JP2838537B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic material, and more particularly to a printing photographic material having improved reflection characteristics.

[Background of the Invention]

In recent years, resin-coated paper, in which polyolefin such as polyethylene is coated on paper, is generally used as a base material for photographic prints, especially in the case of color photosensitive materials, in place of conventional baryta paper.

The polyolefin resin-coated paper is embossed by various methods to provide a non-smooth surface type photographic print base paper such as a silk surface, a fine grain surface, and a mat surface. However, if such embossing is not uniform, there is a problem that the print is difficult to see due to glare.

To obtain an embossed photographic print For a photosensitive material with a smooth surface (glossy) that is not embossed,
A method of embossing a smooth surface with an embossing roll before or after development is known.

However, in such a method of embossing before and after the development processing, the number of processing steps is increased, which hinders rapid processing,
Depending on the degree of use of the embossing roll and the production lot, it is difficult to make the surface state of the embossing roll uniform,
In particular, glare on the glossy surface occurs due to the difference from the difference between the partial non-smooth surfaces of the surface, and the quality of the photographic surface is impaired.
Further, if embossing is performed before the development processing, pressure fogging may occur.

Other methods for obtaining embossed photographic prints include prepressing the support in advance, or transferring the mold on the pressure roll side when pressing the molten polyolefin onto the support. There is a method in which a photographic constituent layer is applied on a stamped support and dried to obtain a desired photographic print.

However, in this method, the uniform and uniform embossing is controlled by controlling the chill roll cooling for embossing the surface of the support and the conditions (for example, temperature, speed, and the amount of the release agent used) when the chill roll is peeled off. It is difficult to obtain the conditions, and the finish of the surface is slightly different depending on the production lot of the chill roll. That is, it was difficult to eliminate glare in the embossed print.

On the other hand, photographic light-sensitive materials use a hydrophilic colloid such as gelatin as a binder. In this case, in order to reduce the adhesion between the light-sensitive materials or other objects in contact with the light-sensitive materials, the light-sensitive materials are used. Particles having an average particle size of 2 to 5 μm, for example, inorganic substances such as silica (silicon dioxide), magnesium oxide, titanium dioxide, and calcium carbonate, and organic substances such as polymethyl methacrylate and cellulose acetate propionate. Methods of incorporating particles of a substance to increase surface roughness, matte and reduce adhesion are well known methods.

It is known that such a matting agent, when used in a large amount, suppresses the maximum density of the printing photosensitive material and deteriorates the graininess of an image.

As measures against glare, for example, Japanese Patent Application Laid-Open
Japanese Patent Application Laid-Open No. 61-63836 discloses an example in which a matting agent is contained and an embossed support is used, but the effect intended for the purpose of the present invention was not sufficiently exhibited.

[Object of the invention]

In view of the above problems, an object of the present invention is to provide a photosensitive material capable of suppressing glare in a photosensitive material for printing and maintaining the maximum density. More specifically, an object of the present invention is to provide a photosensitive material which is suitable for applications such as maps, perspective diagrams, piping diagrams, wiring diagrams, etc., and is easy to see without glare.

[Configuration of the invention]

The object of the present invention is to provide a three-dimensional center plane average roughness SRa of 1.5
One surface of the above white reflective support has a hydrophilic colloid layer including at least one silver halide emulsion layer, and the outermost layer of the hydrophilic colloid layer contains amorphous silica at 0.8 mg / mg.
It is achieved by m ² of silver halide photographic light-sensitive material 250 mg / m ² containing.

Hereinafter, the present invention will be described more specifically. The surface average roughness SRa in the present invention is specified in JIS B 0601-1976. That is, in the roughness curve obtained by removing the long wavelength (low frequency component) from the cross-sectional curve of the surface, the component of l of the measured length is extracted, the center line of the extracted portion is defined as the X axis, and the roughness curve is defined as y. = 1 / l | f (X) | dX means the value of Ra expressed in μm.

As a result of intensive studies, the present inventors have found that when the SRa of the base paper is smaller than 1.5 μm, glare cannot be suppressed, and the maximum concentration decreases when silica is excessively added as a countermeasure. On the other hand, it has been found that if the amount is 1.5 or more, glare can be suppressed by adding an appropriate amount of silica, and the maximum concentration can be kept at an appropriate level.

The silica in the present invention can be silicon dioxide which is usually used as a matting agent, and is dispersed and contained in the non-photosensitive outermost layer of the photosensitive material. To contain, in a hydrophilic binder containing a nonionic, cationic, or anionic surfactant, if necessary, other additives are added, and a high-speed rotation mixer, a homogenizer, an ultrasonic dispersion,
It can be formed by dispersing with a ball mill or the like by an emulsification dispersion method utilizing shear stress, and applying as an outermost layer of a light-sensitive material by any method used in the field of photography. The particle size of the silica used in the present invention is preferably 2.5 μm or less, and the amount added is 100 mg / m ² to 200 mg.
mg / m ² .

In the light-sensitive material of the present invention, the outermost non-photosensitive layer means a surface protective layer and a back layer. In the present invention, the effect is exhibited particularly when the surface protective layer contains a matting agent.

In the present invention, examples of the hydrophilic binder constituting the outermost layer include gelatin, gelatin derivatives, albumin and the like, and gelatin is preferred.

The emulsion-coated support used in the light-sensitive material of the present invention is embossed on a support, when coating a running paper substrate with a polyolefin melt-extruded into a film through a die from an extruder; It can be obtained using a cooling roll that has been processed to form desired irregularities such as a fine grain surface and a mat surface. Here, the melting temperature of the polyolefin in the die is about 250-350 ° C,
It is preferably 280 to 320 ° C., and the running speed of the paper substrate is high.
It is about 50 to 500 m / min, preferably 80 to 250 m / min. In addition, performing patterning with a cooling roll on a polyolefin layer containing titanium oxide coated with a divalent to tetravalent alcohol is effective for accurate embossing and patterning.

The depth of the pattern on the surface of the embossing roll is preferably 49 μm or less, more preferably 2 to 30 μm, and particularly preferably 10 to
25 μm. It is preferable to apply a matting process to the patterned cooling roll in order to transfer the pattern more reliably.

The thickness of the embossed polyolefin is preferably 1.2 to 5 times the pattern depth. The pressure applied on the cooling roll may be 30 kg / cm or less, for example, about 2.5 to 10 kg / cm.

Examples of the polyolefin used herein include homo- or copolymers of α-olefins having about 2 to 8 carbon atoms, such as ethylene and propylene. The polyolefin may contain an antistatic layer, a fluorescent whitening agent, and the like in addition to titanium dioxide.

The paper substrate to be used is only required to be substantially made of paper, and may include synthetic pulp or the like.

The silver halide emulsion used in the present invention is not particularly limited, and can be adjusted by various techniques known in the photographic light-sensitive material industry. That is, it can be applied to various photosensitive materials such as color and black and white. In addition, a method known in the art can be applied to the treatment.

〔Example〕

Hereinafter, the present invention will be described specifically with reference to examples.
Embodiments of the present invention are not limited thereby.

Example 1 (Preparation of Emulsion A) A monodisperse silver bromide emulsion was prepared in the following manner.

An aqueous solution containing ossein gelatin was controlled at 70 ° C., and under vigorous stirring, an aqueous solution of silver nitrate and an aqueous solution of potassium bromide were simultaneously added to the solution by a controlled double jet method to form an octahedron having an average particle size of 0.4 μm. An emulsion was obtained. This emulsion contains 5 mg of sodium thiosulfate and 6 mg of silver per mole of silver.
Of chloroauric acid (tetrahydrate) was added thereto and heated at 75 ° C. for 80 minutes to perform chemical ripening to obtain a silver bromide core emulsion.

The core emulsion thus obtained was further grown by adding an aqueous solution of silver nitrate and an aqueous solution of potassium bromide to obtain an average particle size of 0.7.
A μm octahedral monodispersed core / shell silver bromide emulsion was obtained. After washing with water and desalting, this emulsion was added in an amount of 1.3 mg / mol of silver.
Of sodium thiosulfate and chloroauric acid (tetrahydrate)
Heating was performed at 60 ° C. for 70 minutes for chemical sensitization to obtain an internal latent image type silver halide emulsion.

(Preparation of Sample) The following layers were formed on a support to prepare a sample of the present invention. As the support, a paper support having a basis weight of 100 g / m ² and a 145 μm-thick paper laminated on both sides with four types of polyethylene having different center plane average roughness SRa as shown in Tables 1 and 2 was used.
The numbers indicate the amount with application (mg / dm ² ).

7th layer (protective layer) Gelatin 12.3 Amorphous silica (average particle size 3.0 μm) Amount shown in Tables 1 and 2 6th layer (UV absorbing layer) Gelatin 5.4 UV absorbing agent (UV-1) 1.0 UV absorbing agent (UV -2) 2.8 Solvent (SO-3) 1.2 Fifth layer (blue photosensitive layer) Blue-sensitive emulsion obtained by adding blue-sensitive sensitizing dye (BD-1) to Emulsion A (in terms of silver) 5.0 Gelatin 13.5 Yellow Coupler (YC-1) 8.4 Image stabilizer (AO-2) 3.0 Solvent (SO-1) 5.2 Fogging agent (FA-1) 15.0 mg / mole silver 4th layer (yellow filter layer) Gelatin 4.2 Yellow colloidal silver 1.0 Ultraviolet light Absorbent (UV-1) 0.5 Ultraviolet absorber (UV-2) 1.4 Anti-color mixing agent (AS-1) 0.4 Solvent (SO-3) 0.8 Third layer (green photosensitive layer) Emulsion A has a green-sensitive sensitizing dye ( Green-sensitive emulsion (silver equivalent) sensitized by adding GD-1) 2.7 Gelatin 13.0 Magenta coupler (MC-1) 2.4 Image quality Fixative (AO-1) 2.0 Solvent (SO-4) 3.15 Fogging agent (FA-1) 15.0mg / mole silver Second layer (color mixture prevention layer) Gelatin 7.5 Color mixture prevention agent (AS-1) 0.55 Solvent (SO- 2) 0.72 First layer (red-sensitive layer) Red-sensitive emulsion (silver equivalent) obtained by adding red-sensitive sensitizing dyes (RD-1 and RD-2) to Emulsion A 4.0 Gelatin 13.8 Cyan coupler (CC- 1) 2.1 Cyan coupler (CC-2) 2.1 Image stabilizer (AO-2) 2.2 Solvent (SO-1) 3.3 Fogging agent (FA-1) 15.0 mg / mole silver SA-1, SA as coating aid -2, and HA-1 was added as a hardening agent at 6 mg / g of gelatin for coating.

(Additives used) Each of the obtained samples was subjected to the following two types of exposure and then to the following processing.

Exposure conditions 1. Overall exposure Exposure was performed so that the density after processing was 1.0.

2. Sensitometric exposure [Processing] Processing process Time Temperature Color development 30 seconds to 1 minute 30 seconds 33 ° C Bleaching and fixing 40 seconds 33 ° C Stability 3 times in 20 seconds increments 33 ° C Drying 30 seconds 60 ° C Color developing solution formulation Benzil Alcohol 15 ml Ethylene glycol 15 ml Polyphosphoric acid 2.5 g Potassium sulfite 2.0 g Potassium bromide 1.8 g Potassium carbonate 30.0 g Hydroxylamine sulfate 3.0 g 3-Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethyl aniline / sulfuric acid Salt 4.25 g 5-Methylbenzotriazole 10 mg 1-acetyl-2-phenylhydrazine 0.1 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.0 g Potassium hydroxide 2.0 g Adjusted to pH 10.5 with potassium or sulfuric acid.) Bleach-fixing solution formulation Ammonium thiosulfate (54 Wt%) 150 ml Sodium sulfite 15 g Iron ethylenediaminetetraacetate ( III) Ammonium 55g Sodium ethylenediaminetetraacetate (dihydrate) 4g Glacial acetic acid 8.61g Water was added to adjust 1 (pH was adjusted to 5.4 with ammonia water or hydrochloric acid). 1-Hydroxyethylidene-1,1-diphosphone Acid (60%) 1.6 ml bismuth chloride 0.35 g polyvinylpyrrolidone 0.25 g aqueous ammonia 2.5 ml nitrilotriacetic acid / 3Na 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 50 mg 2-octyl-4-isothiazoline 3-one 50mg Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.0g Water was added to adjust the pH to 1 with potassium hydroxide or hydrochloric acid. 1 (Evaluation) Developed by overall exposure Using the sample, the glossiness was measured under the following conditions using a gloss meter TG-PD manufactured by Tokyo Denshoku.

Glossiness measurement condition (60 ° specular gloss) Optical condition JIS Z-8741 Incident angle 60 ° Reflection angle 60 ° Sample irradiation surface 4 × 1.2cm Silica coating amount, center surface average roughness SRa and relation of glossiness are shown in Table 1. Show. Table 2 shows the relationship between the amount of silica applied, the average roughness of the center plane and the maximum density.

As can be seen from Tables 1 and 2, within the range of the present invention, the glossiness is low, the glare is small, and the maximum density is maintained to obtain a good image.

〔The invention's effect〕

According to the present invention, it was possible to provide a photosensitive material capable of suppressing glare in a photosensitive material for printing and maintaining the maximum density.

Continuation of front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 1/76

Claims (1)

(57) [Claims] 1. A white reflective support having a three-dimensional center plane average roughness SRa of 1.5 or more has a hydrophilic colloid layer including at least one silver halide emulsion layer on one surface thereof. Of which, the outermost layer is amorphous silica of 0.8 mg / m ^{2 to} 250 mg /
The silver halide photographic light-sensitive material, characterized in that m ² containing.