Silver halide photographic sensitive material

Description: TECHNICAL FIELD [Detailed description of the invention]

【0001】

[Industrial application field]

The present invention relates to a silver halide photographic photosensitive material, and more particularly to a silver halide photographic photosensitive material having improved sticking property, scratch resistance and retouchability.

【0002】

[Conventional technology]

Silver halide color photo The so-called 220 type, which is a brownie size with a 6 cm wide slit of the photosensitive material and is wrapped without inserting a light-shielding paper, is a roll of the photosensitive material wrapped around the core, but the light-shielding paper is at the end. It is connected and attached, and after the shooting is completed, the light-shielding paper is wrapped around the top layer of the roll to block light. Therefore, if the light-shielding paper is loosely wrapped around the roll, light leakage will occur. To prevent this, the light-shielding paper is wrapped fairly tightly and sealed with a sticker to preserve the latent image. At this time, the side (emulsion surface) of the roll-shaped photosensitive material having the photographic constituent layer and the opposite side (backing surface) are in close contact with each other, and when left in a high temperature and high humidity atmosphere for a long time, the emulsion surface and the backing surface are in close contact with each other. Is adhered to the emulsion surface, and a ferro surface is generated on the emulsion surface, which causes uneven printing. Also, during shooting, dust in the film chamber inside the camera adheres to the emulsion surface and backing surface and is wound up on the roll as it is. If this dust moves while being strongly pressed between the emulsion surface and the backing surface in the roll, it causes scratches. It is considered that the smoother the outermost surface of the film is, the less the scratches are generated. In order to solve the problem of sticking and scratches, silica, titanium dioxide, magnesium oxide, polystyrene or polymethylpropio are applied to the outermost protective layer. A method is known in which fine particles called a matting agent such as nate are contained to form a so-called matte surface to reduce friction between sheets.

【0003】

However, if the amount of such a surface matting agent is increased to improve the matting property, scratches can be reduced and the sticking property can be improved, but the sharpness is deteriorated. In addition, in photo studios, etc., the image on the developed film may be directly modified (retouched), and this work involves spotting to fill in minute spots with dye etc. from the backing surface side, and images. Apply varnish to the corrected part of the image and write lightly with a correction pencil to correct the wrinkles and unevenness of the face. These operations are performed by a skilled retoucher, but there has been a complaint that if a surface matting agent is used on the outermost surface on the backing surface side in an amount effective against sticking and scratch resistance, retouching becomes difficult.

【0004】

[Problems to be Solved by the Invention]

The present invention has been made under the above circumstances, and an object of the present invention is to provide a silver halide photographic photosensitive material having improved sticking resistance, scratch resistance, and retouchability without impairing sharpness. To do.

【0005】

[Means for solving problems]

An object of the present invention is silver halide having a photographic constituent layer on one side of a transparent support and a layer containing matting particles having a monodisperse degree of 3.3 or less on the other side of the support. Photosensitive material, the matting agent particles are synthetic polymer particles represented by the general formula (1), the layer containing the matting agent particles is the outermost surface layer of the hydrophilic colloid layer, and on a transparent support. At least one red photosensitive layer, green photosensitive layer, blue photosensitive layer, and non-photosensitive layer are provided as photographic constituent layers on one side, and the outermost surface layer and the support on the photographic constituent layer side. It is achieved by a silver halide color photographic photosensitive material, in which the outermost surface layer on the other side above both contains matting particles having a monodispersity of 3.3 or less.

【0006】

That is, the present inventor has obtained the finding that surface physical properties, image sharpness and retouchability can be achieved at the same time by making the particle sizes of the matting agents uniform to some extent, and optimizes the dispersibility of the matting agent. The present invention has been achieved by finding a matting agent that is advantageous for the effect of the above.

【0007】

The matting agent according to the present invention will be described.

【0008】

In the present invention, the matting agent is water-insoluble or poorly water-soluble inorganic or organic particles. Examples of the inorganic particles include silica, colloidal silica, titanium oxide, glass powder, barium sulfate and the like. Examples of the organic particles include synthetic polymers such as polystyrene, polymethylmethacrylate, polycarbonate and polyacrylate copolymers, and natural products such as starch and cornstarch. In particular, the acrylic acid ester-acrylic acid copolymer is useful because it can be completely removed, partially removed, or left in the developing process by adjusting its molar ratio. In the present invention, it is preferable that at least a part of the residue remains.

【0009】

In the present invention, the monodispersity of matting agent particles is the equivalent sphere diameter (ΣNV) as measured by the Coulter counter.²It is a value expressed by the standard deviation / average particle size ratio calculated based on / ΣNV). In the present invention, the monodispersity of the matting agent particles is 3.3 or less, preferably 3.0 or less, and particularly preferably 2.8 or less.

【0010】

A particularly preferable matting agent in the present invention is represented by the general formula (1).

【0011】

[Chemical 2]

<img file="JPH095918A_D0001.tif" />【0012】

In the formula, R₁, R₂, R₃Represents a hydrogen atom, an alkyl group (methyl group, ethyl group, etc.) or an aryl group (phenyl group, etc.), respectively. R₄, R₅Are alkyl groups (methyl group, ethyl group, 2-methoxyethyl group, 2-hydroxyethyl group, i-propyl group, n-butyl group, t-butyl group, 2-ethylhexyl group, etc.), aryl group (phenyl group, etc.), respectively. , P-tolyl group, p-methoxyphenyl group, naphthyl group, etc.) or heterocyclic group (imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, pyridyl group, thiazolyl group, oxazolyl group, frill group, etc.). M represents a hydrogen atom or a cation (sodium ion, potassium ion, lithium ion, ammonium ion, etc.). x, y, z represent the molar ratio of each ethylenically unsaturated compound, z / (x + y) &lt;0.30, preferably z / (x + y) &lt;0.20, more preferably 0.05 &lt;z / ( x + y) &lt;0.12. If the value of z / (x + y) is 0.05 or less, agglutination of the matting agent is likely to occur, which is not preferable, and if it is 0.30 or more, the residue after the development treatment is too small and the physical characteristics after the development treatment are deteriorated.

【0013】

Specific examples of the preferred matting agent particles in the present invention are shown below together with the composition ratio (mol).

【0014】

MMA EMA BMA MAA AA P-1 100 P-2 90 10 P-3 85 10 5 P-4 85 10 5 P-5 80 10 10 P-6 80 10 10 P-7 70 10 20 P-8 75 25 P-9 70 20 10 P-10 60 30 10 P-11 60 20 10 10 Here, MMA stands for methyl methacrylate, EMA stands for ethyl methacrylate, BMA stands for butyl methacrylate, MAA stands for methacrylic acid, and AA stands for acrylic acid.

【0015】

In the present invention, the average particle size of the matting agent is preferably 0.5 μm or more and 20 μm or less, more preferably 1 μm or more and 10 μm or less, and particularly preferably 1.5 μm or more and 5 μm or less.

【0016】

The matting agent of the present invention can be synthesized by the methods described in US Pat. Nos. 4,301,240, 3,767,448, 2,992,101, JP-A-60-126644 and the like.

【0017】

In the present invention, the degree of polymerization of the matting agent is preferably 3,000 to 1,000,000, more preferably 5,000 to 50,000, as an average molecular weight. The amount of the matting agent of the present invention added is 1 m.²It is 1 mg or more and 80 mg or less, preferably 3 mg or more and 60 mg or less. If it is less than 1 mg, the effect of the present invention is not exhibited, and if it is more than 80 mg, the physical characteristics of the coating film are significantly impaired.

【0018】

In the present invention, any known method may be used to adjust the monodispersity of the matting agent particles. For example, the method for dispersing photographic additives described in Japanese Patent Application Laid-Open No. 3-296045 can be used. Further, the so-called classification shown in Japanese Patent Application Laid-Open No. 5-289225 may be performed, but it is not preferable because it requires complicated operations in manufacturing and has a large amount of discarded parts and a low yield. In the present invention, the nozzle ejection method is effective. That is, it is a method of ejecting a solution of a copolymer dissolved in a low boiling point organic solvent (ethyl acetate, butanol, etc.) into agitated water from a fine nozzle having a controlled diameter at a constant speed. Further, the temperature in water, stirring conditions, addition of a protective colloidal agent or surfactant to water, salts, the temperature and concentration of the copolymer solution, the ejection speed and the like can be appropriately adjusted. By this method, not only the average particle size but also the monodispersity can be effectively adjusted.

【0019】

As commercially available products, acrylic polymer particles Mx-150, 300, 500, etc. manufactured by Soken Chemical Co., Ltd. can also be used.

【0020】

Japanese Patent Application Laid-Open No. 5-289225 describes a monodisperse matting agent as a silver halide color photosensitive material for movies. This is an invention made with the intention of preventing the occurrence of Newton's rings and the deterioration of graininess in close contact printing, and improves the sticking property without impairing the sharpness, reduces scratches, and further improves the retouchability. The present invention is intended to have a different purpose and use.

【0021】

In the present invention, the matting agent is contained in at least one layer constituting the backing surface, but it is preferable to contain it in the hydrophilic colloid layer in terms of dispersibility and the like, and the hydrophilic colloid layer is the outermost surface layer. In this case, it is advantageous for the effect of the present invention, and it is more advantageous to include the matting agent of the present invention not only on the outermost surface of the backing surface but also on the outermost surface layer on the side having the photographic constituent layer.

【0022】

As the hydrophilic colloid used as the binder of the backing layer, gelatin such as so-called lime-treated gelatin, acid-treated gelatin, enzyme-treated gelatin, gelatin derivative and modified gelatin (most preferably lime-treated gelatin and acid-treated gelatin); Proteins such as colloidal albumin and casein; Sugar derivatives such as agar, sodium alginate and starch derivatives; Cellulous compounds such as carboxymethyl cellulose and hydroxymethyl cellulose; Synthetic hydrophilic compounds such as polyvinyl alcohol, poly-N-vinylpyrrolidone and polyacrylamide Can be mentioned.

【0023】

In the present invention, the hydrophilic colloid backing layer includes dyes, pigments, hard film agents, surfactants, plasticizers, slip agents, matting agents, polymer latex, antistatic agents, ultraviolet absorbers, and oxidations, in addition to binders. Additives having various functions for improving the quality of photographic photosensitive materials such as inhibitors, thickeners, preservatives, and colloidal silica can be included. For these additives, for example, the description in Research Disclosure (RD), Vol. 176, p. 17643 (December 1978) can be referred to.

【0024】

When the photosensitive material of the present invention is a color photosensitive material, it has at least a red photosensitive layer, a blue photosensitive layer, a green photosensitive layer and a non-sensitive layer as photographic constituent layers, but Research Disclosure (RD) 308119 VII -As described in Section K, auxiliary layers such as a filter layer and an intermediate layer can be provided, and various layer configurations such as a forward layer, a reverse layer, and a unit configuration can be adopted.

【0025】

The following compounds can be used in the silver halide emulsion of the silver halide photographic photosensitive material of the present invention.

【0026】

[table 1]

<img file="JPH095918A_D0002.tif" />【0027】

Known photographic additives that can be used in the present invention are also described in these RDs, and the related description points are shown below.

【0028】

[Items] [Page of RD308119] [RD17643] [RD18716] Color turbidity inhibitor 1002 VII-I Section 25 650 Dye Image Stabilizer 1001 VII-J Section 25 Whitening agent 998 V 24 UV absorber 1003 VIIIC, XIII-C Section 25 ~ 26 Light absorber 1003 VIII 25 ~ 26 Light scatterer 1003 VIII Filter dye 1003 VIII 25 ~ 26 Binder 1003 IX 26 651 Antistatic agent 1006 XIII 27 650 Dural agent 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricant 1006 XII 27 650 Activator / application aid 1005 XI 26 ~ 27 650 Developer (contained in sensitive material) Item 1011 XXB In addition, the description of RD is shown for the couplers that can be used.

【0029】

[Items] [Page of RD308119] [RD17643] Yellow coupler 1001 VII-D VII C ~ G Magenta coupler 1001 VII-D VII C ~ G Cyan coupler 1001 VII-D VII C ~ G Colored coupler 1002 VII-G VII G DIR Coupler 1001 VII-F VII F BAR coupler 1002 VII-F term Other useful residues 1001 Section VII-F Emission coupler Alkali-soluble coupler 1001 VII-E The additive used in the present invention can be added by the dispersion method described in RD308119, page 1007, section XIV.

【0030】

In the present invention, the supports described in RD17643, pp. 28, RD18716, 647-8, and RD308119, 1009, XIX, described above can be used.

【0031】

When the present invention is adopted as a color photosensitive material, it is applied to various color photosensitive materials typified by a color negative film for general use or a movie, a color inversion film for slides or television, a color paper, a color positive film, and a color inversion paper. can do.

【0032】

In order to obtain a dye image using the photosensitive material of the present invention, a commonly known color development process can be performed after exposure.

【0033】

The photosensitive material of the present invention can be developed by the usual methods described in RD17643 pages 28-29, RD18716647 and RD308119 XIX described above.

【0034】

As the hydrophilic colloid used as a binder for the backing layer containing the matting agent of the present invention, gelatin such as so-called lime-treated gelatin, acid-treated gelatin, enzyme-treated gelatin, gelatin derivative and modified gelatin (most preferably lime is used). Treated gelatin and acid-treated gelatin); Proteins such as colloidal albumin and casein; Sugar derivatives such as agar, sodium alginate and starch derivatives; Cellulous compounds such as carboxymethyl cellulose and hydroxymethyl cellulose; Polyvinyl alcohol, poly-N-vinylpyrrolidone, poly Examples thereof include synthetic hydrophilic compounds such as acrylamide.

【0035】

In the present invention, the hydrophilic colloid backing layer containing a matting agent includes dyes, pigments, hardeners, surfactants, plasticizers, slip agents, polymer latex, antistatic agents, and ultraviolet absorbers in addition to binders. , Antioxidants, thickeners, preservatives, colloidal silica and other additives with various functions for improving the quality of photographic photosensitive materials can be included. For these additives, for example, the description in RD 176, Vol. 1764 (December 1978) can be referred to.

【0036】

[Example]

Hereinafter, the present invention will be described in detail with reference to examples, but the embodiments of the present invention are not limited thereto.

【0037】

Example 1 A backing layer was formed by applying in order from the support side to one side of a 100 μm-thick cellulose triacetate film support provided with undercoat layers on both sides.

【0038】

Backing surface hydrophilic colloid 1st layer Gelatin 8.5g / m² Surfactant (SU-1) 10 mg / m² Dural agent (H-1) 2 mg / m² Dural agent (H-2) 38 mg / m²Backing surface hydrophilic colloid second layer Gelatin 1.45g / m² Matte (P-1, average particle size 3 μm, monodispersity 3.7) 15 mg / m² Surfactant (SU-1) 13 mg / m² Surfactant (SU-5) 9.4mg / m² Fluorosurfactant (SU-6) 2.3mg / m² Dural agent (H-1) 15 mg / m² Dural agent (H-2) 23 mg / m²Next, the following compositions were applied in order from the support side to the side of the support opposite to the backing layer side to prepare Sample 101, which is a multilayer color photosensitive material.

【0039】

Here, the amount added to the silver halide photographic photosensitive material is 1 m unless otherwise specified.²Shows the number of grams per hit. Further, silver halide and colloidal silver were shown in terms of silver, and the sensitizing dye was shown in terms of the number of moles per mole of silver halide.

【0040】

First layer: Antihalation layer Black colloidal silver 0.18 UV absorber (UV-1) 0.30 High boiling organic solvent (Oil-1) 0.37 Gelatin 1.59 Second layer: Intermediate layer Gelatin 1.27 Layer 3: Low-sensitivity red-sensitivity layer Silver bromide emulsion A 0.63 Sensitive Dye (SD-1) 1.7 × 10^-4 Snare Dye (SD-2) 1.5 × 10^-4 Sensitive Dye (SD-3) 1.5 × 10^-4 Sensitive Dye (SD-4) 1.3 × 10^-5 Cyan coupler (C-1) 0.71 Colored cyan coupler (CC-1) 0.09 DIR compound (D-1) 0.005 High boiling solvent (Oil-1) 0.65 Gelatin 2.05 Layer 4: Medium-sensitivity red-sensitivity layer Silver bromide emulsion B 0.71 Snare Dye (SD-2) 2.5 × 10^-4 Sensitive Dye (SD-3) 1.4 × 10^-5 Sensitive Dye (SD-4) 2.2 × 10^-4 Cyan coupler (C-1) 0.27 Colored cyan coupler (CC-1) 0.04 DIR compound (D-1) 0.01 High boiling solvent (Oil-1) 0.32 Gelatin 0.83 Layer 5: High-sensitivity red-sensitivity layer Silver bromide emulsion C 1.52 Sensitive Dye (SD-2) 2.1 × 10^-4 Sensitive Dye (SD-3) 1.2 × 10^-5 Sensitive Dye (SD-4) 1.8 × 10^-4 Cyan coupler (C-2) 0.13 DIR compound (D-2) 0.009 High boiling solvent (Oil-1) 0.17 Gelatin 1.04 Layer 6: Intermediate layer High boiling organic solvent (Oil-1) 0.50 Gelatin 1.00 Layer 7: Low-sensitivity green-sensitive layer Silver bromide emulsion A 0.76 Sensitive Dye (SD-1) 6.5 × 10^-4 Sensitive Dye (SD-9) 7.2 × 10^-5 Sensitive Dye (SD-13) 7.5 × 10^-5 Magenta coupler (M-1) 0.10 Magenta coupler (M-2) 0.25 Colored magenta coupler (CM-1) 0.11 DIR compound (D-1) 0.004 DIR compound (D-3) 0.013 High boiling solvent (Oil-2) 0.49 Gelatin 1.10 8th layer: Medium-sensitivity green sensibility layer Silver bromide emulsion B 0.55 Sensitive dye (SD-1) 5.2 × 10^-4 Sensitive Dye (SD-9) 5.8 × 10^-5 Sensitive Dye (SD-13) 5.0 × 10^-5 Magenta coupler (M-1) 0.07 Magenta coupler (M-2) 0.17 Colored magenta coupler (CM-1) 0.08 DIR compound (D-1) 0.002 High boiling solvent (Oil-2) 0.33 Gelatin 0.78 9th layer: High-sensitivity green sensibility layer Silver bromide emulsion C 0.82 Sensitive Dye (SD-6) 1.4 × 10^-4 Sensitive Dye (SD-7) 1.5 × 10^-4 Sensitive Dye (SD-8) 1.4 × 10^-4 Magenta coupler (M-2) 0.10 Magenta coupler (M-3) 0.03 Colored magenta coupler (CM-2) 0.03 DIR compound (D-1) 0.001 DIR compound (D-3) 0.004 High boiling solvent (Oil-2) 0.31 Gelatin 0.91 Layer 10: Intermediate layer High boiling organic solvent (Oil-1) 0.30 gelatin 0.50 11th layer: Yellow filter layer Yellow colloidal silver 0.08 Color Contamination Inhibitor (SC-1) 0.08 High boiling solvent (Oil-2) 0.10 Gelatin 1.00 12th layer: Intermediate layer Gelatin 0.50 Layer 13: Low-sensitivity blue-sensitive layer Silver bromide emulsion A 0.16 Sensitive Dye (SD-9) 1.7 × 10^-4 Sensitive Dye (SD-10) 4.0 × 10^-4 Sensitive Dye (SD'-1) 3.1 × 10^-6 Yellow coupler (Y-1) 0.24 Yellow coupler (Y-2) 0.66 Gelatin 1.19 14th layer: Medium sensitivity blue sensitivity layer Silver bromide emulsion B 0.46 Sensitive Dye (SD-9) 1.3 × 10^-4 Sensitive Dye (SD-10) 3.0 x 10^-4 Sensitive dye (SD'-1) 1.6 x 10^-6 Yellow coupler (Y-1) 0.07 Yellow coupler (Y-2) 0.20 High boiling solvent (Oil-2) 0.05 Gelatin 0.84 Layer 15: High-sensitivity blue-sensitive layer Silver bromide emulsion D 0.41 Sensitive Dye (SD-9) 0.9 × 10^-4 Sensitive Dye (SD-11) 2.0 x 10^-4 Sensitive dye (SD'-1) 1.0 x 10^-6 Yellow coupler (Y-1) 0.06 Yellow coupler (Y-2) 0.18 High boiling solvent (Oil-2) 0.05 Gelatin 0.97 16th layer: 1st protective layer Silver iodide emulsion (average particle size 0.04 μm, silver iodide content 4.0 mol%) 0.30 UV absorber (UV-2) 0.030 UV absorber (UV-3) 0.015 UV absorber (UV-4) 0.015 UV absorber (UV-5) 0.015 UV absorber (UV-6) 0.10 High boiling solvent (Oil-2) 0.07 High boiling solvent (Oil-3) 0.07 Gelatin 1.44 17th layer: 2nd protective layer Polymethylmethacrylate (average particle size 3 μm, P-1, monodispersity 3.7) 0.04 Slipper (WAX-1) 0.04 gelatin 0.55 In addition to the above compositions, compounds SU-1, SU-2, SU-3, SU-4, SU-5, SU-6, viscosity modifier V-1, dural agent H-1, H-2 , Stabilizer ST-1, Anti-fog agent AF-1, AF-2, AF-3, Dye AI-1, AI-2, AI-3, Compound FS-1, FS-2, and Preservative DI-1 Was appropriately added to each layer.

【0041】

The structure of the compound used in the above sample is shown below.

【0042】

[Chemical 3]

<img file="JPH095918A_D0003.tif" />【0043】

[Chemical 4]

<img file="JPH095918A_D0004.tif" />【0044】

[Chemical 5]

<img file="JPH095918A_D0005.tif" />【0045】

[Chemical 6]

<img file="JPH095918A_D0006.tif" />【0046】

[Chemical 7]

<img file="JPH095918A_D0007.tif" />【0047】

[Chemical 8]

<img file="JPH095918A_D0008.tif" />【0048】

[Chemical 9]

<img file="JPH095918A_D0009.tif" />【0049】

[Chemical 10]

<img file="JPH095918A_D0010.tif" />【0050】

[Chemical 11]

<img file="JPH095918A_D0011.tif" />【0051】

[Chemical 12]

<img file="JPH095918A_D0012.tif" />【0052】

[Chemical 13]

<img file="JPH095918A_D0013.tif" />【0053】

[Chemical 14]

<img file="JPH095918A_D0014.tif" />【0054】

The emulsion used for the above sample is as follows. The average particle size is shown as a cube-converted particle size. Emulsion A contains 1 x 10 iridium^-7Contains 1 mol / mol of silver. When emulsion B was observed with an electron microscope, 5 or more transition lines were observed both in the fringe portion of 80% or more (number) of particles and inside the particles. In addition, each emulsion was optimally sensitized with gold and sulfur.

【0055】

[Table 2]

<img file="JPH095918A_D0015.tif" />【0056】

Table 3 shows the matting agent type, monomer composition ratio (molar ratio of the ethylenically unsaturated compound of MAA, AA to MMA, EMA, BMA), dispersity, and addition amount of the hydrophilic colloid second layer of the backing surface of Sample 101. Samples 102 to 110 were prepared in the same manner except that they were changed as described above. The degree of dispersion was changed by classification by centrifugation.

【0057】

[Table 3]

<img file="JPH095918A_D0016.tif" />【0058】

To evaluate the stickiness, prepare four 3.5 cm x 7.0 cm small pieces of each sample with no scratches or dust on both the emulsion surface and the backing surface, stack them in the same direction, and sandwich them with thick paper of the same size. After stopping with a rubber band, the sample was left to stand in an atmosphere of 55 ° C and 80% RH for 3 days, and the ratio (%) of the sticking surface to the total area of the four small pieces for each sample was measured. The smaller the value, the better the stickiness.

【0059】

For the evaluation of scratch resistance, 220 types of brownie films were prepared. The obtained film is loaded into a medium format camera (Mamiya Optical; Mamiya RB67), wound up while shooting to the end of the film, taken out from the camera after winding up, wrapped with shading paper with a force of 5 kg, and then roller support type. Development processing was performed with a developing machine (manufactured by Noritsu Tsuna Ki Co., Ltd .; FRP-1125). Observe 6 frames of the area (1 frame) where the negative image of the developed sample is reflected with a loupe, visually observe scratches with a length of 5 mm or more and a width of 0.2 mm or more, and average the 6 frames to scratch the sample. It was used as an index of ease of attachment.

【0060】

Regarding retouchability, we prepared a sample cut to a length of 10.0 cm and a width of 12.5 cm, and asked five experts who are actually retouching the sheet-like film at the photofinishing laboratory by spotting and pencil correction. We requested the ease of retouching on a 5-point sensory evaluation. The evaluation value of each sample was the average of the scores of 5 people.

【0061】

Standard color development processing Processing process Processing time Processing temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C 780cc Bleaching 45 seconds 38 ± 2.0 ° C 150cc Settlement 1 minute 30 seconds 38 ± 2.0 ° C 830cc Settlement 60 seconds 38 ± 5.0 ° C 830cc Dry 1 minute 55 ± 5.0 ° C- * Replenishment amount is 1m of photosensitive material²It is a winning value.

【0062】

The following were used as the color developing solution, the bleaching solution, the fixing solution, the stabilizing solution and the replenishing solution thereof.

【0063】

Color developer Water 800cc Potassium carbonate 30g Sodium bicarbonate 2.5g Potassium sulfite 3.0g Sodium bromide 1.3g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5g Sodium chloride 0.6g 4-Amino-3-methyl-N-Ethyl-N- (β-Hydroxyethyl) Aniline Sulfate 4.5g Diethylenetriamine pentaacetic acid 3.0g Potassium hydroxide 1.2g Add water to make 1 liter and use potassium hydroxide or 20% sulfuric acid to pH 10.06 Adjust to.

【0064】

Color development replenisher Water 800cc Potassium carbonate 35g Sodium bicarbonate 3g Potassium sulfite 5g Sodium bromide 0.4g Hydroxylamine sulfate 3.1g 4-Amino-Methyl-N-Ethyl-N-Aniline Sulfate (β-Hydroxyethyl) 6.3g Potassium hydroxide 2g Diethylenetriamine pentaacetic acid 3.0g Add water to make 1 liter and adjust to pH 10.18 with potassium hydroxide or 20%. Arrange.

【0065】

Bleach Water 700cc 1,3 Diaminopropane Iron (III) Ammonium Tetraacetate 125g Ethylenediaminetetraacetic acid 2g Sodium nitrate 40g Ammonium bromide 150g Glacial acetic acid 40g Add water to make 1 liter and adjust to pH 4.4 with aqueous ammonia or glacial acetic acid. ..

【0066】

Bleach replenisher Water 700cc 1,3 Diaminopropane Iron (III) Ammonium Tetraacetate 175g Ethylenediaminetetraacetic acid 2g Sodium nitrate 50g Ammonium bromide 200g Glacial acetic acid 56g After adjusting to pH 4.4 with aqueous ammonia or glacial acetic acid, add water to make 1 liter.

【0067】

Fixer Water 800cc Ammonium thiocyanate 120g Ammonium thiosulfate 150g Sodium sulfite 15g Ethylenediaminetetraacetic acid 2g After adjusting to pH 6.2 with aqueous ammonia or glacial acetic acid, add water to make 1 liter.

【0068】

Fixing replenisher Water 800cc Ammonium thiocyanate 150g Ammonium thiosulfate 180g Sodium sulfite 20g Ethylenediaminetetraacetic acid 2g After adjusting to pH 6.5 with aqueous ammonia or glacial acetic acid, add water to make 1 liter.

【0069】

Stabilizer and stable replenisher Water 900cc Paraoctyl phenyl polyoxyethylene ether (n = 10) 2.0g Dimethylolurea 0.5g Hexamethylenetetramine 0.2g 1,2-benzoisothiazolin-3-one 0.1 g Siloxane (UCC L-77) 0.1g Ammonia water 0.5cc After adding water to make 1 liter, adjust the pH to 8.5 with aqueous ammonia or 50% sulfuric acid.

【0070】

The above results are shown in Table 4.

【0071】

[Table 4]

<img file="JPH095918A_D0017.tif" />【0072】

Example 2 Sample 201 in the same manner except that the polymethylmethacrylate matte agent of the 17th layer (second protective layer) on the photographic constituent layer side of Sample 104 of Example 1 was replaced with P-2 having a monodispersity of 3.0 with an equivalent addition amount. Was produced.

【0073】

When evaluated in the same manner as in Example 1, the sticking resistance was further improved to 9.2. That is, it can be seen that the effect of the present invention is further exhibited by adopting the monodisperse matting agent of the present invention on the outermost surface layers of both the backing layer side and the photographic constituent layer side.

【0074】

[Effect of the invention]

The photosensitive material according to the present invention has improved sticking resistance, scratch resistance, and retouchability without impairing sharpness.