JP3005822B2 - Image forming method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide color light-sensitive material related to (hereinafter, simply color photographic material and it is abbreviated) imaging how using <br/> a more particularly developed with high image quality Image formation method using color photosensitive material with excellent processing stability
About the law.

[0002]

BACKGROUND OF THE INVENTION In recent years, miniaturization of cameras has progressed, portability has been improved, and opportunities for taking pictures have greatly increased. However,
Further miniaturization is desired by users, and miniaturization while maintaining high image quality has been widely studied. At present, a 135-size roll film for general use is loaded in a standard-format patrone, which is an obstacle to miniaturization of cameras. In order to reduce the size of the patrone, it is most effective and simple to make the film, that is, the photosensitive material thinner, and it can be achieved by making the thickness of the support of the photosensitive material thinner than the conventional thickness of about 120 μm. . However, by thinning the support, the balance between the physical properties of the support and the photographic component layer is lost,
It became clear that curling, cracking, film peeling, wrinkles, etc. occurred, and further, light pumping from the tongue end of the photosensitive material became remarkable, and undesired fog occurred.

On the other hand, when a thin color light-sensitive material for photography is exposed and developed and then printed on a color light-sensitive material having a silver chloride content of 80 mol% or more, which has rapid processing suitability, a high density of a printed image is obtained. We found a defect that the image quality of the part deteriorated. In addition, a color light-sensitive material for photography having a thin support and a color light-sensitive material for printing having a silver chloride content of 80 mol% or more are used in an automatic developing machine of a system in which at least one of the developing solutions is shared. In this case, when the continuous processing is performed, the disadvantage that the density fluctuation of the print image is large is found.

[0004] Improvements in the above problems are desired.

[0005]

Accordingly, an object of the present invention is an object of the invention, without degrading the physical properties, is to provide an image forming how using excellent color photosensitive materials in the stability of the image density at high quality.

[0006]

The object of the present invention has been attained by the following constitutions.

[0007]

( 1 ) In an image forming method for printing a silver halide color light-sensitive material for photography after imagewise exposing and developing the silver halide color light-sensitive material for printing, the silver halide color light-sensitive material for photography is characterized by Photograph of at least one red-sensitive layer, green-sensitive layer, blue-sensitive layer and non-light-sensitive layer on one side of a transparent support having a transmittance at a wavelength of 550 nm of 80 to 90% and a thickness of 100 μm or less, respectively. A photosensitive layer having a constitutional layer, wherein the thickness of the photographic constitutional layer at 23 ° C. and a relative humidity of 60% is 20 μm or less, and wherein the silver halide color photosensitive material for printing has a silver chloride content of 80 mol% or more. have a, for further shooting
Silver halide color light-sensitive materials and silver halide for printing
Used for developing color photosensitive materials
The image forming method in which at least 10 mole percent and wherein the same der Rukoto of a color developing agent that.

( 2 ) The silver halide color light-sensitive material for photographing and the silver halide color light-sensitive material for printing both contain a magenta coupler represented by the following general formula [MI]. 1 ) The image forming method according to the above.

[0010]

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In the formula, Z represents a group of nonmetal atoms necessary for forming a nitrogen-containing heterocyclic ring, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent. R represents a hydrogen atom or a substituent.

In the present invention, both the color light-sensitive material for photographing and the color light-sensitive material for printing are represented by the general formula [M-
Inclusion of the magenta coupler represented by the formula (I) contributes to improvement in color reproducibility.

Hereinafter, the magenta coupler represented by the general formula [MI] will be described.

In the general formula [MI], the substituent represented by R is not particularly limited, and typically represents a substituent such as alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl and the like. Each group is mentioned, but in addition to these, a halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl,
Sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy,
Heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido,
Sulfamoylamino, alkoxycarbonylamino,
Examples include aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, and heterocyclicthio groups, as well as spiro compound residues and bridged hydrocarbon compound residues.

A substituent represented by R, a group capable of leaving by reaction with an oxidized color developing agent represented by X, a nitrogen-containing heterocyclic ring formed by Z and a ring formed by Z may be present. Preferred ranges and specific examples of the substituents, and preferred ranges of the magenta coupler represented by the general formula [MI] are those described in EP 0327272, page 5, line 23 to page 8, line 52. Is the same.

The following are representative specific examples of the magenta coupler represented by the general formula [MI].

[0017]

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[0018]

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[0019]

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As other specific examples of the above-mentioned typical specific examples, among the compounds described on pages 63 to 82 of Japanese Patent Application No. 2-218720, there are no. 13, 34, 42, 57 to 59, 61, 6
Compounds represented by 2,65 to 67, EP-A-0327272
Among the compounds described on pages 10 to 28, No. 3,5
-20,22-33,35-60,62-77 and the compounds described in JP-A-0235913, pages 36-92, Nos. 1-4,6,8-17, 19-24, 26-43, 45-5
There are compounds represented by 9,61-104,106-121,123-162,164-223.

[0021] The coupler can be used in the Journal of the Chemical Soy
ciety), Perkin I (1977), 2047-2052, U.S. Pat. No. 3,725,067, JP-A-59-99437, and JP-A-58-42045.
No. 59-162548, No. 59-171956, No. 60-33552, No.
60-43659, 60-172982, 60-190779, 62-20945
No. 7, 63-307453 and the like can be synthesized.

The above-mentioned couplers can be used in combination with other types of magenta couplers, and usually from 1 × 10 ⁻³ mol to 1 mol, preferably from 1 × 10 ⁻² mol to 8 × 10 ⁻ mol per mol of silver halide. It can be used in the range of ¹ mol.

In the present invention, the spectral transmittance of a support having a thickness of 100 μm or less is 80 to 90% at 550 nm, preferably 83 to 90%, particularly preferably 85 to 90%. If it is less than 80%, the image quality, particularly the color reproducibility, deteriorates, and the printing time on a color light-sensitive material for printing is undesirably long. If it exceeds 90%, fogging occurs due to light pumping from the tongue end of the film, and when printed on a color photosensitive material for printing having a silver chloride content of 80 mol% or more, high density of printed images is obtained. Deterioration of the image quality, in which the detail of the portion becomes unclear, occurs, and furthermore, if the development and printing are continuously performed, the density fluctuation of the print increases. The spectral transmittance of the support of the present invention can be adjusted using a known dye or pigment, but it is preferable to use an organic dye.

In the present invention, the thickness of the support is 100 μm or less, preferably 50 to 90 μm, particularly preferably 55 to 8 μm.
5 μm.

The present invention has at least one red-sensitive layer, green-sensitive layer, blue-sensitive layer and non-photosensitive layer on one side of the transparent support, The purpose is achieved by a color photographic material for photography having a thickness of 20 μm or less at 60 ° C. and 60% relative humidity, but the thickness of the support is 100 μm or less, and the relative humidity of the multilayer photographic constituent layers is 60% at 23 ° C. The structure of the present invention in which the thickness at 20 mm is 20 μm or less has not been conventionally known.

In the present invention, the thickness of the photographic constituent layer is 20 μm.
m or less, preferably 12 to 20 μm, particularly preferably
14-18 μm. When the thickness is less than 12 μm or more than 20 μm, the effect of the present invention is small.

As the support of the present invention, a cellulose ester film, a polyester film, a polycarbonate film and the like are preferably used. In particular, a cellulose triacetate film, a polyethylene terephthalate film,
Polyethylene naphthalate films are preferred.

The halogen composition of the color light-sensitive material for printing of the present invention has a silver chloride content of 80 mol% or more, preferably 90 mol% or more, particularly preferably 95 to 100 mol%. Silver bromide is preferred as silver halide other than silver chloride.

In the method for developing a color light-sensitive material for photography and a color light-sensitive material for printing according to the present invention, at least 10 parts of a color developing agent in a color developing solution used for each of them.
Although the mol% is the same, it is preferably at least 30 mol%, particularly preferably at least 70 mol%. Most preferably, the color developing solution for the photographic color photographic material and the color photographic material for printing are common and are processed in the same processing bath, or the color developing solution for the photographic color photographic material is used. And a method of supplying one of the color developing solutions for the color light-sensitive material for printing to the other. By using the method of the present invention, the image quality of the high-density portion, which is generated when printing from a thin support photographic color photosensitive material to a printing color photographic material having a silver chloride content of 80 mol% or more, is reduced. Can be prevented. Further, a color light-sensitive material for photography and a color light-sensitive material for printing containing a magenta coupler represented by the general formula [MI] are used in an automatic developing machine of a system in which at least one of the processing solutions is shared. By performing the continuous processing, it is possible to prevent the disadvantage that the density fluctuation of the print image is large. The color developing agent used in the present invention is preferably represented by the following general formula [D].

[0030]

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In the formula, R ₁ , R ₂ , and R ₃ may be the same or different and each represents a methyl group, an ethyl group, a propyl group,
Represents a hydroxyethyl group, a sulfoalkyl group or a β-methanesulfonamidoethyl group. Where R ₁ , R ₂ , R
_At least one of ₃ is a β-methanesulfonamidoethyl group. X represents sulfuric acid, hydrochloric acid, p-toluenesulfonic acid or phosphoric acid.

Preferred compounds represented by the general formula [D] are shown below, but are not limited thereto.

Compound R ₁ R ₂ R ₃ X D-1-C ₂ H ₅ -CH ₂ CH ₂ NHSO ₂ CH ₃ -CH ₃ 3 / 2H ₂ SO ₄ .H ₂ O D-2 -CH ₃ -CH ₂ CH ₂ NHSO ₂ CH ₃ -CH ₃ HCl D-3 -CH ₂ CH ₂ NHSO ₂ CH ₃ -CH ₂ CH ₂ NHSO ₂ CH ₃ -CH ₃ 3 / 2H ₂ SO ₄・ H ₂ O D-4 -CH ₃ -CH ₃ -CH ₂ CH ₂ NHSO ₂ CH ₃ 2PTS D-5 -C ₂ H ₅ -C ₂ H ₅ -CH ₂ CH ₂ NHSO ₂ CH ₃ 3 / 2H ₂ SO ₄・ H ₂ O D-6 -CH ₂ CH ₂ OH -CH ₂ CH ₂ NHSO ₂ CH ₃ -CH ₃ H ₂ SO ₄ D-7 -C ₃ H ₇ -CH ₂ CH ₂ NHSO ₂ CH ₃ -CH ₃ HCl D-8 -CH ₂ CH ₂ SO ₃ H -CH ₂ CH ₂ NHSO ₂ CH ₃ -CH ₃ 1 / 2H ₂ SO ₄ D-9 -C ₂ H ₅ -CH ₂ CH ₂ NHSO ₂ CH ₃ -C ₂ H ₅ HCl where PTS is p-toluene Represents sulfonic acid.

Among the compounds represented by the general formula [D], D-1 is particularly preferably used.

These compounds are used at a concentration of preferably 1.0 × 10 ^-2 mol or more per liter of the color developing solution, but from the viewpoint of the effect of the present invention, from 1.5 × 10 ^-2 to 1 × 10 ^-2 mol.
^-1 mol is more preferred, especially 1.7 × 10 ^{-2 to} 5.0 ×
It is preferred to use a concentration of 10 ^-2 molar.

In the present invention, it is preferable that at least the color developing bath is shared, and other processing baths such as a stop bath, a bleach bath, a bleach-fix bath, a fixing bath, a stabilizing bath, a conditioning bath, and a hardening bath are used. These treatment baths may be separated, but it is preferable that some or all of these other treatment baths are also shared.

In the development processing method of the present invention,
60-129741, 60-129748, 60-147148, 61-13
No. 4759, JP-A-1-154153, JP-A-1-244449, etc., in some or all of the processing steps, a photographing color photosensitive material and a printing color photosensitive material, in the same processing solution tank. Techniques for completing the processing can be used. If these proposals can be realized, only one processing device is required, and the installation space is greatly reduced. Further, since the type of the processing liquid to be used is also reduced, the stock space of the processing liquid is greatly reduced, and the operation can be simplified.

In the present invention, a silver halide emulsion which has been subjected to physical ripening, chemical ripening and spectral sensitization is used.
Additives used in such a process are described in Research Disclosure No. 17643, No. 18716 and No. 308119 (hereinafter abbreviated as RD17643, RD18716 and RD308119, respectively).

The following table shows the locations.

[Items] [RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A 23 648 Spectral sensitizer 996 IV-AA, B, C, D, H, H, I , J section 23-24 648-9 Supersensitizer 996 IV-AE, J section 23-24 648-9 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI Known photographs usable in the present invention Additives for use are also described in Research Disclosure, supra. The following table shows relevant descriptions.

[Item] [Page of RD308119] [RD17643] [RD18716] Anti-turbidity agent 1002 VII-I 25 650 Dye image stabilizer 1001 VII-J 25 Brightener 998 V 24 UV absorber 1003 VIII- C, XIIIC 25-26 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Static inhibitor 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricant 1006 XII 27 650 Activator / Coating aid 1005 XI 26-27 650 Matting agent 1007 XVI Developer (contained in photosensitive material) 1011 XXB Section Various couplers can be used in the present invention. Specific examples are described in the above-mentioned Research Disclosure. The following table shows relevant descriptions.

[Item] [Page of RD308119] [RD17643] Yellow coupler 1001 VII-D VIIC-G Magenta coupler 1001 VII-D VIIC-G Cyan coupler 1001 VII-D VIIC-G Colored coupler 1002 VII-G VIIG DIR coupler 1001 VII-F VIIF BAR coupler 1002 VII-F Other useful residues 1001 VII-F Emission coupler Alkali-soluble coupler 1001 VII-E Additive used in the present invention Can be added by a dispersion method described in RD308119XIV or the like.

In the present invention, the aforementioned RD17643, page 28, RD1
Auxiliary layers such as filter layers and intermediate layers described in pages 8716 647-8 and RD308119, section XVII-K can be provided.

The light-sensitive material of the present invention is obtained by using the above-mentioned RD308119VII-
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in the section K can be adopted.

The present invention can be applied to ordinary color negative films and color reversal films as photographing color photosensitive materials, and can be applied to ordinary color paper and color reversal paper as printing color photosensitive materials.

The light-sensitive material of the present invention is described in RD17643, p.
The development processing method described in XIX, page 18716, 647 and RD308119 can also be used.

[0047]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these examples.

(Production of a support) 100 parts of cellulose triacetate having a degree of acetylation of 61.4% and triphenyl phosphate 15
Was completely dissolved in 738 parts of a mixed solvent consisting of methylene chloride-methyl alcohol, and the following organic dyes (a), (b), and
(c) was added in different amounts to obtain a dope.

[0049]

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Next, each dope was filtered, kept at 27 ° C., uniformly cast on a rotating endless stainless steel band of 6 m (effective length 5.5 m), and the solvent was evaporated until the solvent could be peeled off. It was peeled off from the band and dried to obtain a cellulose triacetate base having a thickness and a spectral transmittance as shown in Table 1.

On the surface of each base, 20 g of gelatin and 4 g of water
An undercoat layer coating solution consisting of 0 g, 20 g of salicylic acid, 600 g of methanol, 1200 g of acetone and 200 g of methylene chloride was applied and dried.

[0052] In all the following examples, the amount of the silver halide photographic light-sensitive material is shown in particular in grams per 1 m ² unless otherwise noted. Silver halide and colloidal silver are shown in terms of silver.

Example 1 On the back surface of a triacetylcellulose film support, layers having the following compositions were sequentially formed from the support side.

Backside first layer alumina sol AS-100 (aluminum oxide) 0.8 g (manufactured by Nissan Chemical Industries, Ltd.) Backside second layer diacetylcellulose 100 mg Stearic acid 10 mg Silica fine particles (average particle size 0.2 μm) 50 mg On the surface of the acetylcellulose film support, each layer having the following composition was sequentially formed from the support side to prepare a multilayer color photographic light-sensitive material sample 101.

First layer: Antihalation layer (HC) Black colloidal silver 0.15 g UV absorber (UV─1) 0.20 g Compound (CC-1) 0.02 g High boiling solvent (Oil─1) 0.20 g High boiling solvent ( Oil-2) 0.20 g gelatin 1.6 g Second layer: intermediate layer (IL # 1) Gelatin 1.3 g Third layer: low-sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (average grain size 0.3 μm, average iodine Content: 2.0 mol%) 0.4 g silver iodobromide emulsion (average grain size: 0.4 μm, average iodine content: 8.0 mol%) 0.3 g sensitizing dye (S─1) 3.2 × 10 ^-4 (mol / silver 1) Mol) Sensitizing dye (S─2) 3.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S─3) 0.2 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C─1) 0.50 g Cyan coupler (C─2) 0.13 g Colored cyan coupler (CC─1) 0.07 g DIR compound (D─1) 0.006 g DIR compound (D─2) 0.01 g High boiling solvent (Oil─1) 0.55 g Gelatin 2.0 g 4th : High sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (average particle size 0.7 [mu] m, an average iodide content of 7.5 mol%) 0.9 g Sensitizing dye (S─1) 1.7 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S # 2) 1.6 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S # 3) 0.1 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C # 2) 0.23 g Colored cyan coupler (CC # 1) 0.03 g DIR compound (D # 2) 0.02 g High boiling solvent (Oil # 1) 0.25 g Gelatin 2.0 g Fifth layer: Intermediate layer (IL # 2) Gelatin 0.8 g Sixth Layer: Low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (average grain size 0.4 μm, average iodine content 8.0 mol%) 0.6 g Silver iodobromide emulsion (average grain size 0.3 μm, average iodine content Amount 2.0 mol%) 0.2 g Sensitizing dye (S # ⁴ ) 6.7 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S # 5) 0.8 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (M─1) 0.17g Magenta coupler (M─2) 0.43g Color Magenta coupler (CM # 1) 0.10g DIR compound (D # 3) 0.02g High boiling point solvent (Oil # 2) 0.7g Gelatin 2.0g 7th layer: High sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion ( Average particle size 0.7 μm, average iodine content 7.5 mol%) 0.9 g Sensitizing dye (S─6) 1.1 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S─7) 2.0 × 10 ^-4 (Mol / silver 1 mol) Sensitizing dye (S # 8) 0.3 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (M # 1) 0.30 g Magenta coupler (M # 2) 0.13 g Colored magenta coupler (CM ─1) 0.04 g DIR compound (D─3) 0.004 g High boiling solvent (Oil─2) 0.35 g Gelatin 2.0 g Eighth layer: Yellow filter layer (YC) Yellow colloidal silver 0.1 g Additive (HS-1) 0.07 g Additive (HS-2) 0.07 g Additive (SC-1) 0.12 g High boiling solvent (Oil # 2) 0.15 g Gelatin 1.0 g Ninth layer: low-sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide milk 0.25 g silver iodobromide emulsion (average particle size 0.4 μm, average iodine content 8.0 mol%) 0.25 g sensitizing dye (S─9 5.8 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y # 1) 0.6g Yellow coupler (Y # 2) 0.32g DIR compound (D # 1) 0.003g DIR compound (D # 2) 0.006g High Boiling point solvent (Oil # 2) 0.18 g Gelatin 2.0 g Tenth layer: high-sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (average grain size 0.8 μm, average iodine content 8.5 mol%) 0.5 g sensitized Dye (S─10) 3.0 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S─11) 1.2 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y (1) 0.18 g Yellow coupler ( Y─2) 0.10 g High boiling point solvent (Oil─2) 0.05 g Gelatin 2.0 g 11th layer: 1st protective layer (PRO─1) Fine grain silver iodobromide (average particle size 0.08 μm) 0.3 g UV absorber ( UV─1) 0.07g UV absorber ( V─2) 0.10 g Additive (HS-1) 0.2 g Additive (HS-2) 0.1 g High boiling solvent (Oil─1) 0.07 g High boiling solvent (Oil─3) 0.07 g Gelatin 0.8 g 12th layer : Second protective layer (PRO─2) Compound A 0.04 g Compound B 0.004 g Polymethyl methacrylate (average particle size 3 μm) 0.02 g Methyl methacrylate: ethyl methacrylate: methacrylic acid = 3: 3: 4 (weight ratio) weight Coalescence (average particle size: 3 μm) 0.13 g Gelatin 0.5 g The silver iodobromide emulsion used in the tenth layer was prepared by the following method.

A silver iodobromide emulsion was prepared by a double jet method using monodispersed silver iodobromide grains having an average particle diameter of 0.33 μm (silver iodide content: 2 mol%) as seed crystals.

Solution <G-1> was heated to a temperature of 70 ° C., pAg 7.8, pH 7.0.
, And a seed emulsion equivalent to 0.34 mol was added with good stirring.

(Formation of Internal High Iodine Phase-Core Phase-) Then, while maintaining the flow ratio of <H-1> and <S-1> at 1: 1, the accelerated flow rate (the flow rate at the end is reduced). 3.6 of initial flow rate
) And added over 86 minutes.

(Formation of External Low Iodine Phase—Shell Phase) Subsequently, while maintaining pAg 10.1 and pH 6.0, <H-2> and <S-2
Was added at a flow rate accelerated at a flow ratio of 1: 1 (the flow rate at the end was 5.2 times the initial flow rate) over 65 minutes.

The pAg and pH during particle formation were controlled using an aqueous potassium bromide solution and a 56% acetic acid aqueous solution. After the particles are formed, the particles are subjected to a water washing treatment by a conventional flocculation method, and then gelatin is added and redispersed.
pAg was adjusted to 5.8 and 8.06, respectively. The resulting emulsion was a monodisperse emulsion containing octahedral silver iodobromide grains having an average grain size of 0.80 μm, a distribution width of 12.4% and a silver iodide content of 8.5 mol%.

<G-1> Ossein gelatin 100.0 g Compound-I 25.0 ml 28% ammonia aqueous solution 440.0 ml 56% acetic acid aqueous solution 660.0 ml Finished with water 5000.0 ml Compound-I: polyethyleneoxy-polypropylene oxysuccinate 2Na salt 10 % Ethanol solution <H-1> Ossein gelatin 82.4g Potassium bromide 151.6g Potassium iodide 90.6g Finish with water 1030.5ml <S-1> Silver nitrate 309.2g 28% ammonia aqueous solution Equivalent with water 1030.5ml <H-2 > Ossein gelatin 302.1 g Potassium bromide 770.0 g Potassium iodide 33.2 g Finished with water 3776.8 ml <S-2> Silver nitrate 1133.0 g 28% ammonia aqueous solution Equivalent finished with water 3776.8 ml In the same way, average particle size of seed crystal , Temperature, pAG, pH,
The above emulsions having different average grain sizes and silver iodide contents were prepared by changing the flow rate, addition time and halide composition.

Each was a core / shell type monodisperse emulsion having a distribution area of 20% or less. Each emulsion was subjected to optimal chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate to give a sensitizing dye, 4-hydroxy-6-
Methyl-1,3,3a, 7-tetrazaindene and 1-phenyl-5-mercaptotetrazole were added.

[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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The sample 101 described above further contains the compound SU-
1, SU-2, a viscosity modifier, a hardener H-1, H-2, a stabilizer ST-1, an antifoggant AF-1, AF-2 (with a weight average molecular weight of 10,000 and 1,100,000), Dye AI-1, A
Contains I-2 and compound DI-1 (9.4 mg / m ² ).

[0073]

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On the other hand, the photographic constituent layer of Sample 101 (23 ° C., 60% R
The thickness of the third layer, the fourth layer, the sixth layer, the seventh layer, and the tenth layer having a thickness of 21 μm in H was 1.0 g / m ^2, and the gelatin coating amount of the ninth layer was 1.3 g / m ^2. Sample 102 was prepared in the same manner as Sample 101, except that g / m ² was used. Hereinafter, as shown in Table 1, samples 103 to 120 were prepared by changing the type of the support and the thickness of the photographic constituent layer.

[0075]

[Table 1]

<Evaluation of Physical Properties> Each of the samples 101 to 120 was cut into a 35 mm width and a 1.2 m length, and a perforation hole of 135 size standard was provided. It was wound on a spool having an outer diameter of 7 mm and loaded on a metal cartridge having an inner diameter of 23 mm.

<Evaluation of curl> After each sample was left in an atmosphere of 30 ° C. and 20% RH for 6 hours, the film was pulled out of the patrone, cut into a length of 20 cm, placed on a horizontal surface, and the degree of curl was visually observed. evaluated. The results are shown in Table 2.

×: The curl is remarkable. Δ: The curl is large. ○: The curl is small. After the film was bent so as to have a curvature radius of 3 mm and left for 10 seconds, the surface of the photographic component layer was observed with a 20-power loupe to evaluate the degree of cracking. Second result
It is shown in the table.

X: Cracks are observed △: Extremely few cracks are observed ○: Cracks are hardly observed (Suitable for small patrone) Samples 101 to 120 are prepared in the same manner as for a small metallic patrone having an inner diameter of 17 mm. After loading, samples 101 to 105 could not be all loaded.
101 to 120 were subjected to white exposure through a step wedge for sensitometry and processed under the following conditions.

Processing step Processing time Processing temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C 780 ml Bleaching 45 seconds 38 ± 2.0 ° C 150 ml Set up 1 minute 30 seconds 38 ± 2.0 ° C 830 ml Stability 60 seconds 38 ± 5.0 ° C. 830 ml drying 1 min 55 ± 5.0 ℃ - * the replenishing amount is a value per photosensitive material 1 m ^2.

The following color developing solutions, bleaching solutions, fixing solutions, stabilizing solutions and replenishers were used.

Color developer water 800 ml Potassium carbonate 30 g Sodium bicarbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 g Hydroxylamine sulfate 2.5 g Sodium chloride 0.8 g 4-Amino-3-methyl-N- Ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Make up to 1000 ml with water, and adjust to pH 10.06 with potassium hydroxide or 20% sulfuric acid.

Color developing replenisher water 800 ml Potassium carbonate 35 g Sodium bicarbonate 3 g Potassium sulfite 5 g Sodium bromide 0.4 g Hydroxylamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl ) Aniline sulfate 6.3 g Potassium hydroxide 2.0 g Diethylenetriaminepentaacetic acid 3.0 g Add water to make 1000 ml, and adjust to pH 10.18 with potassium hydroxide or 20% sulfuric acid.

[0084]Bleach Water 700ml 1,3-Diaminopropanetetraacetate iron (III) ammonium 125g Ethylenediaminetetraacetic acid 2g Sodium nitrate 40g Ammonium bromide 150g Glacial acetic acid 40g Add water to 1000ml and adjust to pH 4.4 with ammonia water or glacial acetic acid I do. Bleach replenisher Water 700ml 1,3-diaminopropanetetraacetic acid iron (III) ammonium 175g ethylenediaminetetraacetic acid 2g sodium nitrate 50g ammonium bromide 200g glacial acetic acid 56g AndFixer Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2.0 g After adjusting the pH to 6.2 using aqueous ammonia or glacial acetic acid, add water to make 1000 ml.Fixer replenisher Water 800ml Ammonium thiocyanate 150g Ammonium thiosulfate 180g Sodium sulfite 20g Ethylenediaminetetraacetic acid 2.0g Adjust the pH to 6.5 with ammonia water or glacial acetic acid, and add water to make 1000ml.Stabilizer and replenisher Water 900 ml p-octylphenol / ethylene oxide 10 mol adduct 2.0 g dimethylol urea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzoisothiazolin-3-one 0.1 g siloxane (UCC L-77) 0.1 g ammonia water 0.5 ml water Add 1000 ml and add ammonia water or 50% sulfuric acid
Adjust to pH 8.5 using. Of each sample obtained by developing
Examination of the unexposed part revealed that some samples had light pie.
Uneven fogging that can be seen from ping is occurring
Was.

X: occurrence of uneven fog is observed Δ: slight occurrence of uneven fog is observed ○: occurrence of uneven fog is hardly observed Table 2 shows the results.

[0086]

[Table 2]

A light-sensitive material prepared in the same manner as in Sample 101, except that the first back surface layer and the second back surface layer of Sample 101 were changed to the following composition, also exhibited the effects of the present invention.

Back surface first layer ionene type polymer 2 g

[0089]

Embedded image

Back surface second layer diacetyl cellulose 107.6 mg Aerosil 200 (particle size: about 0.2 μm silica fine particles) 10.8 mg (manufactured by Nippon Aerosil Co., Ltd.) Citric acid half ethyl ester 6.4 mg Next, the following color photosensitive material for printing was prepared. did.

On a support in which polyethylene was laminated on one side of a paper support and polyethylene containing titanium oxide was laminated on the other side, each layer having the following constitution was placed on the side of the polyethylene layer containing titanium oxide. To prepare a multilayer silver halide color photographic light-sensitive material. The coating solution was prepared as follows.

First layer coating solution 26.7 g of yellow coupler (Y-1), 10.0 g of dye image stabilizer (ST-1), 6.67 g of dye image stabilizer (ST-2),
0.67 g of additive (HQ-1), anti-irradiation dye (A
I-3), 6.67 g of high boiling organic solvent (DNP) in 60 m of ethyl acetate
l, dissolve and add this solution to 20% surfactant (SU-1) 7
The resulting mixture was emulsified and dispersed in 220 ml of a 10% aqueous gelatin solution containing 2 ml using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.68 g of silver) prepared under the following conditions to prepare a first layer coating solution.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.

As a hardener, (H) was added to the second and fourth layers.
-3) and (H-1) were added to the seventh layer. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension.

[0095] The addition amount of the silver halide photographic light-sensitive material is, in particular, shows the number of grams per 1 m ² unless otherwise noted.

[0096]

[Table 3]

[0097]

[Table 4]

[0098]

Embedded image

[0099]

Embedded image

[0100]

Embedded image

[0101]

Embedded image

(Method for Preparing Blue-Sensitive Silver Halide Emulsion) 40
(A) in 1000 ml of a 2% aqueous gelatin solution kept at
Solution) and (solution B) while controlling pAg = 6.5 and pH = 3.0.
At the same time, and further add the following (Solution C) and (Solution D)
The co-addition was performed over 180 minutes while controlling pAg = 7.3 and pH = 5.5. The pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide. For control of pAg, a control solution having the following composition was used.

The composition of the control solution was a mixed halide salt aqueous solution composed of sodium chloride and potassium bromide. The ratio of chloride ion to bromide ion was 99.8: 0.2, and the concentrations of the control solution were A solution and B solution. 0.1 mol / l when mixing
When mixing the solution D and the solution D, it was 1 mol / l.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to make 200 ml. (Solution B) 10 g of silver nitrate was added to make up to 200 ml. (Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Water was added to make up to 600 ml. (D solution) Silver nitrate 300g Water was added to make up to 600ml. After completion of the addition, desalting was performed uniformly using a 5% aqueous solution of Demol N manufactured by Kao Atlas Co. and a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to have a mean particle size of 0.85 μm, a coefficient of variation of 0.07, and silver chloride. Monodisperse cubic emulsion with a content of 99.5 mol%
EMP-1 was obtained. The emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compounds to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-16 6 × 10 ^-4 mol / mol AgX Sensitizing dye BS-14 4 × 10 ^-4 mol / mol AgX Dye-sensitive dye BS-2 1 × 10 ^-4 mol / mol AgX (Preparation method of green-sensitive silver halide emulsion) (solution A) and (B
Liquid) and the addition time of (liquid C) and (liquid D) in the same manner as EMP-1 except that the average particle diameter was 0.43 μm.
A monodispersed cubic emulsion EMP-2 having a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol% was obtained.

EMP-2 at 55 ° C. using the following compounds
After 120 minutes of chemical ripening, a green-sensitive silver halide emulsion (Em-
G) was obtained.

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Stabilizer STAB-16 × 10 ^-4 mol / mol AgX Sensitizing dye GS-14 4 × 10 ^-4 mol / mol AgX ( Preparation Method of Red-Sensitive Silver Halide Emulsion) (A Solution) and (B)
Liquid) and the addition time of (Liquid C) and (Liquid D) in the same manner as EMP-1 except that the average particle size was 0.50 μm.
A monodispersed cubic emulsion EMP-3 having a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol% was obtained.

EMP-3 at 60 ° C. using the following compounds
For 90 minutes with a red-sensitive silver halide emulsion (Em
-R).

Sodium thiosulfate 1.8 mg / mol AgX Chloroauric acid 2.0 mg / mol AgX Stabilizer STAB-1 6 × 10 ^-4 mol / mol AgX Sensitizing dye RS-1 1 × 10 ^-4 mol / mol AgX Fluctuation The coefficient is a coefficient indicating the width of the particle size distribution, and is calculated by (standard deviation of particle size distribution) / (average particle size).

[0110]

Embedded image

Samples 103, 105, 106, 110, 112, 114 and 115
Against the MTF (Modulation Transfer Func) of the dye image
In order to determine the option, the sample was exposed to white light using a dedicated test pattern and subjected to the same development processing as described above. The MTF value of the processed sample was determined by green light using a Konica Micro Densitometer PDM-5.

Each sample had a magenta component of 15 lines / mm.
The MTF value was about 85 and there was no great difference.

Each of the above samples was used as a manuscript, and using the Konica Color Printer KCP-7N3, the print color photosensitive material was enlarged about three times and subjected to the following development processing.
Neutral gray MTF evaluation image samples 103 ', 105',
106 ', 110', 112 ', 114' and 115 'were obtained. The processing conditions are as follows.

Processing Step Temperature Time Color development 35.0 ± 0.3 ° C 45 seconds Bleaching and fixing 35.0 ± 0.5 ° C 45 seconds Stabilization 30-34 ° C 90 seconds Drying 60-80 ° C 60 seconds Color developer pure water 800ml Triethanol Amine 10g N, N-diethylhydroxylamine 5g Potassium bromide 0.02g Potassium chloride 2g Potassium sulfite 0.3g 1-Hydroxyethylidene 1,1-diphosphonic acid 1.0g Ethylenediaminetetraacetic acid 1.0g Catechol-3,5-disulfonic acid disodium salt 1.0 g Diethylene glycol 10 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.0 g Potassium carbonate 27 g Add water to bring the total volume to 1000 ml and adjust to pH = 10.10.

Bleaching / fixing solution Ferric ammonium ammonium diaminetetraacetate dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Water was added to make a total volume of 1000 ml, and potassium carbonate or potassium carbonate was added. Adjust to pH = 5.7 with glacial acetic acid.

Stabilizing solution 5-chloro-2-methyl-4-isothiazolin-3-one 0.2 g 1,2-benzisothiazolin-3-one 0.3 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0g o-Phenylphenol sodium 1.0g Ethylenediaminetetraacetic acid 1.0g Ammonium hydroxide (20% aqueous solution) 3.0g Fluorescent whitening agent (4,4'-diaminostilbene disulfonic acid derivative) 1.5g Add water to make the total volume 1000ml PH is adjusted to 7.0 with sulfuric acid or potassium hydroxide.

The MTF of the high density part of the magenta image of the obtained print sample was measured. However, for the MTF measurement, a reflection type Konica Micro Densitometer PDM-5 was used. Table 3 shows the relative values of the results at 3 lines / mm.

[0118]

[Table 5]

As is clear from Tables 1 to 3, the structure of the present invention is excellent in improving various problems when a thin support is used for miniaturizing a camera.

Example 2 The photographic color light-sensitive material sample 112 of Example 1 was 35 mm wide, 1
Cut 10 pieces at a length of 00ft to provide perforation, 13
The test pattern was continuously exposed according to the 5-size standard. on the other hand,
The printing color light-sensitive material of Example 1 was 89 mm wide and 80 m wide.
10 pieces were cut in length. After developing one of the exposed photographic color photosensitive materials with an automatic developing machine described below, the Konica Color Printer KCP7N3 type is loaded with the developed photographic color photosensitive material and an unexposed print color photosensitive material, and continuously. Printed. The automatic developing machine shown in FIG. 2 was used for developing the color light-sensitive material for photography and the color light-sensitive material for printing. The processing steps and processing conditions of the automatic developing machine are shown below.

Processing Step Processing Time Temperature Refill (m1 / m ² ) (a) 3 minutes 15 seconds 3. Color development phenomenon 38 ± 0.3 ° C 536 (b) 30 seconds 4. Bleaching 45 seconds 36 ± 2.0 ℃ 150 5. 5. 1 minute 30 seconds 36 ± 2.0 ℃ 500 First tank 30 seconds Stable 36 ± 5.0 ℃ 600 7． 7. Second tank 30 seconds Drying 1 minute 60 ± 5.0 ° C. In the above, (a) shows the processing conditions of the color light-sensitive material for photography, and (b) shows the processing conditions of the color light-sensitive material for printing.

The first and second stabilization tanks were of a counter current type, and the replenisher was replenished to the second tank.
The processing liquid used in each processing step is as follows.

Color developer water 800 ml Diethylene glycol 15 g Potassium bromide 23 mg Potassium chloride 3.3 g Potassium sulfite (50% solution) 0.5 ml Potassium carbonate 30 g Ethylenediaminetetraacetic acid 2.0 g N-ethyl-N-β-methanesulfonamidoethyl-3- Methyl-4-aminoaniline sulfate 5.0 g Diethylhydroxylamine 5.0 g Add water to make 1000 ml, and use potassium hydroxide or 20% sulfuric acid to adjust the pH to 10.05.
Adjust to.

Color developing replenisher water 800 ml Diethylene glycol 15 g Potassium bromide 11 mg Potassium chloride 3.0 g Potassium sulfite (50% solution) 0.5 ml Potassium carbonate 30 g Ethylenediaminetetraacetic acid 2.0 g N-ethyl-N-β-methanesulfonamidoethyl-3 -Methyl-4-aminoaniline sulfate 5.5 g Diethylhydroxylamine 7.0 g Add water to make 1000 ml, and adjust to pH 10.30 with potassium hydroxide or 20% sulfuric acid.

[0125]Bleach Water 700 ml 1,3-diaminopropanetetraacetic acid iron (III) ammonium 96 g ethylenediaminetetraacetic acid 2.0 g sodium nitrate 40 g ammonium bromide 150 g glacial acetic acid 40 g adjust. Bleach replenisher Water 700 ml 1,3-diaminopropanetetraacetic acid iron (III) ammonium 125 g ethylenediaminetetraacetic acid 2.0 g sodium nitrate 50 g ammonium bromide 200 g glacial acetic acid 56 g Adjust toFixer Water 800ml Ammonium thiocyanate 120g Ammonium thiosulfate 150g Sodium sulfite 15g Ethylenediaminetetraacetic acid 2.0g After adjusting the pH to 6.2 using aqueous ammonia or glacial acetic acid, add water to make 1000ml.Fixer replenisher Water 800ml Ammonium thiocyanate 150g Ammonium thiosulfate 180g Sodium sulfite 20g Ethylenediaminetetraacetic acid 2.0g Adjust the pH to 6.5 with ammonia water or glacial acetic acid, and add water to make 1000ml.Stabilizer and replenisher Water 900 ml p-octylphenol / ethylene oxide 10 mol adduct 1.0 g hexamethylenetetramine 1.0 g Add water to make 1000 ml, and adjust to pH 8.5 with ammonia water or 20% sulfuric acid. The development process is performed when the automatic developing machine is filled with the above color developer.
Both are filled with bleaching solution, fixing solution and stabilizing solution, and the sample is processed.
While the above color developing replenisher, bleach replenisher, fixing
Fill and stabilize the replenisher according to the above
Was done while refilling. The throughput of one sample is
Photosensitive material (a) / photosensitive material (b) = 1/6 (area ratio)
Continued processing.

On the other hand, as a comparative example, the color developing bath was separated into two parts, the above color developing solution was used as it was for a printing color photosensitive material, and the N-ethyl-N- (β-Methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate (color developing agent A) is equimolar to N-ethyl-N- (β-hydroxyethyl) -3-methyl-4-
Continuous processing was carried out in the same manner (in the same manner for the replenisher) except that aminoaniline sulfate (color developing agent B) was used.

Table 4 shows the results of statistically examining the variation in the density of the neutral gray step wedge image near the magenta density of 1.8 at 600 measurement points in the developed silver halide color photosensitive material for printing. .

[0128]

[Table 6]

The constitution of the present invention in which a color developing bath is used in common has a small variation in density, and a stable print can be obtained even if continuous processing is performed by an automatic developing machine that shares at least one of the developing solutions. Was. On the other hand, in the processing using different color developing agents, the density variation was large. Color developing agent B in color developing bath of color light-sensitive material for photography of comparative example
Was gradually replaced with a color developing agent A,
When the ratio of the color developing agent A exceeded 10 mol%, the variation in the density of the printed image was greatly improved. In addition, color expression
A for the image bath, the photographic material for printing is A, and the photographic material is A: B = 15:
Set the processing conditions to 85 and use the following combinations of
Was done. Photographic Print Comparative Example 1 Sample 112 Sample 25
High silver chloride paper samples of the present invention 112 examples of comparative ones were the silver chlorobromide Example 2 Sample 111 in Example of concentration variations in the combination of high silver chloride paper present invention was 0.10
On the other hand, in the combination of Comparative Examples 1 and 2,
3, 0.15 was shown.

[0130]

According to the present invention, a color photosensitive material for photographing which has high image quality and excellent image density stability without deteriorating physical characteristics.
An image forming method by providing by negative-positive system using a charge
Came. As a result, color photosensitive materials for photography and printing
It has become possible to developing processing efficiency rather good a.

[Brief description of the drawings]

FIG. 1 is a perspective view of a silver halide color light-sensitive material for photography mounted on a small patrone used in the present invention. FIG. 2 is a schematic view of an automatic developing machine used in the present invention.

[Explanation of symbols]

1. Color photosensitive material for photography 2. Spool
3. Patrone 11 ... Color photosensitive material insertion part for photography 12 ... Color photosensitive material insertion part for printing 13 ... Color developing bath 14 ... Bleaching bath
15: Fixing bath 16: Stabilizing bath (first tank) 17: Stabilizing bath (second tank) 18: Drying unit 19: Color photosensitive material collection unit for photography 20: Color photosensitive material collection unit for printing

Continuation of the front page (51) Int.Cl. ⁷ identification code FI G03C 7/413 G03C 7/413 (58) Investigated field (Int.Cl. ⁷ , DB name) G03C 1/795 G03C 7/00 510 G03C 7 / 00 520 G03C 7/413

Claims (2)

(57) [Claims] 1. A method for forming an image on a silver halide color light-sensitive material for printing after imagewise exposing and developing the light-sensitive silver halide color light-sensitive material for printing, the method comprising: On one side of a transparent support having a transmittance at 550 nm of 80 to 90% and a thickness of 100 μm or less, at least one red-sensitive layer, at least one green-sensitive layer,
A blue-sensitive layer and a non-photosensitive layer, wherein the thickness of the photographic layer at 23 ° C. and a relative humidity of 60% is 20 μm or less; It has a photosensitive layer of the above content of 80 mol%, still photographic halo
Silver halide color photosensitive material and silver halide color for printing
-When developing photosensitive materials,
The image forming method in which at least 10 mole percent and wherein the same der Rukoto color developing agent. 2. The silver halide color light-sensitive material for photographing and the silver halide color light-sensitive material for printing both contain a magenta coupler represented by the following general formula [MI]. 2. The image forming method according to 1 . Embedded image [In the formula, Z represents a group of nonmetal atoms necessary for forming a nitrogen-containing heterocyclic ring, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent. R represents a hydrogen atom or a substituent. ]