JPH06194782A - Method for applying photosensitive material - Google Patents

Abstract

PURPOSE:To improve productive efficiency by providing an uniform face having no color shade also in photosensitive material multilayer simultaneous application of 11 layers or more, thereby manufacturing color negative photosensitive materials of 11 layers or more which have been conventionally formed by application in two installments or more by one application without deteriorating photographic performance. CONSTITUTION:In the multilayer simultaneous application of 11 layers or more onto a continuously traveling support body by use of a slide bead applying device or a curtain applying device having a slide surface, for upper layers except the bottom layer, the applying liquid viscosity of the layer having a relatively smaller density between adjacent layers is set higher than the applying solution viscosity of the layer having a larger density, or, of unemulsified layers nipped by two adjacent emulsion layers, the viscosity of at least one layer is set larger than the viscosity of the emulsifier layer. The applying solution viscosity difference is preferably 10cp or more.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multi-layer simultaneous slide bead coating apparatus having 11 or more layers, a curtain coating apparatus having a sliding surface and a coating method, and more particularly to the production of a color photographic light-sensitive material.

[0002]

2. Description of the Related Art In recent years, a technique relating to a multi-layer simultaneous coating method comprising a plurality of layers has been highly developed in connection with the production of a silver halide photographic light-sensitive material which requires many thin layers. As such a multi-layer simultaneous coating method, a coating method using a slide hopper is adopted as a preferable method, and in the slide hopper method, how to increase the number of simultaneous coating layers is a problem from the viewpoint of improving production efficiency. It is considered to be one of

However, if an attempt is made to increase the number of simultaneous coating layers, uneven color density on the slide surface of the slide hopper is likely to be nonuniform, and it is extremely difficult to obtain a uniform coating surface state without color unevenness. Met. Therefore,
Conventionally, in the case of producing a color light-sensitive material having a large number of coating layers, particularly 11 layers or more, it is general to apply the coating twice or more times.

On the other hand, in JP-A-3-219237, the viscosity of the lowermost layer is 15 to 100 cp, and the viscosity of 30 to 100 cp is successively provided on the lowermost layer.
cp or more, and the arithmetic average viscosity of the coating liquid of 7 layers or more is 60
~ 300 cp is disclosed, and also JP-A-3-241338
No. 4-136844 discloses a method by improving the coating liquid formulation, but none of them is a sufficient countermeasure.

[0005]

As described in JP-A-3-219237, there are cases where it is effective to simply adjust the viscosity of each layer by lowering the viscosity of the lowermost layer in contact with the web and increasing the viscosity of the other layers. However, this alone does not necessarily prevent the waviness of the slide surface, and thus it is difficult to obtain a coated surface without color unevenness, and this becomes remarkable especially in the case of a multilayer such as 11 layers or more.

An object of the present invention is to solve the above-mentioned drawbacks of the prior art, and it is a technical object to obtain a uniform surface state without color unevenness by simultaneously coating multiple layers of 11 or more coating solutions. It is an issue. Thus, it is an object to improve the production efficiency by manufacturing the color negative photosensitive material of 11 layers or more, which has been conventionally coated in two or more times in a single coating, without deteriorating the photographic performance. .

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, a multilayer bead of 11 layers or more using a slide bead coating device or a curtain coating device having a sliding surface on a continuously running support. In simultaneous coating, for the upper layers except the lowermost layer, the viscosity of the coating liquid of the layer having a relatively low density between the adjacent layers should be made higher than the viscosity of the coating liquid of the layer having a high density, or sandwiched between two adjacent emulsion layers. The above-mentioned problems can be solved by a method for coating a light-sensitive material characterized by a method for coating a light-sensitive material characterized in that at least one of the non-emulsion layers is made to have a viscosity higher than that of the emulsion layer. The present invention has been completed and the present invention has been completed.

The difference in viscosity of the coating solution is preferably 10 cp or more.

The present invention will be specifically described below.

FIG. 1A shows a slide bead coating apparatus 1
It is sectional drawing which shows an example, and is a coating device which can coat two layers simultaneously. In the figure, a plurality of coating solutions 13 and 14 pass through a pocket 7 and a slit 4 extending in the width direction to reach a slide surface 5, and the coating solution flows down the slide surface to reach a tip (lip) 6 of an applicator. A web running while being held by the backup roll 1 via a liquid pool called a bead 12.
Applied on 10. FIG. 3 shows a decompression device for stabilizing the bead by pulling the bead downward.

Although FIG. 1A shows the case of two layers, the number of coating blocks may be increased when simultaneous coating of 11 layers or more is performed. Therefore, the slits will be 11 or more, the sliding surface will increase, and the liquid will also overlap.

Therefore, the number of superposed layers of the coating liquid on the slide surface gradually increases from the upstream side, and 11 or more liquid layers overlap on the most downstream side (slide surface near the lip). Disturbances and waviness are likely to occur.

FIG. 1 (b) shows an overlapping state of the coating liquids A, B and C flowing out from the slits on the slide surfaces.
As is clear from the figure, the upstream coating solution, for example, A, flows as a multi-layer while overcoming the downstream coating solution B and further B and C.

As a result of diligent studies by the present inventors, it has been found that, in the case of such a coating method, the main cause of the disturbance of the interface on the slide surface is the difference in interface density.

It is possible to prevent the interface from being disturbed to some extent by increasing the viscosity, but in the case of multi-layer coating of 11 or more layers as in the present invention, increasing the viscosity alone is not a sufficient measure. is there.

FIG. 2A is a graph showing the density of each layer in the layer structure of a general color photosensitive material consisting of 11 layers, and FIG. 2B is the case of a color photosensitive material also consisting of 15 layers. . As can be seen from the figure, there is a considerable difference in density between the layers, and especially the non-emulsion layers such as the first intermediate layer, the second intermediate layer, the yellow filter layer, the first protective layer, and the emulsion layer are greatly different in density. Of.

In such a structure, when multiple layers are simultaneously coated, the difference in the density of the interface becomes a problem with respect to the disturbance of the interface, and in particular, a non-emulsion layer (also referred to as an intermediate layer) sandwiched between emulsion layers.
Disturbance of the interface between the upper and lower emulsion layers is likely to occur.

In the present invention, as a measure against such a problem, the viscosity of the coating solution of the layer having a low density is made higher than that of the layer having a high density, or at least one of the above non-emulsion layers is used. It has been found that the problem can be solved by making the viscosity larger than the viscosity of the emulsion layers above and below it. At that time, it is more effective to set the viscosity difference to 10 cp or more. The coating speed in the present invention is 30 to 600 m / mi.
It is set in the range of n. Preferably, a speed of 40 to 400 m / min, more preferably 60 to 250 m / min is adopted.

The support used in the present invention is a transparent support such as polyethylene terephthalate and triacetyl cellulose, a reflective support such as polyethylene laminated paper and the like, and is not limited to a specific support.

[0020]

EXAMPLES Hereinafter, the effects of the present invention will be specifically illustrated by examples.

Regarding the coating layer in the present invention, the following 11
A layer, 15 layer recipe was used.

Unless otherwise specified, the amount of the composition added is the number of grams per 1 m ² . Further, silver halide and colloidal silver are shown in terms of silver. The sensitizing dye is shown in mol per mol of silver halide.

The viscosity was adjusted with an aqueous solution thickener containing styrene and a maleic acid sodium salt copolymer as a main component.

(11-layer formulation) First layer: antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling point solvent (Oil-1) 0.16 Gelatin 1.23 Second layer: First intermediate layer Compound (SC -1) 0.15 High boiling point solvent (Oil-2) 0.17 Gelatin 1.27 Third layer: Low sensitivity (first) red sensitive layer Silver iodobromide emulsion (average grain size 0.38 µm, silver iodide content 8.0 mol%) 0.50 (Average grain size 0.27 μm, silver iodide content 2.0 mol%) 0.21 Sensitizing dye (SD-1) 2.8 × 10 ⁻⁴ Sensitizing dye (SD-2) 1.9 × 10 ⁻⁴ Sensitizing dye (SD-3) ) 1.9 × 10 ^-5 Sensitizing dye (SD-4) 1.0 × 10 ^-4 Cyan coupler (C-1) 0.48 Cyan coupler (C-2) 0.14 Colored cyan coupler (CC-1) 0.021 DIR compound (D-1) ) 0.020 High boiling point solvent (Oil-1) 0.53 Gelatin 1.30 4th layer: High sensitivity (2nd) red sensitive layer Silver iodobromide emulsion (average grain size 1.00 μm Silver iodide content 8.0 mol%) 1.27 Cyan coupler (C-2) 0.12 Colored cyan coupler (CC-1) 0.013 High boiling point solvent (Oil-1) 0.14 Gelatin 0.91 Fifth layer: Second intermediate layer Compound (SC- 1) 0.09 High boiling point solvent (Oil-2) 0.11 Gelatin 0.80 Sixth layer: Low sensitivity (first) green sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content 8.0 mol%) 0.61 Iodine Silver bromide emulsion (average grain size 0.27 μm, silver iodide content 2.0 mol%) 0.20 Sensitizing dye (SD-4) 7.4 × 10 ⁻⁵ Sensitizing dye (SD-5) 6.6 × 10 ⁻⁴ Magenta coupler ( M-1) 0.18 Magenta coupler (M-2) 0.44 Colored magenta coupler (CM-1) 0.12 High boiling point solvent (Oil-2) 0.75 Gelatin 1.95 7th layer: High sensitivity (2nd) green sensitive layer Silver iodobromide emulsion (average grain size 1.00 .mu.m, a silver iodide content of 8.0 mol%) 1.27 sensitizing dye (SD-6) 9.4 × 10 -5 sensitizing dye (S -7) 9.4 × 10 ^-5 〃 (SD-8) 9.4 × 10 -5 Magenta coupler (M-2) 0.084 〃 (M-3) 0.064 Colored magenta coupler (CM-2) 0.012 High boiling solvent (Oil-1 ) 0.27 High boiling point solvent (Oil-2) 0.012 Gelatin 1.00 Eighth layer: Yellow filter layer Yellow colloidal silver 0.08 Color stain inhibitor (SC-2) 0.15 Formalin scavenger (HS-1) 0.20 High boiling point solvent (Oil-2) 0.19 Gelatin 1.10 Ninth layer: Low-sensitivity (first) blue-sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content 8.0 mol%) 0.22 Silver iodobromide emulsion (average grain size 0.27 μm, Silver iodide content 2.0 mol%) 0.03 Sensitizing dye (SD-9) 4.2 × 10 ^-4 Sensitizing dye (SD-10) 6.8 × 10 ^-5 Yellow coupler (Y-1) 0.75 DIR compound (D-1) ) 0.010 High boiling point solvent (Oil-2) 0.30 Gelatin 1.20 10th layer: High sensitivity (2nd) blue sensitive layer Iodobromide Emulsion (average grain size 1.00 .mu.m, a silver iodide content of 8.0 mol%) 0.85 Sensitizing dye (SD-9) 7.3 × 10 -5 Sensitizing dye (SD-11) 2.8 × 10 -5 Yellow coupler (Y-1 ) 0.11 High boiling point solvent (Oil-2) 0.046 Gelatin 0.80 11th layer: protective layer Silver iodobromide emulsion (average grain size 0.08 μm, silver iodide content 1.0 mol%) 0.40 UV absorber (UV-1) 0.026 Ultraviolet absorber (UV-2) 0.013 High boiling point solvent (Oil-1) 0.07 High boiling point solvent (Oil-3) 0.07 Formalin scavenger (HS-1) 0.40 Gelatin 1.31 Alkali soluble matting agent (average particle size 2 μm) 0.15 Polymethyl Methacrylate (average particle size 3 μm) 0.04 Lubricant (WAX-1) 0.04 Gelatin 0.55 Su-1 0.02 Su-2 0.03 H-1 0.024 H-5 0.046 H-9 0.010 (15 layer prescription) 1st layer: Antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling point Medium (Oil-1) 0.16 Gelatin 1.23 Second layer: First intermediate layer Compound (SC-1) 0.15 High boiling solvent (Oil-2) 0.17 Gelatin 1.27 Third layer: Low sensitivity (first) red-sensitive layer Iodour Silver halide emulsion (average grain size 0.38 μm, silver iodide content 8.0 mol%) 0.50 (average grain size 0.27 μm, silver iodide content 2.0 mol%) 0.21 Sensitizing dye (SD-1) 2.8 × 10 ^-4 Sensitizing dye (SD-2) 1.9 × 10 ^-4 Sensitizing dye (SD-3) 1.9 × 10 ^-5 Sensitizing dye (SD-4) 1.0 × 10 ^-4 Cyan coupler (C-1) 0.48 Cyan coupler ( C-2) 0.14 Colored cyan coupler (CC-1) 0.021 DIR compound (D-1) 0.020 High boiling point solvent (Oil-1) 0.53 Gelatin 1.30 4th layer: Medium sensitivity (2nd) red sensitive layer Silver iodobromide Emulsion (average grain size 0.52 μm, silver iodide content 8.0 mol%) 0.62 Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content 8.0 mol%) 0.27 Sensitizing dye (SD-1) 2.3 × 10 ^-4 sensitizing dye (SD-2) 1.2 × 10 ^-4 sensitizing dye (SD-3) 1.6 × 10 ^-5 sensitizing dye (SD-4) 1.2 × 10 ^-4 cyan coupler (C-1) 0.15 Cyan coupler (C-2) 0.18 Colored cyan coupler (CC-1) 0.030 DIR compound (D-1) 0.013 High boiling point solvent (Oil-1) 0.30 Gelatin 0.93 Fifth layer: High sensitivity (third) red sensitive layer Silver iodobromide emulsion (average grain size 1.00 μm, silver iodide content 8.0 mol%) 1.27 Cyan coupler (C-2) 0.12 Colored cyan coupler (CC-1) 0.013 High boiling point solvent (Oil-1) 0.14 Gelatin 0.91 Sixth layer: Second intermediate layer Compound (SC-1) 0.09 High boiling point solvent (Oil-2) 0.11 Gelatin 0.80 Seventh layer: Low sensitivity (first) green sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm , Silver iodide content 8.0 mol%) 0.61 silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content 2.0 mol%) 0.20 sensitizing dye (S -4) 7.4 × 10 ^-5 Sensitizing dye (SD-5) 6.6 × 10 -4 Magenta coupler (M-1) 0.18 Magenta coupler (M-2) 0.44 Colored magenta coupler (CM-1) 0.12 High boiling solvent ( Oil-2) 0.75 Gelatin 1.95 Eighth layer: Medium sensitivity (second) green sensitive layer Silver iodobromide emulsion (average grain size 0.59 μm, silver iodide content 8.0 mol%) 0.87 Sensitizing dye (SD-6) 1.6 × 10 ^-4 Sensitizing dye (SD-7) 1.6 × 10 ^-4 〃 (SD-8) 1.6 × 10 ^-4 Magenta coupler (M-1) 0.058 〃 (M-2) 0.13 Colored magenta coupler (CM- 2) 0.070 DIR compound (D-2) 0.025 DIR compound (D-3) 0.002 High boiling point solvent (Oil-2) 0.50 Gelatin 1.00 9th layer: High sensitivity (3rd) green sensitive layer Silver iodobromide emulsion (average) Grain size 1.00 μm, silver iodide content 8.0 mol%) 1.27 Sensitizing dye (SD-6) 9.4 × 10 ⁻⁵ Sensitizing dye (SD-7) 9.4 × 10 ⁻⁵ 〃 (SD-8) 9.4 × 10 ^-5 Magenta coupler (M-2) 0.084 〃 (M-3) 0.064 Colored magenta coupler (CM-2) 0.012 High boiling solvent (Oil-1) 0.27 High boiling solvent (Oil-) 2) 0.012 Gelatin 1.00 10th layer: Yellow filter layer Yellow colloidal silver 0.08 Color stain inhibitor (SC-2) 0.15 Formalin scavenger (HS-1) 0.20 High boiling point solvent (Oil-2) 0.19 Gelatin 1.10 11th layer: Low Sensitivity (first) blue-sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content 8.0 mol%) 0.22 Silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content 2.0 mol%) ) 0.03 Sensitizing dye (SD-9) 4.2 × 10 ^-4 Sensitizing dye (SD-10) 6.8 × 10 ^-5 Yellow coupler (Y-1) 0.75 DIR compound (D-1) 0.010 High boiling solvent (Oil- 2) 0.30 gelatin 1.20 12th layer: Medium sensitivity (2nd) blue-sensitive layer Silver iodobromide emulsion (average grain size 0.5 9 μm, silver iodide content 8.0 mol%) 0.30 Sensitizing dye (SD-9) 1.6 × 10 ⁻⁴ Sensitizing dye (SD-11) 7.2 × 10 ⁻⁵ Yellow coupler (Y-1) 0.10 DIR compound (D -1) 0.010 High boiling point solvent (Oil-2) 0.046 Gelatin 0.47 13th layer: High sensitivity (3rd) blue sensitive layer Silver iodobromide emulsion (average grain size 1.00 μm, silver iodide content 8.0 mol%) 0.85 Sensitizing dye (SD-9) 7.3 × 10 ^-5 Sensitizing dye (SD-11) 2.8 × 10 ^-5 Yellow coupler (Y-1) 0.11 High boiling solvent (Oil-2) 0.046 Gelatin 0.80 14th layer: Layer 1 Protective layer Silver iodobromide emulsion (average grain size 0.08 μm, silver iodide content 1.0 mol%) 0.40 UV absorber (UV-1) 0.026 UV absorber (UV-2) 0.013 High boiling point solvent (Oil-1) ) 0.07 High boiling point solvent (Oil-3) 0.07 Formalin scavenger (HS-1) 0.40 Gelatin 1.31 15th layer: 2nd protective layer Alkali-soluble matting agent (average particle size) Diameter 2 μm) 0.15 Polymethylmethacrylate (average particle size 3 μm) 0.04 Sliding agent (WAX-1) 0.04 Gelatin 0.55 Su-1 0.02 Su-2 0.03 H-1 0.024 H-9 0.010

[0025]

[Chemical 1]

[0026]

[Chemical 2]

[0027]

[Chemical 3]

[0028]

[Chemical 4]

[0029]

[Chemical 5]

[0030]

[Chemical 6]

[0031]

[Chemical 7]

[0032]

[Chemical 8]

[0033]

[Chemical 9]

[0034]

[Chemical 10]

The above layers are the usual 11 to 15 layers shown in FIG.
Simultaneous coating was performed by adjusting the viscosity of each layer by the layer slide bead coating device as in the following Comparative Examples and Examples. The obtained sample was processed by an ordinary method for processing a color light-sensitive material, and the color unevenness due to the disturbance of the interface was visually judged.

The support used was a 120 μm thick triacetyl cellulose base, and the coating speed was 100 m / min for 11 layers, 15
In the case of a layer, it was set to 80 m / min.

Comparative Example 1 Table 1 shows the densities of the layers having the 11-layer structure. The density of each layer and the viscosity of each layer with the coating amount shown in Table 1 are 20
cp, and the viscosity of the second layer and below was 70 cp. This comparative example is based on the method disclosed in JP-A-3-219237. The results are shown in Table 1.

Comparative Example 2 In this case, the same conventional method as in Comparative Example 1 was used.
This is an example in which the first layer is set to 18 cp and the second and lower layers are set to 120 cp to increase the viscosity. The results are shown in Table 1.

Examples 1 and 2 The viscosity of each layer of the above 11-layer structure is shown in Table 1. In this case, the coating liquid viscosity of the layer having a relatively low density between the adjacent layers (the second, fifth, eighth and eleventh layers) in the present invention is set to the layer having a high density (third, fourth, sixth, seventh, ninth and tenth layers). This is due to the method of increasing the viscosity of the coating liquid of (layer).

The results are also shown in Table 1.

Examples 3 and 4 The viscosities of the layers having the above 11-layer structure are shown in Table 1. In this case, among the non-emulsion layers (fifth and eighth layers) sandwiched by two adjacent emulsion layers in the present invention, the viscosity of at least one layer is adjusted to the emulsion layers (fourth, sixth layer and seventh, ninth layer). ) It is due to the method of increasing the viscosity. The results are also shown in Table 1.

Examples 5 and 6 In this example, the viscosity of each layer of Examples 1 and 2 is further increased. The results are shown in Table 1.

Examples 7 and 8 In this example, the viscosity of each layer of Examples 3 and 4 is further increased. The results are shown in Table 1.

[0044]

[Table 1]

From the results shown in Table 1, even if the viscosities are simply increased as in Comparative Examples 1 and 2, even if the viscosities are increased, the color irregularity due to the disturbance of the interface does not occur. It can be seen that the color unevenness is good without necessarily increasing the viscosity significantly.

(In the case of 15-layer structure) In the same manner as in the example of 11-layer structure described above, the viscosity of each layer was adjusted as shown in Table 2 to obtain Comparative Examples 3 and 4 and Examples 9 to 16. investigated. The results are shown in Table 2.

[0047]

[Table 2]

As a result of Table 2, even in the case of a multi-layer structure such as 15 layers, the result of the viscosity adjustment according to the present invention was as good as the case of 11 layers shown in Table 1 was obtained. However, in this case, it was possible to obtain better results by increasing the viscosity.

[0049]

According to the present invention, even in multi-layer coating of 11 or more layers, a uniform surface condition without color unevenness can be obtained, whereby the coating method is conventionally divided into two or more times without deteriorating photographic performance. By producing a color negative light-sensitive material having 11 layers or more by one coating, it is possible to improve the production efficiency.

[Brief description of drawings]

FIG. 1A is a cross-sectional view of a slide bead coating device. FIG. 1B is an explanatory view of a coating liquid flow state on a slide surface.

FIG. 2 is a graph showing the density of each layer constituting the color light-sensitive material.

[Explanation of symbols]

1 Backup roll 2 Coating device 3 Pressure reducing device 4 Slit 5 Sliding surface 6 Lip 10 Web 12 Bead 13 and 14 Coating liquid

Claims (3)

[Claims] 1. In multi-layer simultaneous coating of 11 or more layers using a slide bead coating device or a curtain coating device having a slide surface on a continuously running support, the upper layer except the lowermost layer is relatively coated between adjacent layers. A coating method of a light-sensitive material, characterized in that the viscosity of a coating solution of a layer having a low density is made higher than the viscosity of a coating solution of a layer having a high density. 2. A non-emulsion sandwiched between two adjacent emulsion layers in multi-layer simultaneous coating of 11 or more layers using a slide bead coating device or a curtain coating device having a sliding surface on a continuously running support. A method for coating a light-sensitive material, wherein the viscosity of at least one of the layers is made higher than that of the emulsion layer. 3. The method for coating a photosensitive material according to claim 1, wherein the difference in viscosity of the coating liquid is 10 cp or more.