners and coating aids, compound CI+) was added just before coating and the strip I
11 [I was applied to prepare a sample. Compound (1-a)
and (+-b), the amount of compound (It) added is as shown in Table 1, and either compound (1-a) and (ib) or compound (II) was used as a comparative sample. Alternatively, a sample was created in which both were removed.

Each sample of this photosensitive material was exposed to white light using a KS-1 type centometer (manufactured by Konishiroku Photo Industry Co., Ltd.) according to the JIS method, and then developed, fixed, washed, and dried with a developer having the composition shown below. The process was carried out using a 3-mm machine capable of carrying out the process. For the sample after development obtained above, calculate the sensitivity from the point showing a density of +1.0 from Capri, express it as a relative sensitivity with the sensitivity of sample size 1 as 100, and at the same time calculate gamma and Capri as shown in Table 1. It was shown to. Also, the image quality shown in Table 1 is $i degree 0
This is a visual judgment of the degree of roughness of the mechanical particles in 8, where ○ indicates good, △ indicates normal, and × indicates a fist that is unusable. The one that I made shows the interim value of Tani 6's number.

As is clear from Table 1 below, compound (1-a) or (+
It can be seen that the deterioration in image quality caused by -b) is effectively improved by compound [ll], and does not have any adverse effect on photographic properties.

Example 2 Iodobromide (containing 35 mol% silver iodide) was added to 40% of the emulsion.
Contains 451 gelatin and exemplified compound (1-a-2
), the high-sensitivity negative emulsion subjected to sulfur sensitization and gold sensitization was subjected to a14 processing, and the compound (+-a-2
) was also prepared in the same manner as above.

After heating each of these to 40°C, it was divided into 18 parts, and the exemplified compounds [u-t], (H-1), (
H-2).

(o-3), [:0-1] were added only to the wrinkles shown in the exposure diagram, and the mixture was coated onto the Tate film base on Cell P-Strif to a film thickness of 4 μm, and dried. The melting point of each sample thus obtained was measured in a 0.2N aqueous sodium hydroxide solution. Also, based on the JIS method, K S -I m
A continuous ρ-ray transfer type autoclave that can be exposed to white light using a sensitometer (manufactured by Konishi Rokusha A Kogyo Co., Ltd.), then coated with water, washed and dried in one page.
It was treated with t# elm.

The developing solution used and the method of measuring image quality were the same as in Example 1.

6'v:, l'ltM, 1k123℃, humidity 65%It
After standing for 13 days, the sensitometric results are shown in Table 2 using the same monovalent method as in Example 1. However, the sensitivity is the relative sensitivity measured by the X-ray sensitometry method described in ITJ.

Margin below ■ However, C11-1), (H-2), (H-3
) is l111! (H-1) is (()tlo)2 (1-1-2) is (H-a) i, l: at-0-00of(I at-o-an.

represents a compound of

Also, (0-1) is an inhibitor, and as is clear from the second light, the unexploded 131J has excellent capri, sensitivity and image quality, and the melting point (hard M) increases by +7.
Koinai 4j lr″=I understand.

Patent applicant: Roku Konishi Photo Industry Co., Ltd. Agent Patent attorney: Bond Akira Sakaguchi (and 1 other person) September 12, 1980 Mr. Kazuo Wakasugi, Commissioner of the Japan Patent Office 1g Display Patent Application No. 142055 2 Invention Name of silver halide photographic light-sensitive material 3 Person making the amendment + 1 (Relationship to the case) Name of applicant (127) Roku Konishi Photo Industry Co., Ltd. 4 Agent 〒105 6 Number of inventions increased by amendment 7 Description subject to amendment (Detailed Description of the Invention Column) 8. Contents of Amendment Contents of Amendment (Japanese Patent Application No. 57-142055) The specification will be amended as follows.

l In the structural formula (I-a-6) on page 22, r
r (:Jl;").

2. Add the following to the bottom line of Table 1 on page 44.

3. On page 46, lines 8 to 10, it says, “However, the sensitivity...
It is. ” will be deleted.

That's it Itozo I! Ne City JF General (Spontaneous) September 3011, 1988 Mr. Kazuo Wakasugi, Commissioner of the Japan Patent Office 1 Indication of the matter Patent Application No. 142055 of 1988 2 Name of the invention Silver halide photographic light-sensitive material [3 Amendments] Person making the amendment/Relationship with case h Applicant name (127) Roku Konishi Photo Industry Co., Ltd. 4 Agents 105 + 6 Number of inventions increased by amendment 7 Description subject to amendment (claims and detailed description of the invention) Explanation column) Contents of amendment (Japanese Patent Application No. 57-142055) The specification will be amended as follows.

l The scope of the claims is amended as follows.

A wood-philic colloid layer containing at least one silver halide emulsion layer is coated on one or both sides of the support, and at least one of the silver halide emulsion layers has the following general formula (L
- In a silver halide photographic light-sensitive material containing at least one of the compounds represented by a) or (I-b), at least one of the wood-philic colloid layers is a support coated with the silver halide emulsion layer. A silver halide photographic light-sensitive material containing 0.001 to 2 mg of at least one compound represented by the following general formula (n) per 1 g of binder in the hydrophilic colloid layer on the body side. 1°-・General formula (I-a) R1, RIT.

(X?)m-s [wherein h and Z2 are unsubstituted or each substituted with a halogen atom, lower alkyl group, lower alkoxy group or phenyl group, biroline ring, thiazoline ring, thiazole ring, benzothiazole ring, naphtho Represents a group of nonmetallic atoms necessary to form a thiazole ring, selenazole ring, benzoselenazole ring, naphthoselenazole ring, oxazole ring, benzoxazole ring, naphthoxazole ring, imidazole ring, benzimidazole ring or pyridine ring, R1 and R2 represent a lower alkyl group, hydroxyalkyl group, carboxyalkyl group, or sulfoalkyl group, and R3 is a lower alkyl group or a hydrogen atom when B3 is 1, and a hydrogen atom when B3 is 0 or 2. Represents an atom, nL and nL represent O or 1, B3 is 0,! or θ 2 , Xl represents an anion, and m represents 1 or 2 (when the compound represented by the general formula (I-a) forms an inner salt, m is 1). ] -・General formula (r-b) [In the formula, Z3 is unsubstituted or /\rogen radical r,
Represents a group of nonmetallic atoms necessary to form a thiazole ring, benzothiazole ring, benzoselenazole ring, benzisoxazole ring, or pyridine ring substituted with a lower alkyl group, lower alkoxy group, or phenyl group, and Z
4 represents a nonmetallic atom group necessary to form a 2-thiohydantoin ring, a 2-thioxazolidine-2,4'-dione ring, or a rhodanine ring, R4 is a lower alkyl group,
represents a carboxy alkyl group or a sulfoalkyl group, R5 represents a lower alkyl group or a hydrogen atom, and n
ri represents O or 1. ] - General formula (II) [In the formula, A represents a sulfur atom or a selenium atom, and B
1 and Bλ each represent a group of nonmetallic atoms necessary to form a heterocycle, and ? represents an anion. ] 2 General formula (I-a) on page 9 of f1m is corrected as follows.

General formula (I-a) 3 The general formula (I-b) on page 10 is corrected as follows.

General formula (I-b) 4 Structural formula (1-b-2) on page 29 is supplemented with I as shown below.
F.

Note 5 The structural formula (I-b-3) on the same page is supplemented as follows.

Note 6 On page 43, line 8, the statement ``Processed by. Sample after development obtained as above'' is corrected as follows.

Processed.

[Developer composition] that's all

Claims (1)

[Claims] A hydrophilic colloid layer containing at least one 1zp gunned emulsion layer is provided on one or both sides of the support, and at least one layer of the p gunned emulsion layer is attached to the core. In the halide photosensitive feather containing at least one compound represented by the following general formula 1g1-a) or (1-IJ), at least one of the hydrophilic colloid layers comprises the silver halide emulsion. 1- Coalescence of the hydrophilic colloid layer on the side of the coated support (0.001 to 2 per binder 12)
R9)'i 1) A chemical compound containing at least one compound represented by the general formula (II). General formula (+-a) [wherein Z and z2 are unsubstituted or each substituted with a halogen atom, a lower alkyl group, a lower alkoxy group or a phenyl group; naphthothiazole ring,
R1 represents a bamboo nonmetallic atom group forming a selenazole ring, benzoselenazole ring, naphthoselenazole ring, oxazole ring, penzoxazole ring, naphthoxazole ring, imidazole ring, benzimidazole ring or pyridine ring; and R2 is a lower argyl group, human ρ
Represents a xy-γ alkyl group, a carboxyalkyl group, or a sulfofurkyl group; % "3 represents a lower furkyl group or a hydrogen atom when R3 is 1; and s represents a hydrogen atom when R3 is O or 2; nl and R2 represent a represents 0 or 1, R3 represents 0, 1 or 2, X room represents A=A), m represents 1 or 0, 2 (general formula L1-a
) When forming a compound h'-inner salt, I
n represents ρ which is 1. ] [In the formula, "3 is a thiazole ring, benzothiazole ring, benzoselenazole ring, benzoinoxazole ring, or pyridine ring, which is unsubstituted or substituted with a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a phenyl group, respectively. Z4 represents a nonmetallic atomic group necessary to form a 2-thiohydantoin compound, a 2-thioxazolidine-2,4'-dione term, or a monodanine ring. , h, represents a lower fulkyl group, carboxyalkyl group or sulfofurkyl group, ``h'' represents a lower fulkyl group or a hydrogen atom, and ``4'' represents 0 or 1. ] General formula C11) [In the formula, A represents a sulfur atom or a selenium atom, B
I and B2 each represent a group of non-metallic atoms necessary to form a heterozygote, and X? represents an anion. ]