JPS58158632A - Photosensitive silver halide material - Google Patents

Abstract

PURPOSE:To inhibit the deterioration of image quality without increasing fog and reducing the high sensitivity even in rapid development at high pH and high temp. while using a sufficient amount of an org. thioether compound by combinedly adding the thioether compound and a specified heterocyclic compound. CONSTITUTION:A compound represented by general formulaI, concretely by formula II, III is added to a silver halide emulsion layer, and an org. thioether compound is added to the emulsion layer and/or a nonphotosensitive layer. By combinedly using both compounds, the deterioration of image quality due to the org. thioether compound and rapid development at high temp. is inhibited very effectively, and stable photographic performance is maintained without increasing fog and reducing the sensitivity.

Description

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

More specifically, silver halide photographic materials are capable of suppressing deterioration of the image quality of photographic images even if they use organic thio-ether compounds that provide extremely effective properties to silver halide photographic materials. Regarding materials.

In recent years, demands have become increasingly complex and diverse regarding the performance of silver halide photographic materials, and in particular, silver halide photographic materials with stable photographic performance and high or ultra-high sensitivity are required. ing.

In particular, in the case of X-ray photosensitive materials, in order to reduce the amount of XS 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, and with less fog and high image quality. Photographic materials are in demand.

Conventionally, one method of increasing the sensitivity of silver halide photographic materials is to use organic thioether compounds as solvents for silver halide or chemical sensitizers during the production of silver halide photographic emulsions. It is known that it can be used or added to a processing solution to enhance the development effect and increase the sensitivity of silver halide photographic materials.

For example, U.S. Patent No. 2,521,926;
No. 1.215, No. 3,038,805, No. 3.057
No. 724, No. 3,062,646, No. 3,506,
No. 443 and No. 3,574,709 disclose a technique for increasing the sensitivity of silver halide by incorporating an organic thio-ether compound during chemical ripening during emulsion production or immediately before coating. .

As described above, organic thioether compounds are compounds that provide extremely effective properties to silver halide photographic materials, but there are significant restrictions on their use. In other words, if an amount exceeding a certain limit is used to increase the sensitivity of a silver halide photographic light-sensitive material, it has the property of deteriorating the image quality of the photographic image and causing a significant deterioration of the photographic properties. .

In particular, due to the demand for rapid processing due to the destruction of X-ray photosensitive materials, image forming processes require short-time development processing of 20 to 30 seconds at high temperatures of 30 to 40 degrees Celsius. This has resulted in the deterioration of the 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 development processing for image formation on silver halide photographic materials. A typical method for obtaining high-quality silver halide photographic materials is to use a "hardening agent" to harden the gelatin (binder) of the photographic material.
known how to use. For example, inorganic compounds such as lipum alum, aldehyde compounds such as formaldehyde, glutaraldehyde, U.S. Patent No. 3,28
8,755, etc.
Compounds with Gen, U.S. I Patent No. 3.635.718
Compounds having reactive ethylenically unsaturated bonds as described in US Patent No. 3,091,53
Organic compounds such as epoxy compounds as described in C. No. 7 and halogen carboxaldehydes such as mucochloric acid are known.

However, when such a hardening agent is added in an amount sufficient to withstand the high-temperature rapid development processing of the /'%R photosensitive feather material, the properties of the silver halide photographic light-sensitive material are affected. (e.g., increase in capri, decrease in sensitivity, change in gradation, decrease in maximum density, etc.) and cause a long-term change in hardening effect called "posterior dura". ing.

Another known method is to increase the amount of gelatin (binder) relative to the amount of silver in the photosensitive material, but this method does not allow It has the disadvantage that processing properties such as developing, fixing, and washing with water are deteriorated.

Therefore, there is currently a strong demand for the emergence of a technology for obtaining high-quality silver halide photographic materials that can withstand high-temperature and rapid development processing by using organic thio-needle compounds in necessary and sufficient quantities. .

The first object of the present invention is to suppress deterioration of the image quality of photographic images even if an organic thioether compound that imparts extremely effective properties to silver halide photographic light-sensitive materials is used in a necessary and sufficient amount. It is an object of the present invention to provide a silver halide photographic light-sensitive material that can be used.

A second object of the present invention is to add an additive to suppress deterioration of the image quality of photographic images in a silver halide photographic light-sensitive material using a silver halide photographic emulsion containing an organic thiophyl compound. An object of the present invention is to provide a photographic material in which silver p-genide is contained in a constituent element of the material.

The third object of the present invention is rapid processing. Under request, high-1
It is an object of the present invention to provide a high-quality silver p-genide photographic material capable of suppressing deterioration of the image quality of photographic images even when subjected to rapid development processing at high temperatures.

The above object of the present invention can be achieved by incorporating a combination of an organic thioether compound and a compound represented by the following general formula [0] into the constituent elements of a silver halide photosensitive material.

General formula symbol ■ [In the above general formula, A and B each represent a nonmetallic atomic group necessary to form a hetero-Iff monkey, and X is an anion (for example, C1-1Br-1c+to4-1OH3SO3-, etc.)
shows. ] The present invention provides an organic thioether compound and the above general formula O
] (hereinafter referred to as compound compound) in a component layer of a silver halide photographic light-sensitive material.
However, in an embodiment in which these two types of compounds are contained in combination, at least one type of each of these two types of compounds may be contained in one component layer, or at least one type of each of these two types of compounds may be contained in one component layer. 7) It is possible to achieve the above-mentioned object of the present invention even if each component is contained separately in two independent component layers. A preferred embodiment of the present invention is to add the above compound into a silver halide emulsion layer, and to contain an organic thio-ether compound in the emulsion layer and/or the non-light-sensitive layer.

The present invention will be explained in detail below.

First, the compound moiety will be explained. The compound moiety represented by the compound moiety is necessary to form a heterocycle of the compound. [However, RI represents a hydrogen atom or a lower alkyl group, and m represents 2 or 3. ] The following compounds are listed as typical examples of the preferred compounds.

[Exemplary compounds]

(A-1) ■ C, h-2) (A, -a) (A-, i) Shin (A-s) (A, -6) A (A-7) The compound storage of the present invention is generally It can be easily synthesized from an azole compound having a methylmercapto group.

Synthesis Example-1 (Synthesis Example of Exemplary Compound (A, -5)) 2-Methylthiobenzothiazole 161P and 1,31-dibu ρ
Mopup Pan 252 was heated at 160° C. for 4 hours. After cooling, the precipitated crystals were collected and recrystallized from ethanol to obtain the target compound 14P in the form of needle-like crystals with a melting point of 260°C.

Synthesis Example-2 (Synthesis Example of Exemplified Compound (A-7:)) Chemical Abstract
ts), Vol. 72, p. 316fi, 6 (1970).

The amount of the compound used in the present invention is approximately 0.001 to 100% per 1f of the total binder in the gelatin hydrophilic colloid layer.
A range of two staves is preferred. In particular, 0.01 to 11119 is desirable, and usually 0.01 to 11119 is added to a solvent such as water or methanol.
It is used by dissolving it to a concentration of 1%. It can be added at any time before the coating and drying steps in the manufacturing process of the photographic material.

The compound storage used in the present invention is
No. 5, No. 48-39169, and No. 49-48172 each disclose a method for curing proteins, a method for creating a hardened image of gelatin,
Alternatively, it is disclosed as a method for curing vinyl polymers, but each of these publications describes the method of curing photographic images of silver halide photographic materials produced by the use of organic thio-ether compounds, which is a feature of the present invention. There is no suggestion whatsoever of suppressing deterioration of image quality. Moreover, the present invention
This does not utilize the hardening action of a binder such as gelatin to suppress the deterioration in the quality of photographic images of silver halide photographic materials that occurs when organic thioether compounds are used. According to the present invention, it is possible to maintain stable strength performance that cannot be obtained by a method that utilizes the hardening effect of a binder such as gelatin. Although this was completely unexpected and surprising, the present inventors have succeeded in minimizing the deterioration of the image quality of photographic images of silver halide photographic light-sensitive materials caused by organic thio-ether compounds by applying a chemical compound. If the hardening effect of conventional binders such as gelatin is used, it may adversely affect the properties of silver halide photographic materials (e.g. increase in capri, decrease in sensitivity, etc.). It has been discovered that there are advantages without any disadvantages.

Both the compound of the present invention and the organic thio-ether compound are known as materials for silver halide emulsions, but it is expected that great benefits can be realized by using them in combination. This could not have been done.

The organic thioether compound in the present invention is preferably a compound represented by the following general formula (5), (2) or sum.

General formula (Q-Rz-(S-Ra), 1-(D-R4)r), (
E) q General formula En General formula Jun ('l'-3-U'-V'-0O-V-U-)2Y In each of the above formulas, n and L represent 1.2 or 3, and '% Q is O
or 1, and p represents 1 or 2. Also, D is -
〇-1-lS-1-〇-Nh-11 0 and E are -OR7% OOR7, -flNI-17,
(R7 is 111 0 0 hydrogen atom or ψ representing an alkyl group having 1 to 5 carbon atoms, or each having 2 or more substituents and having 1 to 3 carbon atoms
represents a substituted alkyl group. The substituent is -OH
,=NH几8,-aooft8,-00NH,,-3o
3H, -0O0H1-8o3 - (ii8 is an alkyl group having 1 to 5 carbon atoms, M is an alkali metal atom ψ, and R2, R3, R,, R5 and R6 are lower alkylene groups, e.g. It is an alkylene group having 1 to 5 carbon atoms.

In addition, T is an alkyl group having 1 to 10 carbon atoms, a phenyl group, an aralkyl group 1 such as -(O)12), -QM(e
ld1~10 (7) integer) or -(0H2), -0OO
R.

(R9 is a lower alkyl group), and U and U' are carbon-
(OH2-1-0H2-(0HO)I20) R-
Alternatively, it represents a bolifluki1 OH3CH3 lene ether group represented by OH3 -(Ol, 1OH20)a-OH-0H2- (a is 2 to 30, and b is an integer of 0 to 2). However, O of the polyfulkyl ether group of U does not bond with ■. Further, U and [1' do not simultaneously form a polyalkylene ether group.

■, V' is -NH- or -〇-, and ■ and V'g cannot be 10- at the same time.

Y is -8-1-〇-1-0R2-1-(0H2-1I
represents an O group (R'IO is an alkyl group having 1 to 1 o carbon atoms);

Typical specific examples of organic thio-ether compounds represented by the general formula C1, 10 or □ are as follows.

[Exemplary compounds]

(a) HOOOH20H0Hz-80H20H2S
OHz 0HOH2000H1 0110H <b)tto(on,)2-s-(CI-12)2-s
-(OH2)2oH(C) HO(OH2)28 (
OH2)2 S (OH□)z S (OH2)20H
(d) [HO-(01→2)2 B (OH2)20.
0Hz-)z(e)(Ho-(aH2)is-(at
-t2)so-(aH2)2)2(r) (n5o□
-o-(On□)4s (O112)2)2b admiration)
(H,0-O-(OH2)4-8-(OH2)4-)
281 (h) (H2O-NH-0-(('J(z)2-8
-(OHz)3-)2・D(+) (Hsc-NH-
o-(on2)3-s-(aH,)3-)z・0(1)
(N11200(OH2)2-8-(OH2)20
ONI-1-0)12-)2(rrl) l-100
0-OH-OH2-8-(OH,,)2-8-CI-1
2-OH-000H11 H2NH2 There is no particular restriction on the method for synthesizing the organic thioether compound used in the present invention, and a general method can be used. For example, British Patent No. 950,089, U.S. Patent No. 3,
Specifications such as No. 021,215 and The Journal of Organic Chemistry Vol. 26, 1991
The descriptions on pages 1995 to 1995 (1961) can be referred to.

The organic thio-ether compound in the present invention is added in at least one step selected from the steps of producing a silver halide grain during emulsion production, during subsequent physical ripening, during chemical ripening, and immediately before coating. be done. It is particularly preferable to add it during precipitate formation, physical ripening, or chemical ripening.

The amount of organic thio ether used in the present invention is preferably 0,001 to 10,000 per mole of silver halide, particularly 0
01-1t is preferable.

Examples of silver halides that can be applied to the /%P silver genide photographic emulsion constituting the photographic light-sensitive material according to the present invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver bromoiodide, and chloroiodide. silver iodobromide and mixtures thereof, with silver iodobromide being the most preferred.

The binder or hydrophilic colloid used in the present invention is most preferably gelatin, but if necessary, sieved gelatin, colloidal algamine, agar, gum arabic, alginic acid, cellulose derivatives, acrylamide, imidized polyacrylic 7mide, It can be used in combination with polymers such as casein, vinyl alcohol polymer, polyvinyl alcohol, polyvinyl vinyl polymer, and hydrolyzed polyvinyl acetate.

The silver halide photographic emulsion used in the present invention includes various known chemical sensitizers, spectral sensitizers, antifoggants, hardening agents,
Gelatin hardener, surfactant, film property improver, thickener,
It may contain additives such as halftone dot improvers. Listing the various additives mentioned above, examples of chemical sensitizers include:
Noble metal sensitizers such as activated gelatin, water-soluble gold salts, water-soluble platinum groups, water-soluble palladium salts, water-soluble pdium salts, and water-soluble iridium salts; sulfur sensitizers; selenium sensitizers; polyamines, primary chloride Chemical sensitization can be carried out using a chemical sensitizer such as a reduction sensitizer such as tin or the like, either alone or in combination.

There are no particular restrictions on the spectral sensitizer, and for example, spectral sensitizers such as cyanine dyes such as zeromethine dyes, monomethine dyes, dimethine dyes, trimethine dyes, or mepcyanine dyes may be used alone or in combination for optical sensitization. be able to.

These techniques are described in U.S. Patent No. 2.688.545.
No. 2,912,329, No. 3.397.06
No. 0, No. 3,615,635, No. 3,628,9
Specification No. 64, British Patent No. 1,195,302, British Patent No. 1,242,588, British Patent No. 1,293,862, West German Patent (OLS) No. 2,030,326, British Patent No. It is also described in the specification of No. 2,121,780, Japanese Patent Publication No. 43-4936, Japanese Patent Publication No. 44-14030, etc. The selection depends on the wavelength range to be sensitized, the sensitivity, etc., the purpose of the photosensitive material,
It can be arbitrarily determined depending on the purpose.

The emulsions used in the invention can contain other additives. For example, stabilizers and anti-capri agents such as 7-zaindenes, triazoles, tetrazoles, imidazolium salts, tetrazolium salts, polyhydroxy compounds; aldehyde-based, aziridine-based, inoxazole-based, vinylsulfone-based, 7-klipyl-based, Hard ffl agents such as albodiimide-based, maleimide-based, methanesulfonate-based, triazine-based, etc. Development accelerators such as hensyl alcohol, polyoxyethylene-based compounds; Ri-pman-based, Claman-based, bisphenol-based, phosphite esters image stabilizers; lubricants such as waxes, glycerides of higher fatty acids, and higher alcohol esters of higher fatty acids;゛In addition, anionic, cationic, and nonionic surfactants can be used as coating aids, permeability improvers for processing #, antifoaming agents, and materials for controlling various physical properties of photosensitive materials. Alternatively, various species of both sexes can be used.

As antistatic agents, diacetyl cellulose, styrene perfluoroalkyl rhidium maleate copolymers, alkali salts of reaction products of styrene-maleic anhydride copolymers and p-aminebenzenesulfonic acid, etc. are effective. Further, examples of the latex added to improve the physical properties of the film include copolymers of acrylic esters, vinyl esters, etc., and other monomers having ethylene groups. Examples of gelatin plasticizers include glycerin and glycol compounds, and examples of thickeners include styrene-sodium maleate copolymers and alkyl vinyl ether-maleino acid copolymers.

The photosensitive material according to the present invention is produced by applying silver halide photosensitive material A11 to baryta paper, polyethylene-coated paper, polyethylene-coated paper, polypyrene synthetic paper, glass paper, etc., as required. , cell p-acetate, cellulose nitrate, polyvinyl acetal, polypropylene, a polyester film such as polyethylene terephthalate, or a support such as polystyrene by a known method.

The silver halide photographic material according to the present invention may be either a black-and-white photographic material or a color photographic material, and can be used for various purposes such as general use, printing, X-ray use, and radiation use, but in particular It exhibits remarkable effects as a high-sensitivity silver iodobromide photographic material.

The silver halide photographic light-sensitive paulownia material according to the present invention may be exposed to smoke time or flash light in addition to ordinary exposure, and can be photographically processed by ordinary methods. The basic photographic processing steps are two development steps and a fixing step, and these two steps S may be performed simultaneously.

The present invention will be described below as an example, but the embodiments of the present invention are not limited thereto.

Example-1 Emulsion IK4 contains 402% of silver iodobromide (containing 3.5 mol% silver iodide) and 452% of gelatin, and is sulfur-sensitized and gold-sensitized. After heating, it was divided into 19 parts, the compounds shown in Table 1 were added in the amounts shown in the same table, and the mixture was coated on a cellulose triacetate film base 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.1. Based on the TIS method, the melting point was measured using a KS-1 type sensitometer (manufactured by Konishiroku Photo Industry Co., Ltd.). , after giving white exposure, developing, fixing,
Processing was performed using a continuous roller conveyance type automatic developing machine that can perform water washing and drying in an integrated manner. The developer used was as follows.

Developing solution formulation (Developing time = 35° C., 30 seconds) Sensitometry was performed on each sample thus obtained, and the photographic properties obtained are shown in Table 1. Note that the sensitivity shown in the table is a relative sensitivity value with the sensitivity of the comparative sample (sample number -1) being 100.

The image quality shown in Table 1 is based on visual judgment of the degree of roughness of developed silver particles at a density of 0.8.

Note that 0 indicates good, Δ is average, and × indicates that it is so bad that it cannot be used. Two of these symbols written together indicate the W intermediate evaluation of each symbol.

As is clear from Table 1, the deterioration in image quality caused by the organic thioether compound was effectively improved by the compound, and it was found that the melting point did not increase.

Example-2 After the second ripening, zaponin was added as a coating aid to an X-ray silver gelatin emulsion containing 2 mol% silver iodide, and the compound was divided into 18 parts, and the compound shown in No. 2k was added. [Add the amount shown in the table and dry ff1Jl to 5μ on the borietele/terephthalate film base. Ii clothed. Each sample obtained in this way was heated to a tube pressure of 60 KVp.
X-ray sensitometry was performed at a tube current of 2 ilt) mA through an X-ray fluorescent screen (manufactured by Tokyo Shibaura Electric Co., Ltd.) with moderate sensitivity and an aluminum step wedge. Each of these samples was subjected to the same development process as in Example 1, and the obtained capri and sensitivity measurement results were used in the second sample.
It was shown on the clothes. In addition, the melting point was measured in the same manner as in Example 1 to evaluate the image quality. The results are shown in Table 2.

Table 2 As is clear from Table 2, the samples of the present invention have excellent Capriilli, sensitivity, and image quality, and moreover, the melting point (dural) does not increase.

Patent applicant: Konishiroku Photo Industry Co., Ltd. Agent: Patent attorney: Nobuaki Sakaguchi (and one other person) 27- 188-

Claims (2)

[Claims] (1) A silver halide photographic material containing an organic thioether compound and a compound represented by the following general formula. General formula 0ゝ-he-7 ■ [In the formula, A and B each represent a group of nonmetallic atoms necessary to form a heterocycle, and X represents an anion Ω (2) Non-metallic atom group A and/or 1 necessary to form the heterocycle of the compound represented by the general formula (2) R1 represents a hydrogen atom or a lower alkyl group. ] The silver halide photographic light-sensitive material according to claim 1, which is characterized by the following: