JP3803334B2 - Hydroxamic acid compounds - Google Patents

Description

  The present invention relates to a novel hydroxamic acid compound that provides a photographically useful effect.

  The silver halide photographic light-sensitive material is required to have high sensitivity, and it is desired that fluctuations in photographic properties due to storage after production of the light-sensitive material and photographic properties from photographing to development processing are small. Among the photographic variations from photographing to development processing, for the prevention of latent image enhancement, Patent Document 1 discloses a method using a combination of a curing agent having an active vinyl group and a triazine compound. However, the above-described method has an insufficient prevention effect, and further improvement has been desired. On the other hand, in a full-color photographic material, a plurality of emulsions having different spectral sensitivities are used to achieve the purpose of full-color photography as a multilayer structure. Although the emulsion used is considerably improved, the latent image is fogged, reinforced, and regressed, which is not always sufficient. For example, 2-hydroxyamino-1,3,5-triazines are effective for improving the storage stability. However, the above-mentioned storage stability improver used in each layer varies depending on each emulsion. For this reason, there has recently been a strong demand for a method for improving the latent image preservability of a specific layer of emulsion.

  Known 2-hydroxylamine-1,3,5-triazines often diffuse and have a drawback of acting on emulsions in layers other than the intended layer. On the other hand, Patent Document 2, Patent Document 3, Patent Document 4, and Patent Document 5 disclose hydroxamic acids having a specific structure, but the purpose of use is different from that of the present application. However, it was insufficient in that it acted only on the emulsion of the other layer. Therefore, there has been a strong demand for the development of a method for greatly improving the storage stability of the latent image of only the target layer.

JP 59-162546 A U.S. Pat. No. 4,339,515 U.S. Pat. No. 4,330,606 JP 59-198453 JP-A-3-293666

An object of the present invention is to provide a compound having a high effect of improving the storage stability of a silver halide emulsion and the storage stability of a latent image . Another object of the present invention is to provide a compound that improves the preservability of the latent image of only certain layers . Another object of the present invention is to provide a compound which, when added, improves the storability of latent images without adversely affecting various photographic properties .

The object of the present invention has been achieved by the following means.
(1) A compound represented by the following general formula (II).

[In the general formula (II), ^{R 1} represents a substituted or unsubstituted alkyl group having 1 to 6 carbon ^{atoms, R a, R b, R} c, and R ^d represents a water MotoHara child, X is - represents oR ^{6, R 6} is a carbon number of 14-22 substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group having a carbon number of 14-22, or a substituted or unsubstituted aryl group having a carbon number of 14 to 22 Represents. ]

(2) In the general formula (II), R ⁶ The compound according to (1), wherein is a substituted or unsubstituted alkyl group having 14 to 22 carbon atoms.

(3) A compound represented by the following general formula (II).

[In general formula (II), R ¹ Represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ^a , R ^b , R ^c And R ^d Each independently may be the same or different and represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, or a substituted or unsubstituted alkenyl group having 2 to 18 carbon atoms, and X represents —OR ⁶ Represents R ⁶ Represents a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 22 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 22 carbon atoms. However, R ^a , R ^b , R ^c And R ^d Are not all hydrogen atoms. ]
(4) In general formula (II), R ⁶ The compound according to (3), wherein is a substituted or unsubstituted alkyl group having 6 to 22 carbon atoms or a substituted or unsubstituted alkenyl group having 6 to 22 carbon atoms.

(5) In general formula (II), R ⁶ The compound according to (3), wherein is a substituted or unsubstituted alkyl group having 14 to 22 carbon atoms or a substituted or unsubstituted alkenyl group having 14 to 22 carbon atoms.
(6) In general formula (II), R ⁶ The compound according to (3), wherein is a substituted or unsubstituted alkyl group having 14 to 22 carbon atoms.

The present invention provides compounds that can improve the storage and latent image stability of the emulsions of the particular layer described above. In order to solve the above problems, the present inventors have conducted intensive studies on compounds that can improve the storage stability of the produced emulsion and the storage stability of the latent image. In particular, as a result of various investigations on the number of carbon atoms and the types of substituents, an entirely new N-alkylhydroxamic acid compound of the present invention having a specific number of substituents or carbon number has been found. Furthermore, the compound of the present invention can be added to the silver halide light-sensitive material to change the hue of the dye formed, affect the dye forming speed of the coupler, accelerate the decomposition of the coupler or the formed dye, It has been found that the object of the present invention can be achieved without degrading the quality of the emulsion or even fogging the emulsion. Further, the compound represented by the general formula (II) of the present invention is a completely new compound which has not been known in the past. This compound has been found to have a photographic utility only by the inventors' research.
Hereinafter, the compound represented by the general formula (II) of the present invention will be described in detail. First, the compound represented by the general formula (I) which is more generalized will be described.

式（Ｉ）中、Ｒ¹ は置換又は無置換のアルキル基を表わす。Ｒ¹ は無置換でも置換基によって置換されていてもよい。Ｒ¹ は好ましくは、炭素数１〜６である。その好ましい具体例を挙げると、メチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、sec−ブチル、ｔ−ブチル、ｎ−ペンチル、イソペンチル、ネオペンチル、ｎ−ヘキシル、である。

In the formula (I), R ¹ represents a substituted or unsubstituted alkyl group. R ¹ may be unsubstituted or substituted by a substituent. R ¹ preferably has 1 to 6 carbon atoms. Preferable specific examples thereof are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, and n-hexyl.

Examples of the substituent for these alkyl groups include alkyl groups, alkenyl groups, aryl groups, heterocyclic groups, halogen atoms, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, cyano groups, nitro groups, alkoxycarbonyl groups, Examples include aryloxycarbonyl group, hydroxyl group, acyl group, acyloxy group, alkyl or arylsulfonyl group, acylamino group, alkyl or arylsulfonamide group, and specific examples include 2-chloroethyl, 2-methoxyethyl, 2- Cyanoethyl, 2-ethoxycarbonylethyl, 3-methylthiopropyl, 2-acetylaminoethyl, 3-hydroxypropyl, 2-acetyloxyethyl, 3-chloroethyl, 3-methoxyethylallyl and prenyl. R ¹ is preferably an unsubstituted alkyl group, particularly preferably a methyl group.

R ² is preferably a branched alkyl group having 20 or more carbon atoms, a linear or branched alkenyl group having 17 or more carbon atoms, and at least one alkoxycarbonyl group, alkenoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, acyl Represents a substituted alkyl or substituted alkenyl group having a total of 12 or more carbon atoms having a substituent selected from a group selected from a group, an alkoxy group, an alkylthio group, an arylthio group, an alkyl or arylsulfonyl group, an aryl group or a heterocyclic group .

This will be described in more detail below. In one preferred embodiment of the compound represented by the general formula (I) , R ² is an unsubstituted alkyl group.

When R ² is an alkyl group, the unsubstituted alkyl group is preferably a branched alkyl group having 20 to 60 carbon atoms. Specific examples thereof include the following structures.

In another preferred embodiment of the compound represented by formula (I) , R ² is a straight chain or branched alkenyl group having 17 to 60 carbon atoms. Specific examples thereof include 1-octadecenyl and 2-octadecenyl.

Another preferred embodiment of the compound represented by the general formula (I) is an alkyl group or an alkenyl group having 12 to 60 carbon atoms in total with R ² substituted by at least one substituent. In this case, the substituent substituted on the alkyl group includes an alkoxycarbonyl group, alkenoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, acyl group, alkoxy group, alkylthio group, arylthio group, alkyl or arylsulfonyl group, aryl group Or a heterocyclic group is preferable.

  Among these, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, and an amino group (including an anilino group) are preferable. Specific examples are given below. Alkoxy group (C1-C22. For example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, n-pentoxy, n-hexyloxy, n-octyloxy, stearyloxy, dodecyloxy, eicosyloxy, docosyloxy Oleyloxy). Specific examples of the alkoxy group include an alkoxy group derived from a higher alcohol having a trade name of Fine Oxocol, 140, 1600, 1800, 180, 180N, 2000, 2600 manufactured by Nippon Chemical Industry Co., Ltd.

  An aryloxy group (having 6 to 16 carbon atoms, such as phenoxy, p-methoxyphenoxy, m-octyloxyphenoxy, o-chlorophenoxy, 2,4-di-t-octylphenoxy); Alkoxycarbonyl group (C2-C23. For example, methoxycarbonyl, ethoxycarbonyl, n-butoxycarbonyl, isopropoxycarbonyl, t-butoxycarbonyl, n-octyloxycarbonyl, n-dodecyloxycarbonyl, pentadecyloxycarbonyl, stearyl. Oxycarbonyl, oleyloxycarbonyl, docosyloxycarbonyl). Furthermore, as an alkoxycarbonyl group, the alkoxycarbonyl group induced | guided | derived from each higher alcohol of the brand name Fineoxocol, 140, 1600, 1800, 180, 180N, 2000, 2600 by Nippon Chemical Industry Co., Ltd. is mentioned as a specific example. It is done.

  An aryloxycarbonyl group (having 6 to 17 carbon atoms, such as phenoxycarbonyl, p-ethoxyphenoxycarbonyl, m-dodecyloxyphenoxycarbonyl, o-fluorophenoxycarbonyl, 2,4-di-t-octylphenoxycarbonyl). Carbamoyl group (C3-C37. For example, dimethylcarbamoyl, diethylcarbamoyl, dioctylcarbamoyl, distearylcarbamoyl, dioleylcarbamoyl, bis- (2-ethylhexyl) carbamoyl, stearyloxypropylcarbamoyl), amino group (C1-22) Eg octylamino, dioctylamino, stearylamino, distearylamino, oleylamino, dioleylamino, methylamino, anilino)

A preferred structure of the compound represented by the general formula (I) is that in which R ¹ is a substituted or unsubstituted alkyl having 1 to 6 carbon atoms, and R ² is represented by the following general formula (IA). .

In the general formula (IA), R ³ is an alkylene group or alkenylene group having 2 to 20 carbon atoms, R ⁴ is a substituted or unsubstituted alkyl group or alkenyl group having 1 to 30 carbon atoms, 6 to 20 carbon atoms A substituted or unsubstituted aryl group and a substituted or unsubstituted heterocyclic group having 2 to 20 carbon atoms are represented. L represents —CO—, —SO ₂ —, —O—, —S—, —COO—, —CON (R ⁵ ) —. R ⁵ represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms. However, when L represents -O-, R < ⁴ > is a C1-C40 substituted or unsubstituted alkyl group. The total number of carbon atoms of R ³ , L and R ⁴ is preferably 12 or more.

In the formula (IA), R ³ represents an alkylene group or alkenylene group having 2 to 20 carbon atoms, preferably 1,2-ethylene group, 1,3-propylene group and substituted 1,2-ethylene group. Specific examples of R ³ are given.

Among these, R ⁴ is preferably a substituted or unsubstituted alkyl group or alkenyl group having 1 to 30 carbon atoms. Among them, a substituted or unsubstituted alkyl group or alkenyl group having 6 to 22 carbon atoms is more preferable. L represents —CO—, —O—, —SO ₂ —, —S—, —COO—, —CON (R ⁵ ) —. Among these, L is preferably —O—, —CO—O—, or —CO—NR ⁵ —.

Among them, R ⁴ -L- represents an alkoxycarbonyl group, an alkenoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an acyl group, an alkoxy group, an alkylthio group, an arylthio group, an alkyl or arylsulfonyl group, or an aryl group. Is preferred. The total number of carbon atoms of R ⁴ , L and R ³ is preferably 12 or more and 60 or less.

The compound represented by the following general formula (II) among the compounds represented by the general formula (I) is the compound of the present invention .

In the general formula (II), R ¹ represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ^a , R ^b , R ^c and R ^d may each independently be the same or different, and hydrogen atom, or an alkyl group substituted or unsubstituted 1 to 18 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 18 carbon atoms, X represents a -O R ^6, R ⁶ is 1 to carbon atoms 22 represents a substituted or unsubstituted alkyl group having 22 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 22 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 22 carbon atoms. R ¹ is preferably a methyl group, an ethyl group or an n-hexyl group. R ^a , R ^b , R ^c and R ^d are all preferably hydrogen atoms or at least one of R ^a , R ^b , R ^c and R ^d is an alkyl or alkenyl group having 5 to 18 carbon atoms, Sometimes others are hydrogen atoms. R ⁶ is preferably an alkyl group or alkenyl group having 6 to 22 carbon atoms. However, when R ^a , R ^b , R ^c and R ^d are all hydrogen atoms, R ⁶ preferably has 14 or more carbon atoms .

One of the most preferred structures in the general formula (II) is that R ^a is an alkenyl group or alkyl group having 12 to 18 carbon atoms, R ^b , R ^c , R ^d are hydrogen atoms, and R ¹ is methyl. A group, an ethyl group or an n-hexyl group, X is —OR ⁶ , and R ⁶ is an alkyl or alkenyl group having 12 to 18 carbon atoms.

Another most preferred structure in the general formula (II) is that R ^c is an alkenyl group or alkyl group having 12 to 18 carbon atoms, R ^a , R ^b , R ^d are hydrogen atoms, and R ¹ is It is a methyl group, an ethyl group or an n-hexyl group, X is —OR ⁶ , and R ⁶ is an alkyl group or alkenyl group having 12 to 18 carbon atoms. Another most preferred structure in the general formula (II) is that R ^a , R ^b , R ^c and R ^d are all hydrogen atoms, and R ¹ is a methyl group, an ethyl group or an n-hexyl group. , X is OR ⁶ , and R ⁶ is an alkyl or alkenyl group having 12 to 18 carbon atoms. Above the most preferred are R ^a, even compounds of the present invention, R ^b, is R ^c, R ^d are all hydrogen atoms, R ⁶ is a myristyl group, a palmityl group or a stearyl group R ¹ is a methyl group, ethyl In the case of a group or n-hexyl group.

The compound represented by the general formula ( II ) preferably has a molecular weight of 250 or more, more preferably 300 or more, and most preferably 330 or more.

  The compound of the present invention needs to be substantially insoluble in water from the viewpoint of not diffusing in the gelatin film. Note that “substantially insoluble in water” means that the solubility in water at 25 ° C. is 5% or less, but preferably 1% or less.

  In some cases, the compound of the present invention can be obtained only as a mixture of isomers and homologues (for example, acid anhydrides and alcohols described later) as synthetic raw materials. Therefore, the compound of the present invention may be easier to produce when synthesized as a mixture of isomers and homologs. At this time, the compound of the present invention is preferably added to the silver halide photosensitive material as a mixture.

  Specific examples of the compound of the present invention are illustrated. However, this does not limit the present invention. Among the following compounds, Exemplified Compounds 1-5, 7-11, 14-30, 34-42, 50, 53-55 are compounds of the present invention.

  The general synthesis method of the compound of the present invention will be described below. The compound of the present invention is obtained by condensing the corresponding carboxylic acid chloride and N-alkylhydroxylamine. The carboxylic acid chloride can be easily obtained by treating the carboxylic acid with thionyl chloride or oxalyl chloride when the corresponding carboxylic acid is easily available. In the case of a complicated carboxylic acid, it can be obtained by synthesizing the carboxylic acid by a synthesis method corresponding to each and then treating with thiotyl chloride or oxalyl chloride. Carboxylic acid can be synthesized according to the following synthesis example. On the other hand, N-alkylhydroxylamine is commercially available in which alkyl is a methyl group. Others can be synthesized by the following method.

  Acetone is added to hydroxylamine and converted to acetoxime, and then reacted with an alkylating agent to synthesize an N-alkyl compound (nitrone). Thereafter, acid treatment is carried out to remove acetone to obtain N-alkylhydroxylamine.

  Representative synthesis examples of the compounds of the present invention are described in detail in the Examples below.

Hereinafter, a photosensitive material using the compound of the present invention (in the description, it may be abbreviated as a photosensitive material or a photosensitive material of the present invention for convenience) will be described.
The addition amount of the compound of the present invention is not particularly limited, but when added to the photosensitive silver halide emulsion layer, it is 1.0 × 10 ^{−4 to} 1.0 × 10 ⁻¹ mol with respect to ¹ mol of Ag in the addition layer. The range is preferable, and the range of 1.0 × 10 ^{−3 to} 5.0 × 10 ⁻² is more preferable. When added to the non-photosensitive layer, it is preferably 1 × 10 ^{−6 to} 3 × 10 ⁻⁴ mol / m ^{2, and} more preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻⁴ mol / m ² .

  The compound of the present invention may be added after being dissolved in a water-soluble solvent (such as methanol, ethanol or acetone), or may be added after being co-emulsified with a coupler or the like by emulsion dispersion. Further, it may be added in advance during the preparation of the emulsion, but the method of adding by emulsification dispersion is most preferable.

  The layer to which the compound of the present invention is added is not particularly limited, but is preferably added to the silver halide emulsion layer, and more preferably to the red photosensitive layer and / or the green photosensitive layer.

  The present invention can be applied to various color light-sensitive materials such as color negative films for general use or movies, color reversal films for slides or television, color papers, color positive films and color reversal papers. Further, it is suitable for the lens-fitted photo film unit described in JP-B-2-32615 and JP-B-3-39784. Further, the present invention can be applied to diffusion transfer type color photographs using heat development, diffusion transfer photographs using auto positive emulsions, and wet reversal color copy materials using auto positive emulsions. The present invention can also be applied to black and white photosensitive materials such as black and white negative films, microfilms, and X-ray films. Photosensitive materials for general color and black-and-white photography are preferred.

  When the present invention is applied to a color photosensitive material, it is sufficient that at least one photosensitive layer is provided on the support. A typical example is a silver halide photographic light-sensitive material having at least one photosensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivity on a support. It is. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light.In a multilayer silver halide color photographic light-sensitive material, the arrangement of unit photosensitive layers is generally The red color-sensitive layer, the green color-sensitive layer, and the blue color-sensitive layer are installed in this order from the support side. However, depending on the purpose, the installation order may be reversed, or the installation order may be such that different photosensitive layers are sandwiched in the same color-sensitive layer. A non-photosensitive layer may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. These may contain couplers, DIR compounds, color mixing inhibitors and the like described later. Further, it may contain a compound having a property of releasing a dye in an image-like or reverse image-like manner and causing a difference in diffusibility between the released dye and the compound before release. A plurality of silver halide emulsion layers constituting each unit photosensitive layer are sequentially exposed to a support, two layers of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in DE 1,121,470 or GB 923,045. It is preferable to arrange so that the degree is low. In addition, as described in JP-A-57-112751, 62-200350, 62-206541, 62-206543, a low-sensitivity emulsion layer is provided on the side away from the support, and a high-sensitivity emulsion is provided on the side close to the support. Layers may be installed. As a specific example, from the side farthest from the support, low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH) / high sensitivity green photosensitive layer (GH) / low sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL) or BH / BL / GL / GH / RH / RL or BH / BL / GH / GL / RL / RH It can be installed in the order of. Further, as described in Japanese Patent Publication No. 55-34932, it can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Further, as described in JP-A-56-25738 and JP-A-62-63936, they can be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support. In addition, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. Examples include an arrangement composed of three layers having different sensitivities in which a low silver halide emulsion layer is arranged and the sensitivities are gradually lowered toward the support. Even in the case of being composed of three layers having different sensitivities, as described in JP-A-59-202464, in the same color-sensitive layer, the medium-sensitive emulsion layer / high They may be arranged in the order of sensitive emulsion layer / low sensitive emulsion layer. In addition, they may be arranged in the order of high sensitivity emulsion layer / low sensitivity emulsion layer / medium sensitivity emulsion layer, or low sensitivity emulsion layer / medium sensitivity emulsion layer / high sensitivity emulsion layer. Further, the arrangement may be changed as described above even when there are four or more layers. In order to improve color reproducibility, main sensitivity layers such as BL, GL, RL and spectral sensitivity distribution described in US 4,663,271, 4,705,744, 4,707,436, JP-A-62-160448, 63-89850 It is preferable to dispose a donor layer (CL) having different multi-layer effects adjacent to or close to the main photosensitive layer.

  The preferred silver halide used in the present invention is silver iodobromide, silver iodochloride, silver iodochlorobromide, silver iodobromide or silver chloride. Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedrons, tetradecahedrons, irregular crystal shapes such as spheres and plates, twin planes, etc. Those having crystal defects of the above or a composite form thereof may be used. The grain size of the silver halide may be fine grains having a diameter of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), pages 22 to 23, “I. Emulsion preparation and types”. No. 18716 (November 1979), 648, No. 307105 (November 1989), pages 863 to 865, and Grafkide, "Physics and Chemistry of Photography", published by Paul Monter Glafkides, Chemie et Phisique Photographique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographic Emulsion Chemistry, Focal Press, 1966), "Production and Coating of Photoemulsions" , Focal Press, Inc. (VLZelikman, et al., Making and Coating Photographic Emulsion, Focal Press, 1964) and the like.

  Also preferred are monodisperse emulsions described in US 3,574,628, 3,655,394 and GB 1,413,748. Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineering, Vol. 14, 248-257 (1970); US 4,434,226, 4,414,310, 4,433,048, 4,439,520 and GB. It can be easily prepared by the method described in 2,112,157. The crystal structure may be uniform, the inside and outside may be composed of different halogen compositions, or a layered structure may be formed. Silver halides having different compositions may be bonded by epitaxial bonding, and may be bonded to a compound other than silver halide, such as rhodium silver or lead oxide. A mixture of particles having various crystal forms may be used. The above emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grain, or a type having a latent image on both the surface and the inside. These emulsions may be negative emulsions or positive emulsions (so-called auto-positive emulsions). The negative emulsion may be a normal emulsion or a heat developable emulsion. Among the internal latent image types, a core / shell type internal latent image type emulsion described in JP-A-63-264740 may be used, and this preparation method is described in JP-A-59-133542. Although the thickness of the shell of this emulsion varies depending on the development processing or the like, it is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

  As the silver halide emulsion, those subjected to physical ripening, chemical ripening and spectral sensitization are usually used. Additives used in such a process are described in RD No. 17643, No. 18716 and No. 307105, and the corresponding parts are summarized in the following table. In the light-sensitive material of the present invention, two or more types of emulsions having at least one characteristic different in grain size, grain size distribution, halogen composition, grain shape, and sensitivity of a photosensitive silver halide emulsion are mixed in the same layer. Can be used. Silver halide grains fogged with the surface of grains described in US 4,082,553, US 4,626,498, silver halide grains with fogged grains described in JP-A-59-214852, colloidal silver as a photosensitive silver halide emulsion layer and It is preferred to apply to / or a substantially light-insensitive hydrophilic colloid layer. The silver halide grains fogged inside or on the surface of the grains are silver halide grains that can be developed uniformly (non-imagewise) regardless of the unexposed and exposed areas of the photosensitive material. The preparation method thereof is described in US Pat. No. 4,626,498 and JP-A-59-214852. The silver halide forming the inner core of the core / shell type silver halide grain in which the inside of the grain is fogged may have a different halogen composition. Any silver chloride, silver chlorobromide, silver iodobromide, or silver chloroiodobromide can be used as the silver halide fogged inside or on the surface of the grain. The average grain size of these fogged silver halide grains is preferably 0.01 to 0.75 μm, particularly preferably 0.05 to 0.6 μm. The grain shape may be a regular grain or a polydisperse emulsion, but it is monodisperse (at least 95% of the silver halide grain weight or number of grains has a grain size within ± 40% of the average grain size). Are preferred).

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a silver halide fine grain which is not exposed during imagewise exposure for obtaining a dye image and is not substantially developed in the developing process, and is preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as necessary. Preferably, it contains 0.5 to 10 mol% of silver iodide. The fine grain silver halide preferably has an average particle size (average value of equivalent circle diameter of projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. The fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. The surface of the silver halide grains does not need to be optically sensitized and does not require spectral sensitization. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as triazole, azaindene, benzothiazolium, mercapto compound or zinc compound in advance. This fine grain silver halide grain-containing layer can contain colloidal silver. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

Photographic additives that can be used in the present invention are also described in the RD, and the description locations related to the following table are shown.
Type of additive RD17643 RD18716 RD307105
1. Chemical sensitizer, page 23, page 648, right column, page 8662. Sensitivity increasing agent Page 648, right column 3. Spectral sensitizer, page 23-24, page 648, right column, page 866-868 Supersensitizer-page 649, right column 4. Brightener 24 pages 647 pages right column 868 pages 5. 5. Light absorber, 25-26 pages, 649, right column, page 873 Filters, -page, left page, 650 Dyes, ultraviolet absorbers Binder page 26 page 651 page left column pages 873-874 Plasticizer, page 27, page 650, right column, page 876 Lubricant 8. Coating aid, page 26-27, page 650, right column, page 875-876, surface active agent 9. Static page 27 page 650 right column pages 876-877 inhibitor
Ten. Mat agent 878-879

Various dye-forming couplers can be used in the light-sensitive material of the present invention, and the following couplers are particularly preferable.
Yellow coupler: coupler represented by formulas (I) and (II) of EP 502,424A; coupler represented by formulas (1) and (2) of EP 513,496A (especially Y-28 on page 18); A coupler represented by the general formula (I) of claim 1 of US Pat. No. 5,134,576; a coupler represented by the general formula (I) of lines 45 to 55 of column 1 of US Pat. No. 5,066,576; A coupler represented by claim 1 on page 40 of EP 498,381A1 (particularly D-35 on page 18); a coupler represented by formula (Y) on page 4 of EP 447,969A1 (particularly Y-1 (Page 17), Y-54 (page 41)); couplers represented by formulas (II) to (IV) in columns 7 to 58 of US Pat. No. 4,476,219 (particularly II-17, 19 (column 17), II -24 (column 19)).
Magenta coupler; JP-A-3-9737 (L-57 (lower right of page 11), L-68 (lower right of page 12), L-77 (lower right of page 13); EP 456,257 A-4 -63 (page 134) ), A-4 -73, -75 (page 139); M-4, -6 (page 26), M-7 (page 27) of EP 486,965; M-45 of paragraph 0024 of Japanese Patent Application No. 4-234120 M-1 in paragraph 0036 of Japanese Patent Application No. 4-36917; M-22 in paragraph 0237 of JP-A-4-362631.
Cyan coupler: CX-1,3,4,5,11,12,14,15 (pages 14-16) of JP-A-4-204843; C-7,10 (page 35) of JP-A-4-43345, 34 35 (page 37), (I-1), (I-17) (pages 42 to 43); a coupler represented by general formula (Ia) or (Ib) of claim 1 of Japanese Patent Application No. 4-236333.
Polymer coupler: P-1, P-5 (page 11) of JP-A-2-44345.

  As couplers in which the coloring dye has an appropriate diffusibility, those described in US 4,366,237, GB 2,125,570, EP 96,873B, DE 3,234,533 are preferable. A coupler for correcting the unwanted absorption of the coloring dye is a yellow colored cyan coupler represented by the formula (CI), (CII), (CIII), (CIV) described on page 5 of EP 456,257A1 (particularly, page 84). YC-86), yellow colored magenta coupler ExM-7 described in the EP (page 202), EX-1 (page 249), EX-7 (page 251), magenta colored cyan coupler CC-9 described in US 4,833,069 (Column 8), CC-13 (Column 10), US 4,837,136 (2) (Column 8), colorless masking couplers represented by formula (A) of claim 1 of WO92 / 11575 (particularly examples on pages 36 to 45) Compound) is preferred. Examples of the compounds (including couplers) that release a photographically useful compound residue by reacting with oxidized developing agent include the following. Development inhibitor releasing compounds: compounds represented by formulas (I), (II), (III) and (IV) described on page 11 of EP 378,236A1 (especially T-101 (page 30), T-104 (31 Page), T-113 (page 36), T-131 (page 45), T-144 (page 51), T-158 (page 58)), EP436, 938A2 Compounds (especially D-49 (page 51)), compounds represented by formula (1) of Japanese Patent Application No. 4-134523 (especially paragraph (23) of paragraph 0027), pages 5 to 6 of EP 440,195A2 Compounds of formula (I), (II), (III) (especially I- (1) on page 29); Bleach accelerator releasing compounds: formulas (I), (I ′) on page 5 of EP 310,125A2 (Especially (60), (61) on page 61) and the compound represented by formula (I) in claim 1 of Japanese Patent Application No. 4-325564 (especially (7) in paragraph 0022); a ligand releasing compound : Compound represented by LIG-X described in claim 1 of US 4,555,478 (especially the compound in columns 21 to 41 of column 12); Leuco dye releasing compound: Compounds 1 to 6 of columns 3 to 8 of US 4,749,641; Fluorescent dye Release compounds: US 4,774,181 Compounds represented by COUP-DYE of Lame 1 (especially compounds 1 to 11 in columns 7 to 10); development accelerators or fogging agent releasing compounds: formulas (1), (2) and (3) in column 3 of US 4,656,123 (Especially (I-22) in column 25) and ExZK-2 on page 75, lines 36 to 38 of EP 450,637A2; a compound that releases a group that becomes a dye only after leaving: Claim 1 of US 4,857,447 A compound represented by formula (I): (especially Y-1 to Y-19 in columns 25 to 36).

As additives other than couplers, the following are preferable.
Oil-soluble organic compound dispersion medium: JP-A 62-215272, P-3, 5, 16, 19, 25, 30, 42, 49, 54, 55, 66, 81, 85, 86, 93 (140-144) Page); Latex for impregnation of oil-soluble organic compound: Latex described in US Pat. No. 4,199,363; Oxidant scavenger for developing agent: Compound represented by formula (I) in columns 54 to 62 of US Pat. No. 4,978,606 (particularly I-, (1), (2), (6), (12) (columns 4-5), US 4,923,787, column 2, line 5-10 (especially compound 1 (column 3); stain inhibitor: EP 298321A Page 4, lines 30 to 33, formulas (I) to (III), especially I-47,72, III-1,27 (pages 24 to 48); antifading agent: A-6,7,20, EP 298321A 21, 23, 24, 25, 26, 30, 37, 40, 42, 48, 63, 90, 92, 94, 164 (pages 69 to 118), US 5, 122, 444, columns 25 to 38 II-1 to III-23 , Especially III-10, EP 471347A, pages 8-12, I-1 to III-4, especially II-2, US 5,139,931, columns 32 to 40, A-1 to 48, especially A-39, 42; color enhancement Materials that reduce the amount of agents or color mixing inhibitors used: EP 411324A, pages 5-24, I-1 to II-15, especially I-46; formalin scavenger: EP 4 77932A, pages 24 to 29, SCV-1 to 28, especially SCV-8; hardeners: JP-A 1-214845, page 17, H-1,4,6,8,14, US 4,618,573, columns 13 to 23 Compounds represented by formulas (VII) to (XII) (H-1 to 54), compounds represented by formula (6) at the lower right of page 8 of JP-A-2-148852, particularly H -14, US 3,325,287 claim 1; Development inhibitor precursor: JP-A 62-168139, P-24, 37, 39 (pages 6-7); US 5,019,492 claim 1, especially Column 7, 28, 29; preservative, antifungal agent: US 4,923,790, columns 3-15, I-1 to III-43, especially II-1, 9, 10, 18, III-25; stabilizer, antifogging Agent: US 4,923,793 columns 6-16 I-1 to (14), especially I-1,60, (2), (13), US 4,952,483 columns 25 to 32 compounds 1 to 65, especially 36: Chemical Sensitizer: Triphenylphosphine selenide, compound 50 of JP-A-5-40324; Dye: a-1 to b-20 on pages 15 to 18 of JP-A-3-156450, especially a-1,12,18,27, 35, 36, b-5, pages 27 to 29, V-1 to 23, especially V-1, EP 445627A, pages 33 to 55, FI-1 to F-II-43, especially FI-11, F-II -8 EP 457153A, pp. 17-28, III-1-36, especially III-1,3, WO 88/04794, 8-26, Dye-1-124, microcrystalline dispersion, EP 319999A, pp. 6-11 Compounds 1-22, especially compounds 1, EP 519306A, compounds D-1 to 87 represented by formulas (1) to (3) (pages 3 to 28), US 4,268,622 compounds 1 to 22 represented by formula (I) (Columns 3 to 10), compounds (1) to (31) (columns 2 to 9) represented by formula (I) of US 4,923,788; UV absorber: represented by formula (1) of JP-A-46-3335 Compounds (18b) to (18r), 101 to 427 (pages 6 to 9), compounds (3) to (66) (pages 10 to 44) represented by formula (I) and formula (III) of EP 520938A Compounds HBT-1 to 10 (page 14), compounds (1) to (31) represented by formula (1) of EP 521823A (columns 2 to 9).

Suitable supports that can be used in the present invention include, for example, the RD. No. 17643, page 28, No. 18716, page 647, right column to page 648, left column, and No. 307105, page 879. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the side having an emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, still more preferably 18 μm or less, and particularly preferably 16 μm or less. The membrane swelling speed T _1/2 is preferably 30 seconds or less, and more preferably 20 seconds or less. T _1/2 is the color developer at 30 ° C., 3 minutes when the saturation film thickness of 90% of the maximum swollen film thickness reached when treated for 15 seconds, the time until the film thickness reaches half thereof It is defined as The film thickness means the film thickness measured at 25 ° C and 55% relative humidity (2 days), and T _1/2 is photographic science and engineering by A.Green et al. (Photogr. Sci. Eng.), 19 卷, 2, 124-129, can be measured by using a type of spherometer (swelling meter). T _1/2 can be adjusted by adding a hardener to gelatin as a binder or changing the aging conditions after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness) / film thickness. In the light-sensitive material of the present invention, a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 to 20 μm is preferably provided on the side opposite to the side having the emulsion layer. This back layer preferably contains the aforementioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surfactant. The swelling rate of this back layer is preferably 150 to 500%.

  The light-sensitive material of the present invention has the RD. No. 17643, pages 28 to 29, No. 18716, page 651, left column to right column, and No. 307105, page 880 to 881. The color developer used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly composed of an aromatic primary amine color developing agent. As this color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples and preferred examples thereof are compounds described in EP 556700A, page 28, lines 43 to 52. Is mentioned. These compounds may be used in combination of two or more depending on the purpose. Color developers are pH buffers such as alkali metal carbonates, borates or phosphates, developers such as chloride salts, bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. In general, an inhibitor or an antifoggant is included. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting Various chelating agents such as ethylenepolytetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanedia Tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, Add ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof.

When reversing is performed, color development is usually performed after black and white development. In this black and white developer, known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone. Or they can be used in combination. The pH of these color developers and black-and-white developers is generally 9-12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of light-sensitive material, and can be reduced to 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also When reducing the replenishment amount, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the treatment tank with air. The processing effect of the contact between the photographic processing solution and air in the processing tank can be evaluated by the aperture ratio (= [contact area between processing solution and air cm ² ] ÷ [processing solution capacity cm ³ ]). The aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method for reducing the aperture ratio, in addition to providing a floating lid or other shielding object on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033, JP-A-63-216050 Mention may be made of the slit development processing methods described. The aperture ratio is preferably reduced not only in both color development and black-and-white development, but also in subsequent steps such as bleaching, bleach-fixing, fixing, washing, and stabilization. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer. The color development processing time is usually set between 2 and 5 minutes, but the processing time can be further shortened by setting the temperature and pH to high and using the color developing agent at a high concentration.

  The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleaching and fixing process) or may be performed individually. Further, in order to speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further, depending on the purpose, it is possible to carry out processing in two continuous baths for bleach-fixing, fixing processing before bleach-fixing processing, or bleaching processing after bleach-fixing processing. As the bleaching agent, for example, polyvalent metal compounds such as iron (III), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents include organic complex salts of iron (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, and other amino acids. Polycarboxylic acids or complex salts such as citric acid, tartaric acid and malic acid can be used. Of these, iron (III) complex salts of aminopolycarboxylic acids such as iron (III) complex salts of ethylenediaminetetraacetic acid and 1,3-diaminopropanetetraacetic acid are preferred from the viewpoint of rapid processing and prevention of environmental pollution. . Furthermore, aminopolycarboxylic acid iron (III) complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions. The pH of the bleaching solution or bleach-fixing solution using these iron (III) complex salts of aminopolycarboxylic acid is usually 4.0 to 8, but it can also be processed at a lower pH in order to speed up the processing.

  A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution, and their pre-bath, if necessary. Specific examples of useful bleach accelerators are described in the following specification: US 3,893,858, DE 1,290,812, 2,059,988, JP-A-53-32736, 53-57831, 53-37418, 53-72623. 53-95630, 53-95631, 53-104232, 53-124424, 53-141623, 53-28426, RD No. 17129 (July 1978). Compound: Thiazolidine derivative described in JP-A-50-140129; Thiourea derivative described in JP-B-45-8506, JP-A-52-20832, 53-32735, US 3,706,561; DE 1,127,715, JP-A-58-16,235 The iodide salts described in DE 966,410 and 2,748,430; the polyamine compounds described in JP-B-45-8836; and other JP-A-49-40,943, 49-59,644, 53-94,927, Compounds described in 54-35,727, 55-26,506, 58-163,940; bromide ions can be used. Of these, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and the compounds described in US 3,893,858, DE 1,290,812 and JP-A-53-95,630 are particularly preferable. Furthermore, the compounds described in US 4,552,834 are also preferred. These bleach accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when a color light-sensitive material for photography is bleach-fixed. In addition to the above compounds, the bleaching solution or the bleach-fixing solution preferably contains an organic acid for the purpose of preventing bleaching stains. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, and specifically, acetic acid, propionic acid, hydroxyacetic acid and the like are preferred. Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts. However, the use of thiosulfates is common. In particular, ammonium thiosulfate is most widely used. A combination of thiosulfate and thiocyanate, a thioether compound, or thiourea is also preferable. As a preservative for the fixing solution or bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in EP 294769A are preferred. Further, aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution. In the present invention, the fixing solution or bleach-fixing solution contains a compound having a pKa of 6.0 to 9.0 for pH adjustment, preferably an imidazole such as imidazole, 1-methylimidazole, 1-ethylimidazole, 2-methylimidazole. It is preferable to add 0.1 to 10 mol per liter.

  The total desilvering time is preferably as short as possible without causing desilvering failure. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. The treatment temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferred temperature range, the desilvering rate is improved and the occurrence of stain after the treatment is effectively prevented. In the desilvering step, it is preferable that the stirring is strengthened as much as possible. Specific methods for strengthening stirring include the method of causing a jet of a processing solution to collide with the emulsion surface of a light-sensitive material described in JP-A-62-183460 and the effect of stirring using a rotating means of JP-A-62-183461. A method of increasing the agitation effect by moving the photosensitive material while bringing the wiper blade in the solution into contact with the emulsion surface and making the emulsion surface turbulent, and the circulation flow rate of the entire processing solution. The method of increasing is mentioned. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution, and the fixing solution. The improvement in stirring is thought to speed up the supply of the bleaching agent and the fixing agent into the emulsion film, and as a result, increase the desilvering rate. Further, the above stirring improving means is more effective when a bleaching accelerator is used, and the acceleration effect can be remarkably increased or the fixing inhibiting action by the bleaching accelerator can be eliminated. The automatic developing machine used for the light-sensitive material of the present invention preferably has the light-sensitive material conveying means described in JP-A-60-191257, JP-A-60-191258 and JP-A-60-191259. As described in the above-mentioned JP-A-60-191257, such a conveying means can remarkably reduce the carry-in of the treatment liquid from the pre-bath to the post-bath, and is highly effective in preventing deterioration of the performance of the treatment liquid. This is particularly effective for shortening the processing time and reducing the replenishment amount of the processing liquid.

  In general, the light-sensitive material of the present invention undergoes a washing and / or stabilization process after desilvering. The amount of water to be washed in the washing process depends on the characteristics of the photosensitive material (for example, depending on the material used such as coupler), the usage, the washing water temperature, the number of washing tanks (the number of washing tanks), the replenishment method such as countercurrent and forward flow, and various other conditions Can be set widely. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method should be determined by the method described in Journal of the Society of Motion Picture and Television Engineers Vol. 64, pages 248-253 (May 1955). Can do. According to the multi-stage countercurrent system described in this document, the amount of water to be washed can be significantly reduced. However, bacteria increase due to an increase in the residence time of water in the tank, and the generated suspended matter adheres to the photosensitive material. Problem arises. As a solution to this problem, the method of reducing calcium ions and magnesium ions described in JP-A-62-288,838 is extremely effective. In addition, isothiazolone compounds described in JP-A-57-8,542, siabendazoles, chlorinated fungicides such as sodium chlorinated isocyanurate, other benzotriazoles, Hiroshi Horiguchi, “Chemistry of Antifungal and Antifungal Agents” ( 1986) Sankyo Publishing, Sanitary Technology Association edited by “Microbial Sterilization, Sterilization, and Antifungal Technology” (1982) Industrial Technology Association, Japanese Society for Antibacterial and Antifungal Studies, “Environmental Antifungal Agent” (1986) It is also possible to use a bactericidal agent. The pH of the washing water in the processing of the light-sensitive material of the present invention is 4 to 9, preferably 5 to 8. The washing water temperature and washing time can also be set depending on the characteristics and application of the photosensitive material. In general, the range of 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C. for 30 seconds to 5 minutes is selected. . Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the water washing. In such stabilization treatment, known methods described in JP-A-57-8543, 58-14834 and 60-220345 can be applied. In addition, there may be a further stabilization treatment following the water washing treatment, and examples thereof include a stabilization bath containing a dye stabilizer and a surfactant used as a final bath of a color photographic material for photographing. Can do. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and fungicides can also be added to the stabilizing bath.

  The overflow liquid accompanying the washing with water and / or the replenishment of the stabilizing liquid can be reused in other processes such as a desilvering process. In the processing using an automatic developing machine or the like, when each processing solution is concentrated by evaporation, it is preferable to correct the concentration by adding water. The light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing. In order to incorporate it, it is preferable to use a precursor of a color developing agent. For example, an indoaniline compound described in US 3,342,597, 3,342,599, Schiff base type compound described in Research Disclosure No. 14,850 and No. 15,159, an aldol compound described in 13,924, a metal salt complex described in US 3,719,492, Mention may be made of the urethane compounds described in 53-135628. The light-sensitive material of the present invention may incorporate various 1-phenyl-3-pyrazolidones for the purpose of accelerating color development, if necessary. Typical compounds are described in JP-A-56-64339, 57-144547, and 58-115438. The processing solution used for processing the light-sensitive material of the present invention is used at 10 ° C to 50 ° C. Usually, temperatures between 33 ° C and 38 ° C are standard, but higher temperatures can accelerate processing and shorten processing time, or conversely, lower temperatures can improve image quality and stability of processing solutions. it can.

  There are no particular limitations on various additives, development processing methods, and the like used when the present invention is applied to a black-and-white photosensitive material. For example, JP-A Nos. 2-68539, 5-11389, and 2- The following corresponding part of 58041 can be preferably used.

1. Silver halide emulsion and production method thereof: JP-A-2-68539, page 8, lower right column, line 6 to line 10, page 10, upper right column, line 12.
2. Chemical sensitization method: Selenium sensitization method described in JP-A-5-11389, page 10, upper right column, line 13 to lower left column, line 16;
3. Antifoggant / stabilizer: JP-A-2-68539, page 10, lower left column, line 17 to page 11, upper left column, line 7 and page 3, lower left column, line 2 to page 4, lower left column of page 4.
4). Spectral sensitizing dye: page 4, lower right column, line 4 to page 8, lower right column and JP-A-2-58041, page 12, left lower column, line 8 to right lower column, line 19.
5). Surfactant and antistatic agent: JP-A-2-68539, page 11, upper left column, line 14 to page 12, upper left column, line 9 and JP-A-2-58041, page 2, lower left column, lines 14 to 5th page, 12th line.
6). Matting agent / plasticizer / sliding agent: page 12, upper left column, line 10 to upper right column, line 10 and JP-A-2-58041, page 5, lower left column, line 13 to page 10, lower left column, line 3 Eye.
7). Hydrophilic colloid: JP-A-2-68539, page 12, upper right column, line 11 to same lower left column, line 16.
8). Hardening agent: page 12, lower left column, line 17 to page 13, upper right column, line 6.
9. Development method: page 15, upper left column, line 14 to lower left column, line 13.

  In addition to the above, the present invention can be applied to diffusion transfer photography, so-called instant photography. An example of this diffusion transfer photograph is described in JP-A-5-297544. The present invention can also be used for a photothermographic material. The photothermographic material that can be used in the present invention may form a monochrome image or a color image. For example, JP-A-60-162251, JP-A-64-13546, JP-A-1-161236, US Patents 4,474,867, 4,478,927, 4,507,380, 4,500,626, 4,483,914, 4,783,396, 4,740,445, JP-A-59-231539, 60-2950, etc. Examples of the heat-developable photosensitive material described can be given. Further, the present invention can be used for a wet reversal color copy material using an autopositive emulsion. This material is described in Sample No. 101 of Example 1 of JP-A-3-125530 and Sample No. 1 of JP-A-2-90145.

  Hereinafter, a silver halide photosensitive material for color diffusion transfer to which the present invention can be applied will be described. The light-sensitive material used in the present invention basically has a light-sensitive silver halide, a binder and a dye-donating compound (sometimes serving as a reducing agent) on a support. These components are often added to the same layer, but can be added separately in separate layers as long as they can react. For example, when a colored dye-donating compound is present in the lower layer of a silver halide emulsion, the sensitivity can be prevented from decreasing.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors of yellow, magenta and cyan, at least three silver halide emulsion layers having sensitivity in different spectral regions are used in combination. For example, a combination of three layers of blue-sensitive layer, green-sensitive layer, and red-sensitive layer, a combination of green-sensitive layer, red-sensitive layer, and infrared-sensitive layer, or a combination of red-sensitive layer, first infrared layer, and second infrared layer and so on. Each light-sensitive layer can take various arrangement orders known for conventional color light-sensitive materials. Each of these photosensitive layers may be divided into two or more layers as necessary. The photothermographic material may be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer, and a back layer.
(Basic composition and preparation method of silver halide grains)
The silver halide which can be used in the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver iodochloride and silver chloroiodobromide, but preferably 30 mol% or less. Silver iodobromide, silver chloride, silver bromide and silver chlorobromide containing silver iodide. The silver halide emulsion used in the present invention may be a surface latent image type or an internal latent image type. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent and optical fogging. Also, so-called multi-structure particles having different halogen compositions in the inside of the particle and on the surface of the particle may be used. Of the multi-structure grains, those having a double structure are sometimes called core-shell emulsions.

  The silver halide used in the present invention is preferably a multi-structure grain, and a core-shell emulsion is more preferred. However, the present invention is not limited to this. The silver halide emulsion used in the present invention is preferably a monodispersed emulsion, and the variation coefficient described in JP-A-3-110555 is preferably 20% or less. More preferably, it is 16% or less, More preferably, it is 10% or less. However, the present invention is not limited to this monodispersed emulsion.

  The average grain size of the silver halide grains used in the present invention is 0.1 μm to 2.2 μm, preferably 0.1 μm to 1.2 μm. The crystal habit of the silver halide grains may be any of a cubic shape, an octahedron shape, a high aspect ratio flat plate shape, a potato shape, and the like. More preferred is a cubic emulsion.

  Specifically, halogens described in US Pat. No. 4,500,266, column 50, US Pat. No. 4,628,021, Journal of Research Disclosure (hereinafter abbreviated as RD) 17029 (1978), Japanese Patent Application Laid-Open No. Sho 62-25159, and the like. Any silver halide emulsion can be used.

  In the process of preparing the silver halide emulsion of the present invention, in the case of performing a so-called desalting step for removing excess salt, a long-known Nudell water washing method in which gelatin is gelatinized as a means for this is used. Inorganic salts consisting of polyvalent anions such as sodium sulfate, anionic surfactants, anionic polymers (eg polystyrene sulfonic acid), or gelatin derivatives (eg aliphatic acylated gelatin, aromatic acylated gelatin) Alternatively, a precipitation method (flocculation) using aromatic carbamoylated gelatin or the like may be used. Preferably, a precipitation method using a compound represented by a precipitating agent (a) or a precipitating agent (b) described later is used, but the present invention is not limited thereto. The above precipitating agent is not used at all, and an ultrafiltration method may be used. The removal of excess salt may be omitted.

The silver halide emulsion used in the present invention may contain heavy metals such as iridium, rhodium, platinum, cadmium, zinc, thallium, lead, iron and chromium for various purposes. These compounds may be used alone or in combination of two or more. The amount added depends on the purpose of use, but is generally about 10 ^-9 to 10 ^-3 mole per mole of silver halide. Moreover, when making it contain, you may put in a particle | grain uniformly and you may make it local on the surface and inside of a particle | grain.

The preferable amount of iridium used in the present invention is 10 ⁻⁹ to 10 ⁻⁴ mol, and more preferably 10 ⁻⁸ to 10 ⁻⁶ mol, per mol of silver halide. In the case of a core-shell emulsion, iridium may be added to the core and / or shell. As the compound, K ₂ IrCl ₆ or K ₃ IrCl ₆ is preferably used.

Moreover, the preferable addition amount of rhodium used in the present invention is 10 ⁻⁹ to 10 ⁻⁶ mol per mol of silver halide. Moreover, the preferable addition amount of iron used in the present invention is 10 ⁻⁷ to 10 ⁻³ mol, more preferably 10 ⁻⁶ to 10 ⁻³ mol, per mol of silver halide. The surface of the silver halide emulsion is obtained by previously doping a part or all of these heavy metals into a fine grain emulsion of silver chloride, silver chlorobromide, silver bromide, silver iodobromide and the like and then adding this fine grain emulsion. A method of locally doping is also preferably used. In the step of forming silver halide grains, a rhodan salt, NH ₃ and a tetrasubstituted thioether compound as shown by the compound (a) described later, an organic thioether derivative described in JP-B-47-11386, or JP Sulfur-containing compounds described in JP-A-53-144319 can be used. Nitrogen-containing compounds as described in JP-B-46-7781, JP-A-60-222842, JP-A-60-122935 and the like can be added at the stage of forming silver halide grains. As a protective colloid used in the preparation of the emulsion of the present invention and as a binder for other hydrophilic colloid, gelatin is advantageously used, but hydrophilic colloid can also be used. For example, gelatin derivatives, gelatin and other polymer graft polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose and cellulose sulfates; sodium alginate, starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetals, poly A variety of synthetic hydrophilic polymer materials such as mono- or copolymers such as -N-vinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, and polyvinyl pyrazole can be used.

  Gelatin is described in lime-processed gelatin, acid-processed gelatin, bulletin, Society of the Scientific, Photography of Japan (Bull.Soc.Sci.Phot., Japan), No. 16: Page 30 (1966). An enzyme-treated gelatin as described above may be used, and a hydrolyzate or enzyme-decomposed product of gelatin can also be used.

  For other conditions, P. Glafkides, "Chemie et Physique Photographique" (published by Paul Montel, 1697), GF Duffin (GFDuffin), "Photo "Graphic Emulsion Chemistry" (published by The Focal Press, 1966), VLZelikman et al, "Making and Coating Photographic Emulsion" (The Focal Press, 1964) may be referred to. That is, any of an acidic method, a neutral method, and an ammonia method may be used, and any one of a one-side mixing method, a simultaneous mixing method, and a combination thereof may be used as a form for reacting a soluble silver salt and a soluble halogen salt.

  A method (so-called back mixing method) in which grains are formed in the presence of excess silver ions can also be used. As one type of the simultaneous mixing method, a method in which pAg in a liquid phase in which silver halide is generated is kept constant, a so-called controlled double jet method can be used.

  In addition, in order to accelerate grain growth, the addition concentration, addition amount or addition rate of silver salt and halogen salt to be added may be increased (Japanese Patent Laid-Open Nos. 55-142329, 55-158124, US Pat. No. 3,650,757). etc).

  During or after the grain formation, the surface of the silver halide grain may be substituted with a halogen that forms a hardly soluble silver halide grain.

  Furthermore, the stirring method of the reaction solution may be any known stirring method. The temperature and pH of the reaction solution during the formation of silver halide grains may be set in any way. The preferred pH range is 2.2 to 6.0, more preferably 3.0 to 5.5.

  The blue-sensitive layer emulsion used in the present invention is described in Japanese Patent Application No. 3-308225. A silver halide emulsion comprising silver halide grains having a layer having a high silver iodide content on the grain surface and chemically sensitized before desalting and addition of iodine ions is particularly preferred.

(Method of adding sensitizing dye)
The method for adding the sensitizing dye may be basically any time. That is, at the beginning of the formation of silver halide emulsion grains (may be added before nucleation), during or after formation, or at the beginning, during or after the desalting step, at the time of redispersion of gelatin, Before, during or after chemical sensitization, or during preparation of a coating solution. Preferably, it is added during and after the formation of silver halide grains, or before and after chemical sensitization. Addition after chemical sensitization means adding a sensitizing dye after all chemicals necessary for chemical sensitization have been added.

  As described in US Pat. No. 4,183,756, it may be present in a reaction system of a soluble silver salt (for example, silver nitrate) and a halide (for example, potassium bromide) before the silver halide grains are formed. As described in Japanese Patent No. 4225666, it may be present in the reaction system after the nucleation of silver halide grains and before the completion of the silver halide grain formation step. A sensitizing dye may be present in the reaction solution simultaneously with the formation of silver halide grains, that is, at the same time when the silver salt and halide are mixed. It is superior in storage stability under high temperature conditions and gradation.

  The concentration of the additive solution, the solvent, the addition time (can be added all at once or over time), temperature, pH, etc. may be any conditions. Moreover, either liquid level addition or in-liquid addition may be sufficient. These conditions are described in detail in JP-A-3-110555.

(Type of sensitizing dye)
The sensitizing dyes used in the emulsions used in the present invention include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.

  Specific examples include sensitizing dyes described in U.S. Pat. No. 4,617,257, JP-A-59-180550, JP-A-60-140335, RD17029 (1978), pages 12-13.

  These sensitizing dyes may be used alone or in combination. The combination of sensitizing dyes is often used for the purpose of supersensitization.

  Along with the sensitizing dye, a dye which itself does not have spectral sensitizing action or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. No. 3,615,641). And those described in JP-A-63-23145).

  In the present invention, in any of the above addition methods, the total addition amount of the sensitizing dye may be added at once, or may be added in several divided portions. Further, a sensitizing dye may be added in the form of a mixture with a soluble silver salt and / or halide.

  The sensitizing dye may be added after being dissolved in water or an organic solvent that is compatible with water such as methanol, ethanol, propanol, fluorinated alcohol, methyl cellosolve, dimethylformamide, acetone or the like. Two or more of the above may be used in combination. Alternatively, it may be added in the form of a dispersion in a water / gelatin dispersion or in the form of a freeze-dried powder. Further, it may be added in the form of powder or solution dispersed using a surfactant.

  The sensitizing dye used in the emulsion of the present invention may be, for example, those described in JP-A-3-296745 and JP-A-4-31854.

  The amount of the sensitizing dye used is suitably 0.001 to 20 g, preferably 0.01 to 2 g, per 100 g of silver used in the emulsion production.

(Chemical sensitization)
The silver halide emulsion used in the present invention can be used without being chemically sensitized but is preferably chemically sensitized to increase the sensitivity. Chemical sensitization may be sulfur sensitization, gold sensitization, reduction sensitization, or a combination thereof.

  In addition, chemical sensitization with a compound containing a chalcogen element other than sulfur such as selenium or tellurium, or chemical sensitization with a noble metal such as palladium or iridium may be combined with the above chemical sensitization.

A method of adding an inhibitor such as a nitrogen-containing heterocyclic compound typified by 4-hydroxy-6-methyl- (1,3,3a, 7) -tetraazaindene is also preferably used. A preferable range of the addition amount is 10 ^-1 to 10 ^-5 mol per mol of silver halide.

  The pH during chemical sensitization is preferably 5.3 to 10.5, more preferably 5.5 to 9.5.

  The sulfur sensitizer is a compound containing sulfur that can react with active gelatin or silver, for example, thiosulfate, allylthiocarbamide, thiourea, allyl isothiocyanate, cystine, p-toluenethiosulfonic acid, rhodan, Mercapto compounds are used. In addition, those described in US Pat. Nos. 1,574,944, 2,410,689, 2,278,947, 2,728,668, 3,656,955, and the like can also be used.

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg / m ^{2 to} 10 g / m ² in terms of silver.

The silver halide emulsion may be used as it is, but is usually used after chemical sensitization. Known emulsions for light-sensitive materials can be used alone or in combination with known sulfur sensitization, reduction sensitization, noble metal sensitization and selenium sensitization. Such chemical sensitization can also be performed in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Laid-Open No. 62-253159). The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

  When the present invention is applied to a photothermographic material, an organic metal salt can be used as an oxidizing agent together with the photosensitive silver halide. Among such organic metal salts, an organic silver salt is particularly preferably used.

  Organic compounds that can be used to form the organic silver salt oxidizing agent include benzotriazoles, fatty acids and other compounds described in US Pat. No. 4,500,626, columns 52-53. Also useful are silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in JP-A-60-113235, and acetylene silver described in JP-A-61-249044. Two or more organic silver salts may be used in combination.

The above organic silver salt may be used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per mol of photosensitive silver halide. The total coating amount of photosensitive silver halide and organic silver salt is suitably 50 mg to 10 g / m ² in terms of silver.

  In the present invention, various antifoggants or photographic stabilizers can be used. Examples thereof include azoles and azaindenes described on pages 24 to 25 of RD17643 (1978), nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-168442, or JP-A-59-111636. Mercapto compounds and metal salts thereof, and acetylene compounds described in JP-A-62-87957 are used.

A hydrophilic material is preferably used for the binder of the constituent layers of the light-sensitive material and the dye-fixing element. Examples thereof include those described on pages (26) to (28) of JP-A-62-253159. Specifically, a transparent or translucent hydrophilic binder is preferable, for example, proteins such as gelatin and gelatin derivatives, cellulose derivatives, natural compounds such as polysaccharides such as starch, gum arabic, dextran and pullulan, polyvinyl alcohol, Examples include polyvinyl pyrrolidone, acrylamide polymer, and other synthetic polymer compounds. Further, a superabsorbent polymer described in JP-A-62-245260, that is, a homopolymer of a vinyl monomer having —COOM or —SO ₃ M (M is a hydrogen atom or an alkali metal) (For example, sodium methacrylate, ammonium methacrylate, Sumikagel L-5H manufactured by Sumitomo Chemical Co., Ltd.). Two or more of these binders can be used in combination.

In the case of employing a system in which a very small amount of water is supplied for thermal development, it is possible to quickly absorb water by using the above super absorbent polymer. In addition, when a superabsorbent polymer is used in the dye fixing layer or its protective layer, it is possible to prevent the dye from being retransferred from the dye fixing element to another after transfer. In the present invention, the coating amount of the binder is preferably 20 g or less per 1 m ² , particularly 10 g or less, more preferably 7 g or less.

  Various layers of the photosensitive material or dye-fixing element (including the back layer) have various polymers for the purpose of improving film physical properties such as dimensional stabilization, curling prevention, adhesion prevention, film cracking prevention, and pressure increase / decrease prevention. Latex can be included. Specifically, any of polymer latexes described in JP-A Nos. 62-245258, 62-136648, and 62-110066 can be used. In particular, if a polymer latex having a low glass transition point (40 ° C. or lower) is used for the mordanting layer, cracking of the mordanting layer can be prevented, and if a polymer latex having a high glass transition point is used for the back layer, an anti-curling effect can be obtained. can get.

  As the reducing agent used in the present invention, those known in the field of photosensitive materials can be used. Moreover, the dye-donating compound which has the reducing property mentioned later is also contained (in this case, another reducing agent can also be used together). In addition, a reducing agent precursor that does not itself have a reducing property but develops a reducing property by the action of a nucleophile or heat during the development process can also be used.

  Examples of the reducing agent used in the present invention include U.S. Pat. No. 4,500,626, columns 49-50, 4,483,914, columns 30-31, 4,330,617, 4,590,152, JP-A-60-140335, pages (17)-(18), 57-40245, 56-138736, 59-178458, 59-53831, 59-182449, 59-182450, 60-119555, 60-128436 to 60-128439, 60-198540, 60-181742, 61-259253, Nos. 62-244404, 62-131253 to 62-131256, and European Patent No. 220,746A2, pages 78-96, etc. There is Kasa.

  Combinations of various reducing agents such as those disclosed in US Pat. No. 3,039,869 can also be used.

  When a diffusion-resistant reducing agent is used, an electron transfer agent and / or electron transfer agent is used as necessary to promote electron transfer between the diffusion-resistant reducing agent and the developable silver halide. A precursor can be used in combination.

  The electron transfer agent or its precursor can be selected from the above-mentioned reducing agents or their precursors. It is desirable that the electron transfer agent or its precursor has a higher mobility than the non-diffusible reducing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols.

  The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent is not particularly limited as long as it does not substantially move in the layer of the photosensitive material among the reducing agents described above, preferably hydroquinones, Examples thereof include sulfonamidophenols, sulfonamidonaphthols, compounds described as electron donors in JP-A No. 53-110827, and dye-donating compounds having resistance to diffusion and reduction described later.

  In the present invention, the reducing agent is added in an amount of 0.01 to 20 mol, particularly preferably 0.1 to 10 mol, per mol of silver.

  In the present invention, when a silver ion is reduced to silver under a high temperature condition, a compound that generates or releases a mobile dye corresponding to this reaction or in reverse reaction, that is, a dye-donating compound is added. Contain.

Examples of dye-donating compounds other than formulas (I) and (II) that can be used in the present invention can be represented by the following general formula [LI].
(Dye-G) q-Y [LI]
Dye represents a dye group, a dye group temporarily short-waved or a dye precursor group (particularly one that gives magenta or cyan color), and q, G, and Y are synonymous with q, G, and Y in formula (II). It is.

  Hydrophobic additives such as dye-donating compounds and diffusion-resistant reducing agents can be introduced into the layer of the light-sensitive material by a known method such as the method described in US Pat. No. 2,322,027. In this case, JP-A-59-83154, 59-178451, 59-178452, 59-178453, 59-178454, 59-178455, 59-178457, etc. The high boiling point organic solvent as described can be used in combination with a low boiling point organic solvent having a boiling point of 50 ° C. to 160 ° C., if necessary.

  The amount of the high-boiling organic solvent is 10 g or less, preferably 5 g or less, based on 1 g of the dye-donating compound used. Further, 1 cc or less, further 0.5 cc or less, particularly 0.3 cc or less is appropriate for 1 g of binder.

  A dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943 can also be used.

  In the case of a compound that is substantially insoluble in water, it can be dispersed and contained as fine particles in a binder other than the above method.

  In dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, those listed as surfactants on pages (37) to (38) of JP-A-59-157636 can be used.

  In the present invention, a compound capable of stabilizing the image simultaneously with activation of development can be used in the photosensitive material. Specific compounds preferably used are described in columns 51 to 52 of US Pat. No. 4,500,626.

  In the present invention, a non-diffusible filter dye can be contained for the purpose of improving the sharpness. If necessary, a filter dye having absorption in the infrared region can be used. Details of such filter dyes are described in Japanese Patent Application Nos. 2-137855, 4-217243, 4-276744, and 5-45834.

  In a system for forming an image by diffusion transfer of a dye, a dye fixing element is used together with a photosensitive material. The dye fixing element may be separately coated on a support separate from the photosensitive material or may be coated on the same support as the photosensitive material. The relationship described in column 57 of US Pat. No. 4,500,626 can be applied to the present application as the relationship between the light-sensitive material and the dye-fixing element, the relationship with the support, and the relationship with the white reflective layer.

  The dye-fixing element preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used. Specific examples thereof include U.S. Pat. No. 4,500,626, columns 58 to 59 and JP-A-61-88256, pages (32) to (41). And mordants described in JP-A-62-244043 and JP-A-62-244036. Further, a dye-accepting polymer compound as described in US Pat. No. 4,463,079 may be used.

  The dye fixing element may be provided with auxiliary layers such as a protective layer, a release layer, and an anti-curl layer as necessary. In particular, it is useful to provide a protective layer.

A hydrophilic material is preferably used for the binder of the constituent layers of the light-sensitive material and the dye-fixing element. Examples thereof include those described in JP-A-62-253159, pages (26) to (28). Specifically, a transparent or translucent hydrophilic binder is preferable, for example, proteins such as gelatin and gelatin derivatives, cellulose derivatives, natural compounds such as polysaccharides such as starch, gum arabic, dextran and pullulan, polyvinyl alcohol, Examples include polyvinyl pyrrolidone, acrylamide polymer, and other synthetic polymer compounds. Further, a superabsorbent polymer described in JP-A-62-245260, that is, a homopolymer of a vinyl monomer having —COOM or —SO ₃ M (M is a hydrogen atom or an alkali metal) (For example, sodium methacrylate, ammonium methacrylate, Sumikagel L-5H manufactured by Sumitomo Chemical Co., Ltd.). Two or more of these binders can be used in combination.

  In the case of employing a system in which a very small amount of water is supplied for thermal development, it is possible to quickly absorb water by using the superabsorbent polymer described above. In addition, when a superabsorbent polymer is used in the dye fixing layer or its protective layer, it is possible to prevent the dye from being retransferred from the dye fixing element to another after transfer.

In the present invention, the coating amount of the binder is preferably 20 g or less per 1 m ² , particularly 10 g or less, more preferably 7 g or less.

  In the constituent layers of the light-sensitive material and the dye-fixing element, a high-boiling organic solvent can be used as a plasticizer, a sliding agent, or a peelability improving agent between the light-sensitive material and the dye-fixing element. Specific examples include those described in JP-A-62-253159, page (25), JP-A-62-245253, and the like. Furthermore, for the above purpose, various silicone oils (all silicone oils from dimethyl silicone oil to modified silicone oil in which various organic groups are introduced into dimethylsiloxane) can be used. For example, various modified silicone oils described in “Modified Silicone Oil” technical data P6-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name: X-22-3710) are effective. Silicone oils described in JP-A-62-215953 and JP-A-63-46449 are also effective.

  An anti-fading agent may be used for the light-sensitive material and the dye-fixing element. Examples of the anti-fading agent include an antioxidant, an ultraviolet absorber, and a certain metal complex. Examples of the antioxidant include a chroman compound, a coumaran compound, a phenol compound (for example, hindered phenols), a hydroquinone derivative, a hindered amine derivative, and a spiroindane compound. In addition, compounds described in JP-A 61-159644 are also effective.

  Examples of ultraviolet absorbers include benzotriazole compounds (US Pat. No. 3,533,794, etc.), 4-thiazolidone compounds (US Pat. No. 3,352,681 etc.), benzophenone compounds (Japanese Patent Laid-Open No. Sho 46- 2784, etc.) and other compounds described in JP-A Nos. 54-48535, 62-136641, 61-88256, and the like. Further, an ultraviolet absorbing polymer described in JP-A-62-260152 is also effective.

  As the metal complex, U.S. Pat. Nos. 4,241,155, 4,245,018, columns 3-36, 4,254,195, columns 3-8, JP-A-62-174741, 61-88256 (27)-(29), 63-199248, JP-A-1-75568, 1-74272 and the like.

  Examples of useful anti-fading agents are described in JP-A-62-215272, pages (125) to (137).

  The anti-fading agent for preventing discoloration of the dye transferred to the dye fixing element may be previously contained in the dye fixing element, or may be supplied to the dye fixing element from the outside such as a photosensitive material. .

  The above antioxidants, ultraviolet absorbers and metal complexes may be used in combination.

  A fluorescent whitening agent may be used for the light-sensitive material and the dye-fixing element. In particular, it is preferable to incorporate a fluorescent brightening agent in the dye fixing element or to supply it from the outside such as a photosensitive material. Examples thereof include compounds described in K. Veenkataraman, “The Chemistry of Synthetic Dyes”, Volume V, Chapter 8, JP-A-61-143752. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyril compounds, and the like can be given. The optical brightener can be used in combination with an anti-fading agent.

  Examples of the hardener used in the constituent layer of the light-sensitive material and the dye-fixing element include U.S. Pat. No. 4,678,739, column 41, JP-A Nos. 59-116655, 62-245261, and 61-18842. And a hardener described in 1. More specifically, aldehyde hardeners (formaldehyde, etc.), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide) Ethane, etc.), N-methylol hardeners (dimethylol urea, etc.), or polymer hardeners (compounds described in JP-A-62-234157, etc.).

  In the constituent layers of the light-sensitive material and the dye-fixing element, various surfactants can be used for the purpose of coating aid, improvement of peelability, improvement of slipperiness, antistatic and development promotion. Specific examples of the surfactant are described in JP-A Nos. 62-173463 and 62-183457.

  The constituent layers of the light-sensitive material and the dye-fixing element may contain an organic fluoro compound for the purpose of improving smoothness, preventing static charge, and improving peelability. Representative examples of organic fluoro compounds include fluorine surfactants described in JP-B-57-9053, columns 8 to 17, JP-A-61-20944, 62-135826, and fluorine oil. And hydrophobic fluorine compounds such as oily fluorine compounds or solid fluorine compound resins such as tetrafluoroethylene resin.

  A matting agent can be used for the light-sensitive material and the dye-fixing element. As the matting agent, in addition to the compounds described on page 29 of JP-A-61-88256 such as silicon dioxide, polyolefin or polymethacrylate, JP-A-63-274944 such as benzoguanamine resin beads, polycarbonate resin beads and AS resin beads. No. 63-274922. The matting agent can be used for non-glossing of the surface of the dye-fixing element (image surface) in addition to the purpose of preventing adhesion, adjusting slipperiness and preventing Newton's ring.

  In addition, the constituent layers of the light-sensitive material and the dye-fixing element may contain a thermal solvent, an antifoaming agent, an antibacterial and antibacterial agent, colloidal silica, and the like. Specific examples of these additives are described in JP-A-61-88256, pages (26) to (32).

  In the present invention, an image forming accelerator can be used for the light-sensitive material and / or the dye-fixing element. The image forming accelerator includes an oxidation-reduction reaction between a silver salt oxidizing agent and a reducing agent, an acceleration of a reaction such as generation of a dye from a dye-donating substance or decomposition of the dye or release of a diffusible dye, and a photosensitive material layer. It has functions such as facilitating the transfer of dyes from the dye to the dye fixing layer. From the physicochemical functions, bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, surfactants, silver Or it classify | categorizes into the compound etc. which interact with a silver ion. However, these substance groups generally have a composite function, and usually have some of the above-mentioned promoting effects. Details of these are described in U.S. Pat. No. 4,678,739, columns 38-40.

  Examples of the base precursor include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement, and the like. Specific examples thereof are described in U.S. Pat. No. 4,511,493 and JP-A-62-65038.

  In a system in which heat development and dye transfer are simultaneously performed in the presence of a small amount of water, it is preferable that a base and / or a base precursor is contained in the dye fixing element in order to improve the storability of the photosensitive material.

  In addition to the above, the hardly soluble metal compounds described in European Patent Publication No. 210,660 and US Pat. No. 4,740,445 and compounds capable of complexing with the metal ions constituting the hardly soluble metal compounds ( Combinations of complex-forming compounds) and compounds that generate bases by electrolysis as described in JP-A No. 61-232451 can also be used as base precursors. The former method is particularly effective. The hardly soluble metal compound and the complex forming compound are advantageously added separately to the light-sensitive material and the dye-fixing element.

  In the present invention, various development stoppers can be used for the light-sensitive material and / or the dye-fixing element for the purpose of always obtaining a constant image with respect to variations in processing temperature and processing time during development.

  A development terminator here means that after proper development, the base is quickly neutralized or reacted with the base to lower the base concentration in the film and to interact with a compound or silver and silver salt that inhibits development and suppresses development. It is a compound. Specific examples include an acid precursor that releases an acid upon heating, an electrophilic compound that causes a substitution reaction with a base that coexists upon heating, a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. Further details are described in JP-A-62-253159, pages (31) to (32).

  In the present invention, a support capable of withstanding the processing temperature is used as the support for the light-sensitive material and the dye-fixing element. Generally, paper and a synthetic polymer (film) are mentioned. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those containing pigments such as titanium oxide in these films, and further made from polypropylene. Film method synthetic paper, blended paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (particularly cast coated paper), metal, cloth, glass and the like are used.

  These can be used alone or as a support laminated on one or both sides with a synthetic polymer such as polyethylene.

  In addition, the support described in JP-A-62-253159, pages (29) to (31) can be used.

  A hydrophilic binder, a semiconductor metal oxide such as alumina sol or tin oxide, carbon black or other antistatic agents may be applied to the surface of these supports.

  As a method for exposing and recording an image on a photosensitive material, the image information is exposed by emitting light from a light emitting diode or various lasers via an electrical signal, the image information is exposed to a CRT, a liquid crystal display, an electroluminescence display, a plasma display, etc. There is a method of outputting to an image display apparatus and exposing directly or via an optical system. Specifically, the exposure methods described in JP-A-2-129625, Japanese Patent Application Nos. 3-338182, 4-009388, and 4-281442 can be used.

  As the light source for recording an image on the photosensitive material, the light source described in US Pat. No. 4,500,626, column 56, such as a light emitting diode, a laser light source, and a CRT light source, can be used.

Next, the magnetic recording layer preferably used in the present invention will be described. The magnetic recording layer is obtained by coating a support with an aqueous or organic solvent-based coating liquid in which magnetic particles are dispersed in a binder. Magnetic particles include ferromagnetic iron oxide such as γFe ₂ O _3, Co deposited γFe ₂ O _3, Co coated magnetite ,, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal system Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite, etc. can be used. Co-coated ferromagnetic iron oxides such as Co-coated γFe ₂ O ₃ are preferred. The shape may be any of needle shape, rice grain shape, spherical shape, cubic shape, plate shape and the like. Preferably at least 20 m ² / g in S _BET is the specific surface area, and particularly preferably equal to or greater than 30 m ² / g. The saturation magnetization (σs) of the ferromagnetic material is preferably 3.0 × 10 ^{4 to} 3.0 × 10 ⁵ A / m, and particularly preferably 4.0 × 10 ^{4 to} 2.5 × 10 ⁵ A / m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, the magnetic particles may be treated on the surface with a silane coupling agent or a titanium coupling agent as described in JP-A-6-61032. Further, magnetic particles having a surface coated with inorganic or organic substances as described in JP-A-4-259911 and 5-81652 can also be used.

  The binder used for the magnetic particles is a thermoplastic resin, a thermosetting resin, a radiation curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer, a natural product polymer (cellulose) described in JP-A-4-19569. Derivatives, sugar derivatives, etc.) and mixtures thereof. The above resin has a Tg of -40 ° C to 300 ° C and a weight average molecular weight of 20,000 to 1,000,000. Examples thereof include vinyl copolymers, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose derivatives such as cellulose acetate butyrate, cellulose tripropionate, acrylic resins, and polyvinyl acetal resins, and gelatin is also preferable. Cellulose di (tri) acetate is particularly preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. Examples of isocyanate-based crosslinking agents include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and the like, and reaction products of these isocyanates with polyalcohols (for example, tolylene diene). Reaction products of 3 mol of isocyanate and 1 mol of trimethylolpropane), polyisocyanates formed by condensation of these isocyanates, and the like are mentioned, for example, in JP-A-6-59357.

As a method for dispersing the above-mentioned magnetic substance in the binder, a kneader, a pin type mill, an annular type mill, etc. are preferable, as in the method described in JP-A-6-35092. Dispersants described in JP-A-5-088283 and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm, more preferably 0.3 μm to 3 μm. The weight ratio of the magnetic particles to the binder is preferably from 0.5: 100 to 60: 100, more preferably from 1: 100 to 30: 100. The coating amount of the magnetic particles is 0.005 to 3 g / m ² , preferably 0.01 to ² g / m ² , more preferably 0.02 to 0.5 g / m ² . The transmission yellow density of the magnetic recording layer is preferably 0.01 to 0.50, more preferably 0.03 to 0.20, and particularly preferably 0.04 to 0.15. The magnetic recording layer can be provided on the entire surface or in a stripe shape on the back surface of the photographic support by coating or printing. As a method for applying the magnetic recording layer, an air doctor, blade, air knife, squeeze, impregnation, reverse roll, transfer roll, gravure, kiss, cast, spray, dip, bar, extraction, etc. can be used. The coating solution described in 341436 and the like is preferable.

  The magnetic recording layer may have functions such as lubricity improvement, curl adjustment, antistatic, adhesion prevention, head polishing, etc., or another functional layer may be provided to give these functions. A polishing agent for non-spherical inorganic particles in which at least one of the particles has a Mohs hardness of 5 or more is preferable. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide, and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. The surface of these abrasives may be treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as that for the magnetic recording layer is preferable. Photosensitive materials having a magnetic recording layer are described in US 5,336,589, 5,250,404, 5,229,259, 5,215,874, and EP 466,130.

  Next, the polyester support preferably used in the present invention will be described. For details including the photosensitive material, treatment, cartridge, and examples described later, the published technical report, public technical number 94-6023 (Invention Association; 1994.3.15). .)It is described in. The polyester used in the present invention is formed with diol and aromatic dicarboxylic acid as essential components, and 2,6-, 1,5-, 1,4- and 2,7-naphthalenedicarboxylic acid, terephthalic as aromatic dicarboxylic acid Examples of the acid, isophthalic acid, phthalic acid, and diol include diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol. Examples of this polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 mol% to 100 mol% of 2,6-naphthalenedicarboxylic acid. Of these, polyethylene 2,6-naphthalate is particularly preferred. The average molecular weight range is about 5,000 to 200,000. The Tg of the polyester of the present invention is 50 ° C. or higher, more preferably 90 ° C. or higher.

Next, the polyester support is heat-treated at a heat treatment temperature of 40 ° C. or more and less than Tg, more preferably Tg−20 ° C. or more and less than Tg, in order to make it difficult to cause curl. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. This heat treatment time is 0.1 hours to 1500 hours, more preferably 0.5 hours to 200 hours. The heat treatment of the support may be performed in a roll shape or may be performed while being conveyed in a web shape. The surface may be improved by providing irregularities on the surface (for example, applying conductive inorganic fine particles such as SnO ₂ and Sb ₂ O ₅ ). Further, it is desirable to devise such as applying a knurl to the end portion and slightly raising only the end portion to prevent the winding portion from being cut off. These heat treatments may be carried out at any stage after forming the support, after the surface treatment, after applying the back layer (antistatic agent, slip agent, etc.) and after applying the undercoat. Preferred is after application of the antistatic agent. This polyester may be kneaded with an ultraviolet absorber. In order to prevent light piping, the purpose can be achieved by kneading commercially available dyes or pigments for polyester such as Mitsubishi Kasei's Diaresin and Nippon Kayaku's Kayaset.

In order to adhere the support and the light-sensitive material constituting layer, it is preferable to perform a surface treatment. Examples of the surface activation treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and ozone oxidation treatment. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable. Next, regarding the undercoating method, a single layer or two or more layers may be used. As a binder for the undercoat layer, starting from a copolymer starting from a monomer selected from vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, etc. Examples include polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, and gelatin. Examples of compounds that swell the support include resorcin and p-chlorophenol. As the gelatin hardener for the undercoat layer, chromium salts (such as chromium alum), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine) Etc.), epichlorohydrin resins, active vinyl sulfone compounds and the like. SiO ₂ , TiO ₂ , inorganic fine particles or polymethyl methacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

Examples of the antistatic agent preferably used include a carboxylic acid, a carboxylate, a polymer containing a sulfonate, a cationic polymer, and an ionic surfactant compound. Most preferred as the antistatic agent is at least one selected from ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₃ , V ₂ O _5. The volume resistivity of the seed is 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less. The particle size is 0.001 to 1.0 μm Crystalline metal oxide or a composite oxide thereof (Sb, P, B, In , S, Si, C, etc.), and also sol-like metal oxides or composite oxides thereof. The addition amount to the photographic material, 5 to 500 mg / m ² is preferably particularly preferably 10 to 350 mg / m ^2. The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is preferably 1/300 to 100/1, more preferably 1/100 to 100/5.

  The light-sensitive material of the present invention preferably has slipperiness. The slip agent-containing layer is preferably used for both the photosensitive layer surface and the back surface. A preferable slip property is a dynamic friction coefficient of 0.25 or less and 0.01 or more. The measurement at this time represents the value when transported at a rate of 60 cm / min for a stainless steel ball having a diameter of 5 mm (25 ° C., 60% RH). In this evaluation, even if the counterpart material is replaced with the photosensitive layer surface, the value is almost the same level. Examples of slip agents that can be used in the present invention include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and polyorganosiloxanes include polydimethylsiloxane, polydiethylsiloxane, Styrylmethylsiloxane, polymethylphenylsiloxane, and the like can be used. As the additive layer, the outermost layer of the emulsion layer or the back layer is preferable. In particular, polydimethylsiloxane and esters having a long chain alkyl group are preferred.

  The light-sensitive material of the present invention preferably contains a matting agent. The matting agent may be either the emulsion surface or the back surface, but is particularly preferably added to the outermost layer on the emulsion side. The matting agent may be soluble in the processing solution or insoluble in the processing solution, and is preferably a combination of both. For example, polymethyl methacrylate, poly (methyl methacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. The particle size is preferably 0.8 to 10 μm, the particle size distribution is preferably narrow, and 90% or more of the total number of particles is preferably contained between 0.9 and 1.1 times the average particle size. It is also preferable to add fine particles of 0.8 μm or less at the same time in order to improve matting properties, for example, polymethyl methacrylate (0.2 μm), poly (methyl methacrylate / methacrylic acid = 9/1 (molar ratio), 0.3 μm)), polystyrene Examples thereof include particles (0.25 μm) and colloidal silica (0.03 μm).

Next, the film cartridge preferably used in the present invention will be described. The main material of the cartridge used in the present invention may be metal or synthetic plastic. Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Furthermore, the cartridge of the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonions, anions, cations and betaine surfactants or polymers can be preferably used. These antistatic cartridges are described in JP-A Nos. 1-312537 and 1-312538. In particular, the resistance at 25 ° C. and 25% RH is preferably 10 ¹² Ω or less. Usually, plastic patrone is manufactured using a plastic kneaded with carbon black or pigment to provide light shielding properties. The size of the patrone may be the same as the current 135 size. To reduce the size of the camera, it is also effective to reduce the diameter of the current 135 size 25 mm cartridge to 22 mm or less. The volume of the cartridge case is 30 cm ³ or less, preferably 25 cm ³ or less. The weight of the plastic used for the cartridge and the cartridge case is preferably 5 to 15 g.

  Furthermore, a cartridge that feeds a film by rotating a spool may be used. Alternatively, the film tip may be housed in the cartridge main body, and the film tip may be sent out from the port portion of the cartridge by rotating the spool shaft in the film feed direction. These are disclosed in US 4,834,306 and 5,226,613. The photographic film used in the present invention may be a so-called raw film before development or a developed photographic film. Further, the raw film and the developed photographic film may be stored in the same new cartridge, or may be different cartridges.

  EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

Example 1 (Synthesis Example 1)
Synthesis of compound 1

(1) 135 g of n-octadecanol and 50 g of succinic anhydride were placed in a 300 ml three-necked flask and reacted at 120 ° C. for 6 hours. Thereto was added 50 ml of ethyl acetate for crystallization. The obtained crystals were collected by filtration under reduced pressure and washed with ethyl acetate. 165 g of intermediate A was obtained by air-drying the crystals. (Yield 89.1%)
(2) 30 g of Intermediate A and 30 ml of methylene chloride were placed in a 200 ml three-necked flask, and 1 ml of dimethylformamide was added with stirring. At an internal temperature of 20 ° C., 12.3 g of oxalyl chloride was added dropwise over 30 minutes, followed by further reaction for 1 hour. Intermediate B was obtained by distilling off the remaining oxalyl chloride and methylene chloride under reduced pressure using an aspirator. The obtained intermediate B was directly used in the next step.
(3) To a 1.0 liter three-neck flask, 2.40 g of sodium hydroxide and 100 ml of water were added and dissolved, and then ice-cooled. After adding 5.0 g of N-methylhydroxylamine hydrochloride under nitrogen flow at an internal temperature of 10 ° C., 10.1 g of sodium hydrogen carbonate and 100 ml of ethyl acetate were further added. While vigorously stirring, the internal temperature was kept at 5 to 10 ° C., and a mixture of 25 g of intermediate B and 200 ml of ethyl acetate was added dropwise over 30 minutes. After reacting for 2 hours, the reaction solution was heated to 50 ° C. and separated. The organic layer was washed twice with water and dried over magnesium sulfate. After filtration, the crude product obtained by distilling off the solvent under reduced pressure with an evaporator was purified by silica gel column chromatography (ethyl acetate: hexane = 1: 10) to obtain 19.1 g of Compound 1. (Yield 79.8%)

Example 2 (Synthesis Example 2)
Synthesis of compounds 21 and 22

(1) 300 g of octadecenyl succinic anhydride and 232 g of octadecanol were placed in a 1.0 liter three-necked flask and reacted at 80 ° C. for 9 hours. After cooling to 60 ° C., crystallization was performed by adding 300 ml of acetonitrile and allowing to cool to room temperature. To this was added 200 ml of acetonitrile and filtered under reduced pressure. The obtained crystals were washed well with acetonitrile and then recrystallized from acetonitrile to obtain 511 g of a mixture of Intermediate C and Intermediate D. (Yield 96.0%)

(2) 200 g of a mixture of intermediates C and D and 200 ml of methylene chloride were placed in a 1.0 liter three-necked flask, and 2.0 ml of dimethylformamide was added. To this mixed solution, 53.2 g of oxalyl chloride was added dropwise at 20 ° C. over 30 minutes. After further reacting for 2 hours, the oxalyl chloride and methylene chloride remaining in an aspirator were distilled off under reduced pressure to obtain acid chlorides of intermediates C and D. The obtained acid chloride was used as it was in the next step.
(3) N-methylhydroxamic acid hydrochloride 29.4 g, sodium hydroxide 14.1 g, sodium hydrogen carbonate 59.1 g, intermediate C, D acid chloride, total amount of (2) above, water 500 ml, ethyl acetate Using 900 ml, a reaction was carried out in exactly the same manner as in Synthesis Example 1 (3), whereby crystals of a mixture of compounds 21 and 22 were obtained. By separating using silica gel column chromatography, 70 g of the target compound 21 and 25 g of the compound 22 were obtained.

Reference Example 1 (Synthesis Example 3)
Synthesis of Compound 56

(1) 81 g of di-n-octylamine, 33.6 g of succinic anhydride, and 100 ml of acetonitrile were placed in a three-necked flask and reacted at 40 ° C. for 1 hour. Water was added and the mixture was extracted with ethyl acetate. The organic layer was washed twice with water, dried over magnesium sulfate and concentrated to obtain 106 g of oily intermediate E. The obtained E was directly used in the next step.
(2) 50 g of intermediate E, 100 ml of methylene chloride and 0.2 ml of dimethylformamide were placed in a three-necked flask and stirred. At room temperature, 19.2 g of thionyl chloride was added dropwise and reacted at 40 ° C. for 30 minutes. The remaining thionyl chloride and methylene chloride were distilled off under reduced pressure using an aspirator to obtain 52.7 g of Intermediate F.
(3) 200 ml of water, 6.1 g of sodium hydroxide, and 12.8 g of N-methylhydroxylamine hydrochloride were stirred in a nitrogen gas atmosphere. Next, 12.8 g of N-methylhydroxylamine, 25.7 g of sodium bicarbonate, and 200 ml of ethyl acetate were added. Under ice cooling, a solution prepared by dissolving 42.7 g of intermediate F in 50 ml of methylene chloride was added dropwise. After reacting for 30 minutes, the temperature was raised to 40 ° C. and liquid separation was performed. The organic layer was washed with water twice and then concentrated under reduced pressure to obtain a crude product of compound 36. The product was purified by silica gel column chromatography to obtain 39.2 g of a purified product.
Compounds 1 to 56 can be synthesized according to the above-described synthesis method.

The physical property values of the compound of the present invention are described below. A typical compound will be described.
Compound 4
Appearance White crystal melting point 68-69 ° C
NMR spectrum (300MHz)
δ (CDCl ₃ ): 0.90 (3H, d, J6), 1.27 (22H, bs), 1.61 (2H, dt, J ₁ 12, J ₂ 6), 2.61 (2H, bs), 2.70 (2H, bs) , 3.24 (1.5H, bs), 3.40 (1.5H, bs), 4.08 (2H, t, J6), 8.10 (1H, bs)
Compound 21
Appearance Waxy solid melting point 52 ° C
NMR spectrum (300MHz)
δ (CDCl ₃ ): 0.90 (6H, t, J6), 1.30 (56H, bs), 1.61 (2H, t, J6), 1.99 (2H, dd, J ₁ 12, J ₂ 6), 2.10 (1H, m), 2.32 (1H, m), 2.51 (1H, m), 2.73 (1H, m), 3.00 (1H, bs), 3.23 (1.5H, bs), 3.42 (1.5H, bs), 4.03 (2H , t, J6), 5.30 (1H, m), 5.50 (1H, dt, J ₁ 16, J ₂ 6), 8.12 (1H, bs)
Compound 22
Appearance White crystal melting point 68 ℃
NMR spectrum (300MHz)
δ (CDCl ₃ ): 0.89 (6H, t, J6), 1.27 (56H, bs), 1.62 (2H, t, J6), 1.98 (2H, dd, J ₁ 12, J ₂ 6), 2.32 (3H, m), 2.69 (1H, m), 3.01 (1H, bs), 3.21 (1.5H, bs), 3.34 (1.5H, bs), 4.08 (2H, m), 5.30 (1H, dt, J ₁ 16, J ₂ 6), 5.49 (1H, dt, J ₁ 16, J ₂ 6), 8.10 (1H, bs)

Compound 27
Appearance Waxy solid melting point 47 ℃
NMR spectrum (300MHz)
δ (CDCl ₃ ): 0.90 (6H, t, J6), 1.30 (54H, bs), 1.61 (2H, t, J6), 1.99 (2H, dd, J ₁ 12, J ₂ 6), 2.10 (1H, m), 2.32 (1H, m), 2.51 (1H, m), 2.73 (1H, m), 3.00 (1H, bs), 3.23 (1.5H, bs), 3.42 (1.5H, bs), 4.03 (2H , t, J6), 5.30 (1H, m), 5.50 (1H, dt, J ₁ 16, J ₂ 6), 8.12 (1H, bs)

Compound 28
Appearance White crystal melting point 65 ℃
NMR spectrum (300MHz)
δ (CDCl ₃ ): 0.90 (6H, t, J6), 1.30 (54H, bs), 1.61 (2H, t, J6), 1.99 (2H, dd, J ₁ 12, J ₂ 6), 2.10 (1H, m), 2.32 (1H, m), 2.51 (1H, m), 2.73 (1H, m), 3.00 (1H, bs), 3.23 (1.5H, bs), 3.42 (1.5H, bs), 4.03 (2H , t, J6), 5.30 (1H, m), 5.50 (1H, dt, J ₁ 16, J ₂ 6), 8.12 (1H, bs)
The structure of other compounds was also confirmed by NMR spectrum or mass spectrum. Compounds 14, 16, 17, 18, 19, 20, 23, 24, 25, 26, 27, 34 were oils.

Reference example 2
A sample 101, which is a multilayer color photosensitive material composed of each layer having the composition shown below, was prepared on an undercoated cellulose triacetate film support.
(Composition of photosensitive layer)
For silver halide and colloidal silver, the coating amount is the amount expressed in g / m ² unit of silver, for couplers, additives and gelatin, the amount expressed in g / m ² unit, and for the sensitizing dye The number of moles per mole of silver halide in the same layer is shown. In addition, the symbol which shows an additive has the meaning shown below. However, if there are multiple utilities, one of them is listed.
UV: UV absorber, Solv: High boiling point organic solvent, ExF: Dye, ExS: Sensitizing dye, ExC: Cyan coupler, ExM: Magenta coupler, ExY: Yellow coupler, Cpd: Additive

First layer (Anti-halation layer)
Black colloidal silver 0.15
Gelatin 2.33
UV-1 1.9 × 10 ^-2
UV-2 4.7 × 10 ^-2
UV-3 8.6 × 10 ^-2
ExF-3 5.0 × 10 ^-3
ExM-3 2.3 × 10 ^-2
Solv-1 0.16
Solv-2 0.10

Second layer (intermediate layer)
Gelatin 0.88
Polyethyl acrylate latex 2.6 × 10 ^-1
ExC-7 5.0 × 10 ^-2

3rd layer (low sensitivity red sensitive emulsion layer)
Silver iodobromide Emulsion A Silver coating amount 0.24
Silver iodobromide emulsion B Amount of coated silver 0.65
Gelatin 1.75
ExS-1 6.9 × 10 ^-4
ExS-2 4.0 × 10 ^-4
ExS-5 6.7 × 10 ^-4
ExS-7 1.4 × 10 ^-5
ExC-1 3.0 × 10 ^-1
ExC-5 2.0 × 10 ^-1
ExC-9 2.2 × 10 ^-2
Cpd-4 5.3 × 10 ^-2
ExC-4 6.1 × 10 ^-2

Fourth layer (medium sensitivity red emulsion layer)
Silver iodobromide Emulsion C Amount of coated silver 0.67
Gelatin 0.94
ExS-1 3.5 × 10 ^-4
ExS-2 2.0 × 10 ^-4
ExS-5 3.4 × 10 ^-4
ExS-7 6.9 × 10 ^-6
ExC-1 1.3 × 10 ^-1
ExC-4 4.6 × 10 ^-2
ExC-5 8.6 × 10 ^-2
ExC-6 1.1 × 10 ^-2
ExC-7 4.6 × 10 ^-2
Cpd-4 2.1 × 10 ^-2

5th layer (High sensitivity red emulsion layer)
Silver iodobromide emulsion D Silver coating amount 0.67
Gelatin 0.68
ExS-1 3.2 × 10 ^-4
ExS-2 1.8 × 10 ^-4
ExS-5 3.1 × 10 ^-4
ExS-7 4.8 × 10 ^-5
ExC-1 5.1 × 10 ^-2
ExC-6 9.0 × 10 ^-3
ExC-4 2.0 × 10 ^-2
ExC-9 1.0 × 10 ^-2
Cpd-4 2.1 × 10 ^-3
Solv-1 0.08
Solv-2 0.04

6th layer (intermediate layer)
Gelatin 0.62
Cpd-1 0.08
Polyethyl acrylate latex 4.1 × 10 ^-2
Solv-1 4.0 × 10 ^-2

7th layer (low sensitivity green emulsion layer)
Silver iodobromide Emulsion E coated silver 0.14
Gelatin 0.49
ExS-8 5.7 × 10 ^-5
ExS-4 9.0 × 10 ^-4
ExS-5 1.8 × 10 ^-4
ExM-1 0.26
Solv-1 0.15
Solv-3 7.0 × 10 ^-3

8th layer (medium sensitive green emulsion layer)
Silver iodobromide emulsion F Silver coating amount 0.08
Silver iodobromide Emulsion E Amount of coated silver 0.01
Gelatin 0.14
ExS-8 4.3 × 10 ^-5
ExS-4 6.8 × 10 ^-4
ExS-5 1.3 × 10 ^-4
ExM-1 4.9 × 10 ^-2
ExM-7 1.0 × 10 ^-2
ExY-1 5.0 × 10 ^-3
Solv-1 3.3 × 10 ^-2
Solv-3 1.5 × 10 ^-3

9th layer (high-sensitivity green-sensitive emulsion layer)
Silver iodobromide emulsion G Amount of coated silver 0.60
Gelatin 0.60
ExS-4 5.0 × 10 ^-4
ExS-5 9.9 × 10 ^-5
ExS-8 3.2 × 10 ^-5
ExM-7 2.4 × 10 ^-2
ExM-1 8.4 × 10 ^-2
ExY-1 6.7 × 10 ^-2
ExC-1 6.0 × 10 ^-3
ExC-4 8.0 × 10 ^-3
Cpd-6 8.0 × 10 ^-3
Solv-1 0.12
Solv-2 0.06
Solv-3 6.0 × 10 ^-3

10th layer (intermediate layer)
Gelatin 0.39
UV-2 1.4 × 10 ^-2
UV-3 1.6 × 10 ^-2
UV-5 4.2 × 10 ^-2
Cpd-1 2.6 × 10 ^-2
Polyethyl acrylate latex 1.4 × 10 ^-2
Solv-1 2.8 × 10 ^-2
11th layer (a donor layer with a multi-layer effect on the red-sensitive layer)
Silver iodobromide emulsion H Silver coating amount 1.12
Silver iodobromide emulsion I Silver coating amount 0.26
Gelatin 1.61
ExS-3 6.4 × 10 ^-4
ExM-2 2.7 × 10 ^-2
ExM-1 2.0 × 10 ^-1
ExM-7 1.7 × 10 ^-1
ExY-2 2.0 × 10 ^-1
Solv-1 0.50
12th layer (yellow filter layer)
Yellow colloidal silver 3.3 × 10 ^-2
Gelatin 0.61
Cpd-1 4.3 × 10 ^-2
Cpd-2 7.9 × 10 ^-2
Cpd-5 1.0 × 10 ^-3
Solv-1 4.7 × 10 ^-2

13th layer (low sensitivity blue-sensitive emulsion layer)
Silver iodobromide emulsion J Silver coating amount 0.62
Gelatin 1.67
ExS-9 8.8 × 10 ^-4
ExY-2 1.2 × 10 ^-1
ExY-3 3.5 × 10 ^-1
ExC-9 6.3 × 10 ^-2
ExC-1 3.0 × 10 ^-2
ExC-10 8.4 × 10 ^-2
Solv-1 0.33

14th layer (high-sensitivity blue-sensitive emulsion layer)
Silver iodobromide emulsion K Coating silver amount 0.14
Silver iodobromide emulsion L Silver coating amount 0.10
Silver iodobromide emulsion M Silver coating amount 0.22
Gelatin 1.00
ExS-6 4.4 × 10 ^-4
ExY-2 7.6 × 10 ^-2
ExY-3 1.1 × 10 ^-1
ExY-6 3.1 × 10 ^-1
ExC-1 1.8 × 10 ^-2
ExC-10 2.3 × 10 ^-2
Solv-1 1.7 × 10 ^-1

15th layer (first protective layer)
Fine grain silver iodobromide Emulsion N Amount of coated silver 0.06
Gelatin 0.51
UV-2 4.0 × 10 ^-2
UV-3 4.9 × 10 ^-2
UV-5 0.12
Cpd-3 0.10
ExF-4 2.1 × 10 ^-3
ExF-5 6.3 × 10 ^-3
Solv-4 2.0 × 10 ^-2
Polyethyl acrylate latex 9.0 × 10 ^-2

16th layer (2nd protective layer)
Fine grain silver iodobromide Emulsion N Amount of coated silver 0.18
Gelatin 0.84
B-1 (Diameter 2.0μm) 8.0 × 10 ^-2
B-2 (Diameter 2.0μm) 8.0 × 10 ^-2
B-3 3.5 × 10 ^-2
W-5 1.8 × 10 ^-2
H-1 0.18

  In addition to the above, the sample thus prepared included 1,2-benzisothiazolin-3-one (average 200 ppm based on gelatin), n-butyl-p-hydroxybenzoate (about 1,000 ppm), and 2-phenoxyethanol. (About 10,000 ppm). Furthermore, W-1 to W-6, B-1 to B-6, F in order to improve storage stability, processability, pressure resistance, antifungal / antibacterial properties, antistatic properties and coating properties as appropriate for each layer. -1 to F-17 and iron, lead, gold, platinum, iridium and rhodium salts are contained.

In Table 1,
(1) Emulsions A to M are reduction sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-91938.
(2) Emulsions A to M are subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye and sodium thiocyanate described in each photosensitive layer according to the examples of JP-A-3-237450. It has been subjected.
(3) In preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426.
(4) Dislocation lines as described in JP-A-3-237450 have been observed using a high-voltage electron microscope in tabular grains and normal crystal grains having a grain structure.
(5) Emulsions A to M contain iridium inside the grains by the method described in BH Carroll, Photographic Science and Engineering, 24, 265 (1980).

Except that the compound of the general formula (II) or the comparative compound was co-emulsified with the coupler of this layer in the fourth layer of Sample 101 and added so as to be 5 × 10 ⁻² mol per 1 mol of Ag of this layer. Samples 102 to 125 and 127 were produced as shown in Table 2 in accordance with the method for producing Sample 101. In addition, when two compounds are described, they were mixed at a molar ratio of 1: 1 so that the total number of moles was 5 × 10 ⁻² mole relative to 1 mole of Ag.

  Evaluation of photographic variation after shooting until processing was performed by the following method. After giving these exposures for light sensitive material sensitometry, after storing for 3 days under forced deterioration conditions of 60 ° C. and 50 ° C. and 80%, the following color development processing was performed at 38 ° C., and the processed samples were prepared. The density was measured with a red filter and a blue filter. The magnitude of the difference in sensitivity between this and a sample that was developed immediately after exposure was evaluated.

After exposing the color photographic light-sensitive material as described above, it was processed by the method described below.
(Processing method)
Process Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C
White 3 minutes 00 seconds 38 ℃
Washing with water 30 seconds 24 ℃
3 minutes 00 seconds 38 ℃
Washing with water (1) 30 seconds 24 ℃
Washing with water (2) 30 seconds 24 ℃
Stable 30 seconds 38 ℃
Dry 4 min 20 sec 55 ° C

Next, the composition of the treatment liquid will be described.
(Color developer) (Unit: g)
Diethylenetriaminepentaacetic acid 1.0
1-hydroxyethylidene-1,1-diphosphonic acid 3.0
Sodium sulfite 4.0
Potassium carbonate 30.0
Potassium bromide 1.4
Potassium iodide 1.5 mg
Hydroxylamine sulfate 2.4
4- [N-ethyl-N-β-hydroxyethylamino]-
2-Methylaniline sulfate 4.5
Add water 1.0 liter pH 10.05

(Bleaching solution) (Unit: g)
Ethylenediaminetetraacetic acid sodium ferric acid salt trihydrate 100.0
Ethylenediaminetetraacetic acid disodium salt 100.0
3-mercapto-1,2,4-triazole 0.03
Ammonium bromide 140.0
Ammonium nitrate 30.0
Ammonia water (27%) 6.5 ml Water added 1.0 liter pH 6.0

(Fixing solution) (Unit: g)
Ethylenediaminetetraacetic acid disodium salt 0.5
Ammonium sulfite 20.0
Ammonium thiosulfate aqueous solution (700 g / liter) 295.0
Acetic acid (90%) 3.3
1.0 liter with water, pH 6.7

(Stabilizer)
p-nonylphenoxypolyglycidol (average glycidol polymerization degree 10) 0.2
Ethylenediaminetetraacetic acid 0.05
1,2,4-triazole 1.3
1,4-bis (1,2,4-triazole-1-
Ilmethyl) Piperazine 0.75
Hydroxyacetic acid 0.02
Hydroxyethyl cellulose (Daicel Chemical HEC SP-2000) 0.1
1,2-Benzisothiazolin-3-one 0.05
1.0 liter with water, pH 8.5

  For sensitivity display of photographic properties, a logarithmic value of the reciprocal of the exposure amount required for the optical density to be higher than the fog by 1.0 was used. The change in photographic properties before processing after photographing was expressed as the relative sensitivity (difference in logarithmic value) to the sensitivity of those stored under forced deterioration conditions after exposure and processed immediately after exposure. The closer this value is to 0, the smaller the change in photographic properties.

  The evaluation was carried out on both the photographic change of the red-sensitive layer to which the compound of the general formula (II) was added and the blue-sensitive layer as the non-added layer. When the compound of the general formula (II) or the comparative compound is added, the photographic properties of the blue-sensitive layer change compared to the case where the compound is not added (sample 101). This indicates that the compound has diffused into the additive layer), which is not preferable.

  The results are shown in Table 2.

  As shown in Table 2, the light-sensitive material using the compound of the general formula (II) of the present invention has little change in photographic properties over time until the post-processing of the additive layer (red photosensitive layer), and the non-added layer It is clear that the (blue-sensitive layer) is preferable without deteriorating the variation with time. Further, the compound of the general formula (II) of the present invention had no effect on other photographic properties, and had no effect on the storage stability of the non-added layer.

Reference example 3
Reference Example 2 Other than those shown in Table 2, the compounds 5, 7-11, 14, 15, 23, 29, 34-42, 50, 53-55 of the present invention were also evaluated. However, these compounds showed an effect of preferably reducing the photographic change with time when left after photographing.

Reference example 4
Even when the compound of the present invention was used in the green photosensitive layer or the blue photosensitive layer, as in Reference Example 2, the storage stability of the added layer was improved, and the non-added layer was not affected and showed a favorable effect.

Reference Example 5
Instead of the sample 101 of Reference Example 2, a sample 201 shown below was produced. Except that the compound of the general formula (II) or the comparative compound was co-emulsified with the coupler of this layer in the fourth layer of the sample 201 and added to 5 × 10 ⁻² mol with respect to 1 mol of Ag of this layer. Samples 202 to 225 and 227 were manufactured according to the method for manufacturing the sample 201. In addition, when two compounds are described, they were mixed at a molar ratio of 1: 1 so that the total number of moles was 5 × 10 ⁻² mole relative to 1 mole of Ag. When these were used to evaluate the compounds of the present invention, the same preferable performance as in Reference Example 2 was exhibited.

1) Support The support used in this reference example was produced by the following method. 100 parts by weight of commercially available polyethylene-2,6-naphthalate polymer and 2 parts by weight of Tinuvin P.326 (manufactured by Ciba-Geigy) as an ultraviolet absorber were dried by a conventional method and then melted at 300 ° C. Later, it was extruded from a T-shaped die, stretched 3.0 times at 140 ° C, then stretched 3.0 times at 130 ° C, and then heat-fixed at 250 ° C for 6 seconds to obtain a PEN film with a thickness of 90 µm. It was. Further, a part thereof was wound around a stainless steel core having a diameter of 20 cm, and a thermal history of 110 ° C. and 48 hours was given.
2) Application of undercoat layer The support was subjected to corona discharge treatment, UV discharge treatment, glow discharge treatment, and flame treatment on both sides, and then an undercoat solution having the following composition was applied to each surface. An undercoat layer was provided on the high temperature side during stretching. For the corona discharge treatment, a solid state corona treatment machine 6KVA model manufactured by Pillar Pillar is used, and a 30 cm wide support is treated at 20 m / min. At this time, the processed object was processed at 0.375 KV · A · min / m ² from the current and voltage readings. The discharge frequency during the treatment was 9.6 KHz, and the gap clearance between the electrode and the dielectric roll was 1.6 mm. The UV discharge treatment was performed under heating at 75 ° C. Further, in the glow discharge treatment, irradiation was performed with a cylindrical electrode at 3000 W for 30 seconds.

3g gelatin
Distilled water 25ml
Sodium α-sulfo-di-2-ethylhexyl succinate 0.05g
0.02g formaldehyde
Salicylic acid 0.1 g
Diacetylcellulose 0.5 g
p-Chlorophenol 0.5 g
Resorcin 0.5 g
Cresol 0.5 g
(CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.02 g
Trimethylolpropane aziridine 3-fold molar adduct 0.02g
Trimethylolpropane-toluene diisocyanate 3-fold molar adduct 0.02 g
Methanol 15ml
Acetone 85ml
0.01g formaldehyde
Acetic acid 0.01g
Concentrated hydrochloric acid 0.01g

3) Coating of Back Layer An antistatic layer, a magnetic recording layer, and a sliding layer having the following composition were coated as a back layer on one side of the support after the undercoating.
3-1) Coating of antistatic layer 3-1-1) Preparation of conductive fine particle dispersion (tin oxide-antimony oxide composite dispersion) Stannic chloride hydrate 230 parts by weight and antimony trichloride 23 parts by weight A part was dissolved in 3000 parts by weight of ethanol to obtain a uniform solution. To this solution, a 1N aqueous sodium hydroxide solution was added dropwise until the pH of the solution reached 3, to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The obtained coprecipitate was left at 50 ° C. for 24 hours to obtain a reddish brown colloidal precipitate.

  The reddish brown colloidal precipitate was separated by centrifugation. In order to remove excess ions, water was added to the precipitate and washed by centrifugation. This operation was repeated three times to remove excess ions. 200 parts by weight of colloidal precipitate from which excess ions have been removed are redispersed in 1500 parts by weight of water, sprayed in a baking furnace heated to 650 ° C., and bluish tin oxide-antimony oxide composite having an average particle size of 0.005 μm A fine powder was obtained. The specific resistance of the fine particle powder was 5 Ω · cm. Prepare a mixture of 40 parts by weight of the above fine particle powder and 60 parts by weight of water to pH 7.0, coarsely disperse with a stirrer, and then use a horizontal sand mill (trade name Dynomill; manufactured by WILLYA. BACHOFENAG) until the residence time reaches 30 minutes. Prepared by dispersing. The average particle size of the secondary aggregate at this time was about 0.04 μm.

3-1-2) Coating of conductive layer A conductive layer according to the following formulation was applied to a dry film thickness of 0.2 μm and dried at 115 ° C. for 60 seconds.
Conductive fine particle dispersion prepared in 3-1-1) 20 parts by weight Gelatin 2 parts by weight Water 27 parts by weight Methanol 60 parts by weight P-chlorophenol 0.5 parts by weight Resorcin 2 parts by weight Polyoxyethylene nonylphenyl ether 0.01 parts by weight The resistance of the obtained conductive film was 10 ^8.0 (100 V) and had excellent antistatic performance.
3-2) Coating of magnetic recording layer Magnetic material Co-coated γ-Fe ₂ O ₃ (major axis 0.14 μm, uniaxial 0.03 μm needle shape, specific surface area 41 m ² / g, saturation magnetization 89 emu / g, surface Is surface-treated with 2% by weight of Fe ₂ O ₃ with aluminum oxide and silicon oxide, coercive force 930 Oe, Fe ⁺² / Fe ⁺³ ratio is 6/94) 1100 g of water 220 g and poly (polymerization degree) 16) 150 g of silane coupling agent of oxyethylenepropyl trimethoxysilane was added and kneaded well with an open kneader for 3 hours. This coarsely dispersed viscous liquid was dried at 70 ° C. for one day and night, after removing water, heated at 110 ° C. for 1 hour to produce surface-treated magnetic particles. Furthermore, it knead | mixed with the open kneader again with the following prescription.

Surface-treated magnetic particles 1000g
Diacetylcellulose 17g
Methyl ethyl ketone 100g
Cyclohexanone 100g
Furthermore, it was finely dispersed at 200 rpm for 4 hours with a sand mill (1 / 4G) according to the following formulation.
100g of the above kneaded product
Diacetyl cellulose 60g
Methyl ethyl ketone 300g
Cyclohexanone 300g
Furthermore, diacetylcellulose and a trimethylolpropane-toluene diisocyanate triple molar adduct as a curing agent were added in an amount of 20 wt% with respect to the binder. The resulting liquid was diluted with equal amounts of methyl ethyl ketone and cyclohexanone so that the viscosity of the liquid was about 80 cP. The coating was performed on the conductive layer with a bar coater so that the film thickness was 1.2 μm. The magnetic material was applied so that the amount was 0.6 g / m ² . Further, silica particles (0.3 μm) as a matting agent and aluminum oxide (0.5 μm) as an abrasive were added so as to be 10 mg / m ² , respectively. Drying was carried out at 115 ° C. for 6 minutes (all rollers and conveyors in the drying zone were at 115 ° C.). When using a blue filter in Status M of X- write, increment of the color density of D ^B of the magnetic recording layer was about 0.1. The magnetic recording layer had a saturation magnetization moment of 4.2 emu / m ² , a coercive force of 923 Oe, and a squareness ratio of 65%.

3-3) Preparation of sliding layer The following prescription liquid was apply | coated so that the solid content application amount of a compound might become as follows, and it was made to dry at 110 degreeC for 5 minutes, and the sliding layer was obtained.
Diacetylcellulose 25mg / m ²
C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ (Compound a) 6 mg / m ²
C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H (Compound b) 9 mg / m ²
Compound a / Compound b (6: 9) was heated and dissolved at 105 ° C. in a solvent of xylene and propylene glycol monomethyl ether (volume ratio 1: 1), and this liquid was mixed with 10 times the amount of propylene glycol monomethyl ether ( 25 ° C.) to obtain a fine dispersion. Furthermore, after diluting in 5 times the amount of acetone, it was re-dispersed with a high-pressure homogenizer (200 atm) to form a dispersion (average particle size 0.01 μm) and then used. The obtained sliding layer has excellent characteristics, with a dynamic friction coefficient of 0.06 (5 mmφ stainless hard balls, load of 100 g, speed of 6 cm / min) and static friction coefficient of 0.07 (clip method). In addition, the slip coefficient with the emulsion surface described later was also a dynamic friction coefficient of 0.12.

4) Coating of light-sensitive material layer Next, on the opposite side of the back layer obtained above, each layer having the following composition was applied in multiple layers to prepare a color negative film. This is designated as sample 201.

The main materials used in each layer are classified as follows:
ExC: Cyan coupler UV: Ultraviolet absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin hardener ExS: Sensitizing dye The number corresponding to each component is expressed in g / m ² units For silver halide, the coating amount in terms of silver is shown. However, for the sensitizing dye, the coating amount with respect to 1 mol of silver halide in the same layer is shown in mol units.

(Sample 201)
First layer (Anti-halation layer)
Black colloidal silver 0.09
Gelatin 1.60
ExM-1 0.12
ExF-1 2.0 × 10 ^-3
Solid disperse dye ExF-2 0.030
Solid disperse dye ExF-3 0.040
HBS-1 0.15
HBS-2 0.02

Second layer (intermediate layer)
Silver iodobromide emulsion M Silver 0.065
ExC-2 0.04
Polyethyl acrylate latex 0.20
Gelatin 1.04

3rd layer (low sensitivity red sensitive emulsion layer)
Silver iodobromide emulsion A Silver 0.25
Silver iodobromide emulsion B Silver 0.25
ExS-1 6.9 × 10 ^-5
ExS-2 1.8 × 10 ^-5
ExS-3 3.1 × 10 ^-4
ExC-1 0.17
ExC-3 0.030
ExC-4 0.10
ExC-5 0.020
ExC-6 0.010
Cpd-2 0.025
HBS-1 0.10
Gelatin 0.87

Fourth layer (medium sensitivity red emulsion layer)
Silver iodobromide emulsion C Silver 0.70
ExS-1 3.5 × 10 ^-4
ExS-2 1.6 × 10 ^-5
ExS-3 5.1 × 10 ^-4
ExC-1 0.13
ExC-2 0.060
ExC-3 0.0070
ExC-4 0.090
ExC-5 0.015
ExC-6 0.0070
Cpd-2 0.023
HBS-1 0.10
Gelatin 0.75

5th layer (High sensitivity red emulsion layer)
Silver iodobromide emulsion D Silver 1.40
ExS-1 2.4 × 10 ^-4
ExS-2 1.0 × 10 ^-4
ExS-3 3.4 × 10 ^-4
ExC-1 0.10
ExC-3 0.045
ExC-6 0.020
ExC-7 0.010
Cpd-2 0.050
HBS-1 0.22
HBS-2 0.050
Gelatin 1.10

6th layer (intermediate layer)
Cpd-1 0.090
Solid disperse dye ExF-4 0.030
HBS-1 0.050
Polyethyl acrylate latex 0.15
Gelatin 1.10

7th layer (low sensitivity green emulsion layer)
Silver iodobromide emulsion E Silver 0.15
Silver iodobromide emulsion F Silver 0.10
Silver iodobromide emulsion G Silver 0.10
ExS-4 3.0 × 10 ^-5
ExS-5 2.1 × 10 ^-4
ExS-6 8.0 × 10 ^-4
ExM-2 0.33
ExM-3 0.086
ExY-1 0.015
HBS-1 0.30
HBS-3 0.010
Gelatin 0.73

8th layer (medium sensitive green emulsion layer)
Silver iodobromide emulsion H Silver 0.80
ExS-4 3.2 × 10 ^-5
ExS-5 2.2 × 10 ^-4
ExS-6 8.4 × 10 ^-4
ExC-8 0.010
ExM-2 0.10
ExM-3 0.025
ExY-1 0.018
ExY-4 0.010
ExY-5 0.040
HBS-1 0.13
HBS-3 4.0 × 10 ^-3
Gelatin 0.80

9th layer (high-sensitivity green-sensitive emulsion layer)
Silver iodobromide emulsion I Silver 1.25
ExS-4 3.7 × 10 ^-5
ExS-5 8.1 × 10 ^-5
ExS-6 3.2 × 10 ^-4
ExC-1 0.005
ExC-6 0.005
ExM-1 0.020
ExM-4 0.025
ExM-5 0.040
Cpd-3 0.040
HBS-1 0.25
Polyethyl acrylate latex 0.15
Gelatin 1.33

10th layer (yellow filter layer)
Yellow colloidal silver 0.015
Cpd-1 0.16
Solid disperse dye ExF-5 0.060
Solid disperse dye ExF-6 0.060
Oil-soluble dye ExF-7 0.010
HBS-1 0.60
Gelatin 0.60

11th layer (low sensitivity blue-sensitive emulsion layer)
Silver iodobromide emulsion J Silver 0.09
Silver iodobromide emulsion K Silver 0.09
ExS-7 8.6 × 10 ^-4
ExC-8 7.0 × 10 ^-3
ExY-1 0.050
ExY-2 0.22
ExY-3 0.50
ExY-4 0.020
Cpd-2 0.10
Cpd-3 4.0 × 10 ^-3
HBS-1 0.28
Gelatin 1.20

12th layer (high sensitivity blue-sensitive emulsion layer)
Silver iodobromide emulsion L Silver 1.00
ExS-7 4.0 × 10 ^-4
ExY-2 0.10
ExY-3 0.10
ExY-4 0.010
Cpd-2 0.10
Cpd-3 1.0 × 10 ^-3
HBS-1 0.070
Gelatin 0.70

13th layer (first protective layer)
UV-1 0.19
UV-2 0.075
UV-3 0.065
HBS-1 5.0 × 10 ^-2
HBS-4 5.0 × 10 ^-2
ExF-8 2.1 × 10 ^-3
ExF-9 6.3 × 10 ^-3
Gelatin 1.8

14th layer (2nd protective layer)
Silver iodobromide emulsion M Silver 0.10
H-1 0.40
B-1 (diameter 1.7 μm) 5.0 × 10 ^-2
B-2 (Diameter 1.7 μm) 0.15
B-3 0.05
S-1 0.20
Gelatin 0.70

  Furthermore, W-1 to W-3, B-4 to B-6, F in order to improve storage stability, processability, pressure resistance, antifungal / antibacterial properties, antistatic properties and coating properties as appropriate for each layer. -1 to F-17, and iron salt, lead salt, gold salt, platinum salt, palladium salt, iridium salt, rhodium salt.

In Table 3,
(1) Emulsions J to L were reduction sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-91938.
(2) Emulsions A to I were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. Has been.
(3) In preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426.
(4) Dislocation lines as described in JP-A-3-237450 are observed in tabular grains using a high-voltage electron microscope.
(5) Emulsion L is a double-structured grain containing an internal high iodine core as described in JP-A-60-143331.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 below was dispersed by the following method. That is, 21.7 ml of water and 3 ml of 5% aqueous solution of p-octylphenoxyethoxyethoxyethane sulfonic acid soda and 5 g of 5% aqueous solution of p-octylphenoxypolyoxyethylene ether (polymerization degree 10) 0.5 g are added to a 700 ml pot mill. Then, 5.0 g of dye ExF-2 and 500 ml of zirconium oxide beads (diameter 1 mm) were added, and the contents were dispersed for 2 hours. A BO-type vibrating ball mill manufactured by Chuo Koki was used for this dispersion. After the dispersion, the contents were taken out and added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle diameter of the dye fine particles was 0.44 μm.

  Similarly, solid dispersions of ExF-3, ExF-4, and ExF-6 were obtained. The average particle diameters of the dye fine particles were 0.24 μm, 0.45 μm, and 0.52 μm, respectively. ExF-5 was dispersed by the microprecipitation dispersion method described in Example 1 of European Patent Application Publication (EP) No. 549,489A. The average particle size was 0.06 μm.

Reference Example 6
A sample was prepared by adding 5 × 10 ⁻² mol of the compounds 4, 27 and 28 of the present invention to 4th, 5th and 6th layers of the sample 101 of JP-A-6-118533 and Example 1, respectively. This sample was allowed to stand for 7 days under a forced deterioration condition of 50 ° C. and 60% after exposure, and then evaluated by performing color reversal processing described in JP-A-6-118533, p37-38. The compound of the present invention was added. The light-sensitive material exhibited favorable performance in that the increase in sensitivity when left after exposure was small and the decrease in the maximum color density was small compared to the light-sensitive material not added.

Reference Example 7
Preparation of Emulsion A A container containing 25 g of potassium bromide, 15 g of potassium iodide, 1.9 g of potassium thiocyanate, and 24 g of gelatin in 1 liter of water is kept at 60 ° C., and the ordinary ammonia method is used. A silver nitrate aqueous solution and a potassium bromide aqueous solution were added by double jet to prepare a relatively plate-like thick silver iodobromide emulsion having an iodine content of 10 mol% and an average grain size of 1.0 μm. Thereafter, the temperature was lowered to 35 ° C., and soluble salts were removed by the coagulation sedimentation method. Then, the temperature was raised to 40 ° C. and 82 g of gelatin was added, and the pH was adjusted to 6.40 and pAg 8.80 with sodium hydroxide and sodium bromide. . After raising the temperature to 61 ° C., 0.95 g of 2-phenoxyethanol was added, and 213 mg of sensitizing dye-A shown below was further added. Ten minutes later, sodium thiosulfate pentahydrate 1.2 mg, potassium thiocyanate 28 mg, and chloroauric acid 0.4 mg were added. After 65 minutes, the mixture was rapidly cooled to solidify.

Preparation of Emulsion B A container containing 25 g of potassium bromide, 9 g of potassium iodide, 7.6 g of potassium thiocyanate, and 24 g of gelatin in 1 liter of water is kept at 40 ° C. and stirred with vigorous stirring. A silver nitrate aqueous solution and a potassium bromide aqueous solution were added by a double jet method to prepare a relatively amorphous silver iodobromide emulsion having an iodine content of 6 mol% and an average grain size of 0.6 μm. Thereafter, the temperature was lowered to 35 ° C., and soluble salts were removed by a sedimentation method. Then, the temperature was raised to 40 ° C., 110 g of gelatin was added, and the pH was adjusted to 6.60 and pAg 8.90 with sodium hydroxide and sodium bromide. After raising the temperature to 56 ° C, 0.8 mg chloroauric acid, 9 mg potassium thiocyanate, 4 mg sodium thiosulfate were added. After 55 minutes, 180 mg of Dye-A was added, and 10 minutes later, it was quenched and solidified.

Preparation of coated sample Prepared by the production method described in Japanese Patent Application Laid-Open No. Sho 62-1115035, the emulsion coating surface is pre-drawn in advance,
Compound-I 60 mg / m ²
Diacetylcellulose 143 mg / m ²
Silicon oxide 5 mg / m ²

The following layers were applied on a triacetylcellulose support on which a coating was applied to prepare a coated sample 601.

First layer (Anti-halation layer)
Gelatin 1.0 g / m ²
Compound-II 140 mg / m ²
Compound-III 15 mg / m ²
Dye-I 26 mg / m ²
Dye-II 16 mg / m ²

Second layer (intermediate layer)
Gelatin 0.4 g / m ²
Polypotassium-p-vinylbenzenesulfonate 5 mg / m ²

Third layer (emulsion layer)
Emulsion B Silver coating amount 1.36 g / m ²
Gelatin 2.0 g / m ²
4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 15 mg / m ²
C ₁₈ H ₃₅ O (CH ₂ CH ₂ O) ₂₅ H 10 mg / m ²
Compound-IV 1.5 mg / m ²
Polypotassium-p-vinylbenzenesulfonate 50 mg / m ²
Bis- (vinylsulfonylacetamide) ethane 65 mg / m ²

Fourth layer (emulsion layer)
Emulsion A Amount of coated silver 4.2 g / m ²
Gelatin 6.5 g / m ²
Dextran (average molecular weight 150,000) 1.2 g / m ²
4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 41 mg / m ²
C ₁₈ H ₃₅ O (CH ₂ CH ₂ O) ₂₅ H 23 mg / m ²
Trimethylolpropane 500 mg / m ²
Polypotassium-p-vinylbenzenesulfonate 88 mg / m ²
Polyacrylic acid 54 mg / m ²

5th layer (surface protective layer)
Gelatin 0.8 g / m ²
Compound-V 13 mg / m ²
Compound-VI 50 mg / m ²
Compound-VII 1.8 mg / m ²
Polypotassium-p-vinylbenzenesulfonate 6 mg / m ²
Polymethylmethacrylate fine particles (average particle size 3μm) 24 mg / m ²
Compound-VIII 50 mg / m ²

  18.9 g of Compound 4 of the present invention, 19.0 g of poly-t-butylacrylamide (molecular weight 100,000), 9.5 g of high boiling point organic solvent (Sovl-1), 38.0 g of surfactant (W-1) In addition to 300 cc of ethyl acetate, it was dissolved by heating. This was added to a 10% gelatin aqueous solution, and emulsified and dispersed with a home mixer for 10 minutes. This emulsion was added to the third and fourth layers of Sample 601 so that Compound 4 of the present invention was 0.1 mol with respect to 1 mol of Ag to prepare Sample 603. A sample obtained by removing only the compound 4 of the present invention from the emulsion of the sample 603 was used as a sample 602, and a sample obtained by using the compound 27 instead of the compound 4 of the present invention was used as a sample 604. These samples were stored at 30 ° C. and 65% RH for 14 days after application. Each sample was tested in the following manner.

(1) Measurement of sensitivity Each sample was exposed for 1/100 second through an optical wedge. A tungsten light source with a color temperature of 2854K was passed through a color temperature change filter to obtain a color temperature of 5400K, and this was used to perform light wedge exposure. This was developed, fixed, washed and dried using an automatic processor. For each sample, a constant density (optical density of 0.5) higher than the fog density was measured using the same method to obtain sensitivity and fog. The development conditions are as follows.
Processing solution Temperature Time Development HPD 26.5 ° C 55 seconds Fixing Super Fujix DP2 26.5 ° C 76 seconds Washing Water 20 ° C 95 seconds Drying 50 ° C 69 seconds

  The photographic stability over time when the photosensitive material was left after photographing was evaluated by the following method. Samples 601 to 604 were exposed by the method described above, and then left for 14 days under conditions of 40 ° C. and 60% RH. This was processed and measured by the method described above. The results are shown in Table 4 as relative values for samples processed immediately after exposure. The closer this value is to 0, the smaller the change with time, which is preferable.

From Table 4, it is apparent that the photographic material containing the compound of the present invention is remarkably improved in photographic stability over time when left standing after photographing.
Reference Example 8
A sample 201 of Reference Example 5 was prepared in the same manner as the sample 201 of Reference Example 5 except that the compounds shown in Table 5 were added to the fourth, fifth, and ninth layers in the amounts shown in Table 5. The temporal change in photographic properties was evaluated in the same manner as in Reference Example 2, but only the temporal conditions were 35 ° C. and 60% for one month. As is apparent from Table 5, the light-sensitive material of the present invention is excellent in storage stability.

Claims (6)

A compound represented by the following general formula (II).

[In the general formula (II), ^{R 1} represents a substituted or unsubstituted alkyl group having 1 to 6 carbon ^{atoms, R a, R b, R} c, and R ^d represents a water MotoHara child, X is - represents oR ^{6, R 6} is a carbon number of 14-22 substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group having a carbon number of 14-22, or a substituted or unsubstituted aryl group having a carbon number of 14 to 22 Represents. ] In the general formula (II), R ⁶ The compound according to claim 1, wherein is a substituted or unsubstituted alkyl group having 14 to 22 carbon atoms. A compound represented by the following general formula (II).

[In general formula (II), R ¹ Represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ^a , R ^b , R ^c And R ^d Each independently may be the same or different and represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, or a substituted or unsubstituted alkenyl group having 2 to 18 carbon atoms, and X represents —OR ⁶ Represents R ⁶ Represents a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 22 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 22 carbon atoms. However, R ^a , R ^b , R ^c And R ^d Are not all hydrogen atoms. ] In general formula (II), R ⁶ The compound according to claim 3, wherein is a substituted or unsubstituted alkyl group having 6 to 22 carbon atoms or a substituted or unsubstituted alkenyl group having 6 to 22 carbon atoms. In general formula (II), R ⁶ The compound according to claim 3, wherein is a substituted or unsubstituted alkyl group having 14 to 22 carbon atoms or a substituted or unsubstituted alkenyl group having 14 to 22 carbon atoms. In general formula (II), R ⁶ The compound according to claim 3, wherein is a substituted or unsubstituted alkyl group having 14 to 22 carbon atoms.