JPH0545797A - Antistaticized silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material high in transparency and good in stability of a coating fluid and antistaticity. CONSTITUTION:This silver halide photographic sensitive material is characterized by containing the tin dioxide sol particles having a particle diameter of <=100nm and prepared in an aqueous solution at 150-350 deg.C in a gelatin layer containing a nonionic hardening agent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly to an antistatic silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material uses a transparent film as a base, but it has a low conductivity and causes various problems. 1 of these problems
One is that when a coating solution containing silver halide is applied to a film, it is applied at a high speed with a coater, but it is rubbed by a roller and charged while being rubbed, and when this discharges, the silver halide is fogged. It is to make it (electrostatic fog).

If the conductivity of the film is increased and antistatic is applied in advance, electrostatic fog can be prevented when the silver halide emulsion is coated. Further, when a user uses a photosensitive material, if they are easily charged, dust and dust may adhere to the photosensitive material, and undesired images such as pinholes may be formed during exposure and photographic processing. There is a problem that workability deteriorates because the materials stick together. There is also a problem that these photosensitive materials are discharged through human hands.

What is important in these problems is that the antistatic property is good both before and after the processing such as development, fixing and washing, and the strength of the gelatin film is weakened by the antistatic property. And the transparency of the film is not deteriorated.
According to Japanese Patent Publication No. 61-174542, an antistatic layer made of a conductive polymer is provided between the backing layer and the base, the antistatic property is enhanced through this layer, and the adhesion between this layer and the backing layer is improved. The use of aziridine hardeners to improve is described.

However, the aziridine hardener hardens the skin and is not preferable in terms of safety and hygiene. Further, since an antistatic layer made of a conductive polymer is provided between the base and the backing layer, it is adhered to the backing layer. Was not sufficient and the drying property was poor. Furthermore, these polymers, which are ion-conducting, have the drawback of having low electrical conductivity in low-humidity atmospheres, and it is considered that antistatic properties must exert their effect only in low-humidity atmospheres. I have to say that it is disadvantageous.

On the other hand, Japanese Patent Laid-Open Nos. 55-47663 and 5
5-47664, 55-182613, 5
No. 6-161301, it is described that the antistatic property is enhanced by including a crystalline metal oxide in gelatin. However, it is very difficult to produce ultrafine particles of crystalline metal oxide, and in view of economic efficiency, the particle size is 100 nm or more.

Therefore, light scattering is likely to occur and the transparency is low, which is extremely disadvantageous as a film material. In order to further increase the conductivity, the metal oxide is doped with a dissimilar metal, but when this doping causes the metal oxide to be colored in various colors, it is applied on the film.
It had the drawback of giving a bad impression. Further, crystalline tin dioxide is unlikely to be a colloidal solution, and if the coating solution is left standing for several hours, these crystals precipitate.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photographic film light-sensitive material having a good antistatic property, which has a high transparency and a stable coating solution stability. To provide a silver film light-sensitive material.

[0009]

The above object of the present invention is to cure tin dioxide sol particles prepared in an aqueous solution having a particle size of 100 nm or less at 150 to 350 ° C. as a conductive agent and cured by a nonionic hardener. This is achieved by the silver halide photographic light-sensitive material contained in the gelatin layer.

Particles having a particle size of 100 nm or less according to the present invention include
It means the diameter when considering the volume of each particle as a sphere, and means that the average of the diameter is 100 nm or less. In the case of particles larger than this, light scattering is large, which is unsuitable as a film material, and when doped with a dissimilar metal, coloring is very noticeable.

The tin dioxide sol particles of the present invention are tin dioxide sol particles prepared at a temperature of 150 to 350 ° C. in an aqueous solution. Since they are prepared in an aqueous solution, a fine particle sol can be prepared and at 150 ° C. Since the above temperature is applied, electron conductivity is improved. Since it is a fine particle, it is difficult to judge whether it is crystalline or amorphous, but it is considered appropriate to consider it as semi-crystalline when examined by X-ray diffraction. It means tin dioxide that is not an amorphous sol. As described in Japanese Patent Publication No. 35-6616, an amorphous sol is tin dioxide made from tin hydroxide in an aqueous solution at a temperature of about 100 ° C, and it is almost amorphous when viewed by X-ray. There is no crystalline form. Since it is colloidal, there is no problem that tin dioxide precipitates in the coating solution, but it has the drawbacks of high resistance and large humidity dependence.

On the other hand, crystalline tin dioxide is described in JP-A-56-
As described in No. 143430, it is tin dioxide produced when prepared in a gas at a temperature as high as 900 ° C. In this case, it has a low resistance value and excellent antistatic property, but it is fired at a high temperature. In addition, the particles are large and have drawbacks in transparency and colorability, and sedimentation occurs because they do not become colloidal particles in an aqueous solution.

The tin dioxide sol particles of the present invention have both good points of colloidal particles and good crystallinity, and the resistance value is slightly inferior to that of crystalline particles, but the transparency, coloring and sedimentation Colloidal tin dioxide particles with excellent properties.

A method for preparing these tin dioxide sol particles is described in JP-B-2-58213 and JP-A-2-261886. When an antistatic film is made using these tin dioxide sol particles, tin dioxide sol is dispersed in gelatin to make a coating solution. However, if this gelatin solution contains an ionic hardener, gelation or viscosity It is not preferable to increase.

The coating amount of this tin dioxide sol is 0.1 to 10 g, and preferably 0.3 to 3.0 g, per 1 m ² as a solid content. If it is less than this coating amount, the conductivity is deteriorated and the role of antistatic is not fulfilled. If the amount is more than this amount, the transparency will be deteriorated even if it is fine particles, which is a practical problem.

The binder of the tin dioxide sol used in the present invention is mainly gelatin, but other proteins such as colloidal albumin and casein, cellulose compounds such as carboxymethyl cellulose, hydroxyethyl cellulose, diacetyl cellulose and triacetyl cellulose, agar, Sugar derivatives such as sodium alginate and starch derivatives,
Synthetic hydrophilic colloids such as polyvinyl alcohol, poly-N-vinylpyrrolidone, vinyl polymers and copolymers such as polyacrylic acid, polyacrylamide, polyvinyl acetate and polyacrylic acid ester, natural products such as rosin and shellac, and the like. Aqueous emulsions of derivatives, styrene-butadiene copolymers, polyacrylic acid, polyacrylic acid esters and their derivatives, polyvinyl acetate, vinyl acetate-acrylic acid ester copolymers, polyolefins, olefin-vinyl acetate copolymers, etc. Part can be used.

The weight ratio of gelatin to tin dioxide sol is 1% to 300%, preferably 10% to 150%. If the gelatin content is too low, the adhesion to the base will be poor, and if the gelatin content is too high, the resistance will be high.

The nonionic hardener used in the present invention means a non-ionized hardener, and is specifically as shown below.

[0019]

[Chemical 1]

[0020]

[Chemical 2]

[0021]

[Chemical 3]

[0022]

[Chemical 4]

[0023]

[Chemical 5]

The ionic hardeners other than the present invention are as shown below.

[0025]

[Chemical 6]

[0026]

[Chemical 7]

[0027]

[Chemical 8]

The film used in the present invention is a cellulose nitrate film, a cellulose acetate film, a cellulose acetate butyrate film, a cellulose acetate propionate film, a polystyrene film, a polyethylene terephthalate film, a polycarbonate film or a laminate thereof. is there.

[0029]

EXAMPLES The present invention will be described in more detail below with reference to examples. Example 1 65 g of stannic chloride hydrate, 1.5 g of antimony trichloride and 12 g of hydrochloric acid were mixed, and this solution was gradually added to 400 g of aqueous ammonia bicarbonate solution (NH ₃ 2.5%), and the resulting gel was filtered. After the separation, the gel was washed with water until chlorine was eliminated. Next, 0.2% ammonia water was added to 100 g of this gel and heated in an autoclave at 200 ° C. for 6 hours to obtain a tin dioxide sol having an average particle size of 5 nm. Using this tin dioxide sol, the following solution (A) was prepared.

Solution (A) 10% SNP-4N 10 g Gelatin 10 g The above tin dioxide sol (as 10%) 50 g Various hardening agents 0.5 g Water was added to 1000 ml Next solution (B) made.

Solution (B) 10% SNP-4N 20 g Gelatin 50 g 1% Acid Violet 520A (manufactured by Adel Haen) 50 g Various hardening agents 2.5 g Water was added to 1000 ml This solution (A) was 1 m ^The solution (B) was coated with two layers at a time by using an extrusion bar so that the amount of gelatin was 0.4 g per ^{2 and the amount of} gelatin was 3.0 g per m ^2.
Heated at 0 ° C for 1 day. The sample after heating was cut and processed using GR-14 automatic developing solution manufactured by Konishi Rokusha. Developed by Mitsubishi Paper Mills Ltd. MRA CD-111, 35 ° C. for 20 seconds,
The fixing is CF-711 at 35 ° C. for 20 seconds.

The antistatic ability of the sample before and after the treatment was 2
It was left for 2 hours in an atmosphere of 5 ° C. and 20% RH (relative humidity), and its surface resistance was measured by a HREA surface resistance meter, Model HT-210 manufactured by Mitsubishi Petrochemical Co., Ltd. As a measure of surface resistance, 10 ¹² Ω or more is impossible, and 10 ¹¹ or less is a good level. The transparency was visually judged by stacking five processed films. ○ marks are good, Δ marks are slightly bad, and X marks are bad. The results are shown in Table 1.

[0033]

[Table 1]

As shown in Table 1, it can be seen that when an ionized hardener is used, the film becomes cloudy and the transparency decreases, and the resistance value also increases.

Example 2 The solutions (A) and (B) used in Example 1 were tested for stability over time. First, 5 ml each of the solutions (A) and (B) were mixed and kept at 40 ° C. 1 hour after mixing the liquid and 2
After 4 hours, their viscosities were measured with a Tokyo Keiki E-type viscometer. The results are shown in Table 2.

[0036]

[Table 2]

As shown in Table 2, the liquid using the nonionic hardener is transparent and has little change in viscosity. On the other hand, the one using an ionic hardener has a large increase in viscosity, and the liquid becomes cloudy, which is not preferable considering the coating step.

[0038]

According to the present invention, a silver halide photographic light-sensitive material having high transparency and good stability of a coating solution and having good antistatic property can be obtained.

Claims (1)

[Claims] 1. 150 to 350 having a particle size of 100 nm or less
Silver halide photographic light-sensitive material, characterized in that it contains tin dioxide sol particles prepared in an aqueous solution at 0 ° C in a gelatin layer hardened with a nonionic hardener, and the layer is antistatic. ..