JPS63109438A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the excellent anti-static property and the suitable sliding property of the titled material by using a specific gelatin layer to a backing layer or by laminating a gelatin layer on the backing layer. CONSTITUTION:The backing layer of the titled material which is provided at least one layer of the silver halide emulsion layer on one side of a substrate 1, and provided the backing layer on another side of the substrate 1 is composed of the gelatin layer which contains at least one of a compd. selected from ethylene diamine tetraacetate derivative, pyrophosphoric acid and metaphosphoric acid, etc., and at least one of a compd. shown by formula I. While, the backing layer is formed by laminating at least one of the compd. shown by formula I on the gelatin layer contg. at least one of the compd. selected from ethylene diamine tetraacetate derivative, pyrophosphoric acid and metaphosphoric acid, etc. In formula I, R1-R3 are each alkyl or aralkyl group or a group derivated from said groups, R4 is hydrogen atom, alkyl, aralkyl, aryl, a heterocyclic ring group or a group derivated from said groups, X<-> is an anion.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material with improved antistatic properties.

[Conventional technology]

Many problems occur when static electricity is charged during the manufacturing process of silver halide photographic materials (hereinafter referred to as "photosensitive materials"). In other words, many of the substances used as supports for photosensitive materials are generally hydrophobic and have the property of being easily charged with static electricity. During the process of applying various coating layers including the photosensitive layer and transporting them during drying, electrical charges are generated due to friction with manufacturing equipment and peeling, and when this discharges, the photosensitive material coated with the photosensitive layer is exposed to light, and after development, uneven exposure due to irregular static electricity called static marks occurs. Also, in the process of packaging manufactured photosensitive materials,
Contact with the equipment used to transport the photosensitive material causes the photosensitive material to be electrostatically charged, creating static marks. Further, when a photosensitive material is loaded into a photographic device such as a camera for use, the photosensitive material may come into contact with a member for transporting the material and generate static marks. Furthermore, when an exposed photosensitive material is developed, static marks are generated because the photosensitive material comes into contact with a conveying member of a processing machine, such as a roller. Electrostatic charging not only causes static marks to occur on the photosensitive material, but also makes it easier for dust to adhere to the photosensitive material, resulting in various problems caused by the adhered dust. The more sensitive the photosensitive material is, the more likely it is that static marks will occur, but in addition to the recent increase in the sensitivity of photosensitive materials, high-speed automatic processing has increased the chances of static marks being subjected to harsh mechanical handling. There is a tendency for it to occur more frequently. Conventionally, various substances have been used to prevent charging of photosensitive materials. For example, conductivity can be imparted to a photosensitive material by treating the surface of the support with a hygroscopic substance or a conductive substance, or by incorporating these substances into the constituent layers of the photosensitive material, especially its surface layer. Measures are being taken to make it difficult for static electricity to accumulate. However, many of these substances are not only insufficient for highly sensitive photosensitive materials, especially at low humidity, but also reduce the antistatic effect over time and cause adhesion failure between photosensitive materials at high humidity. Not only is it not necessarily suitable for use with photosensitive materials, but it also has the disadvantage of poor sliding properties, causing feeding failures and scratches when applied to long movie films. be. In addition, in Japanese Patent Publication No. 11568/1983, [(R+)(Rz)(R*)N''-NHCOR4] is used as an antistatic agent.
Although Xenal7 Schilch F radiium salts have been described, their antistatic performance is still insufficient.

[Purpose of the invention]

The present invention has been made in view of the above-mentioned circumstances, and its purpose is to have excellent antistatic properties and appropriate slip properties, and a feeling that is resistant to scratches.
The backing layer of a light-sensitive material having at least one silver halide emulsion layer on one side of the support and a backing layer on the other side contains at least one compound selected from the following group [I]. and at least one compound represented by the following general formula (II),
or a gelatin layer containing at least one compound represented by the general formula [ff] is layered on a gelatin layer containing at least one compound selected from group [I]. [I] Ethylenediaminetetraacetic acid derivative, pyrophosphoric acid,
Metaphosphoric acid, tripolyphosphoric acid, hexametaphosphoric acid, oxalic acid,
Alkali metal salts of silicic acid, tartaric acid, molybdic acid, chromic acid, and tungstic acid. General formula (II) In the formula, R+, R2 and R3 each represent an alkyl group, an aralkyl group or a group derived therefrom, and R3
is a hydrogen atom, an alkyl group, an aralkyl group, an aryl group,
Represents a heterocyclic group or a group derived therefrom. X represents an anion. The present invention will be described in more detail below. The backing layer in the present invention is a non-photosensitive layer using gelatin as a binder, and preferably has a one-layer or two-layer structure, and is particularly preferably a two-layer structure. A multilayer structure can also be adopted if necessary. Note that hydrophilic colloids having similar properties to gelatin, such as natural or synthetic hydrophilic polymers, can be optionally used in combination with gelatin. These hydrophilic colloids can be used in a range of 0.1 to 10 g/m'. Compounds of Group I contained in the backing layer include ethylenediaminetetraacetic acid derivatives, pyrophosphoric acid, metaphosphoric acid, tripolyphosphoric acid, hexametaphosphoric acid, oxalic acid, silicic acid, tartaric acid, molybdic acid, chromic acid, and alkali of tungstic acid. Metal salts, especially ethylenediaminetetraacetic acid,
Alkali metal salts of tripolyphosphoric acid are preferred, and examples include disodium ethylenediaminetetraacetic acid and sodium tripolyphosphate. The method for incorporating the compound of group [I] into the backing layer is as follows:
These compounds may be added after being dissolved in a hydrophilic solvent such as water or alcohols. The amount added depends on the type of compound,
Although it may vary depending on the layer structure of the backing layer, etc., 10-3
〜597m2 is preferable, more preferably 10−2〜L
It is used in the range of g7m'. Further, the amount is preferably 0.01 to 20% by weight based on the hydrophilic colloid used in the backing layer. Next, the acylhydrazinium salt represented by the general formula (II) will be explained. In general formula (II), the alkyl group represented by R+, Rt, R3 and R4 has a carbon atom number of 1
-20 alkyl groups are preferred, and may be substituted with halogen atoms, hydroxyl groups, cyano groups, nitro groups, alkoxy groups, etc. The aralkyl group represented by R+, Rt, Rs and R4 is preferably a benzyl group, a phenethyl group, etc., and may have a substituent. The aryl group represented by R4 is preferably a phenyl group, which may be substituted with a halogen atom, an alkyl group, an alkoxy group, or the like. The heterocyclic group represented by R4 is 5
A membered or 6-membered heterocyclic group is preferred. X is an acid anion, preferably CQ, Br, I, (40,, BF., etc.) Representative specific examples of the compound of general formula CII) used in the present invention are shown below. These compounds are known as antistatic agents for photosensitive materials, and can be synthesized by the method described in Japanese Patent Publication No. 49-11567 and No. 49-11568. In order to incorporate the compound represented by the general formula (IT) into the backing layer, it may be added by dissolving it in a hydrophilic solvent such as water or an alcohol, similarly to the compounds of the layer group 1 above. Addition! No. 11 is preferably 0.01 to 5 g/m", particularly preferably 0.05 to Ig/m". The amount of hydrophilic colloid in the backing layer is preferably 0.01 to 20 jd%. In addition, when used in a single layer configuration in combination with a compound of group [I], 10
It is used in a range of 1000% by weight. The backing layer used in the present invention may further contain a matting agent, a slipping agent, a surfactant, a dye, a thickener, a hardening agent, a polymer latex, etc., if necessary. Regarding these matting agents, slipping agents, surfactants, and hardening agents, please refer to Research Disclosure (Research Disclosure).
Disclosure), No. 17643, (19
7g) Those described in Sections XVI, X 11, xI and X can be used arbitrarily. The thickness of the backing layer in the present invention is 0.1 to 10 μm
When the backing layer is composed of two layers, the ratio of the thickness of the upper layer to the lower layer is preferably 1:3 to 3:1. In the light-sensitive material of the present invention, all those commonly used as supports for light-sensitive materials can be used. Examples include cellulose acetate film, cellulose acetate butyrate film, polystyrene film, polyethylene terephthalate film, laminates thereof, and paper. More specifically, examples include paper coated with or laminated with baryta or an α-olefin polymer, particularly an α-olefin polymer having 2 to 10 carbon atoms, such as polyethylene or polypropylene. The silver halide emulsion layer provided on the opposite side of the backing layer of the present invention is a generally well-known emulsion layer for black-and-white photosensitive materials such as those for X-ray, printing, movies, and monochrome negatives, and emulsion layers for color negatives and inversion. It may be any emulsion layer for a color photosensitive material having a multilayer structure, such as for color use or color paper use, and is not limited in any way.

【Example】

The present invention will be explained in more detail with reference to specific examples below, but the embodiments of the present invention are not limited thereto. Note that % does not indicate weight % unless otherwise specified. Example-1 1.5% sodium tripolyphosphate was added to a 7% aqueous gelatin solution containing saponin as a coating aid and formalin as a hardening agent.
9 was added to prepare a coating solution, and the sodium tripolyphosphate was coated on a polyethylene terephthalate film subjected to subbing treatment at a rate of 0.19/s+'. This film was divided into 5 parts. For comparison, a film was also prepared using the same coating solution except that sodium tripolyphosphate was omitted. Next, a coating solution in which 701Q of a 4% aqueous solution of Exemplified Compounds 1, 3, 7, and 14 was added per tQ of a 5% gelatin aqueous solution containing a coating aid, a matting agent, and a hardening agent was applied to the above film. A backing layer with a two-layer structure was formed by coating and drying to give a film thickness of s''.As shown in Table 1, the same coating solution except for the exemplified compounds was also coated and used as a blank.Backing of these films On the other side of the layer, 8% silver nitrate
Then, apply an indirect radiographic emulsion containing 5% gelatin, further apply a protective layer containing gelatin, dry and
Ray film samples [I] to (7) were created. The surface specific resistance value (23° C. and 55% relative humidity) of the backing layer of each of these samples was measured. After each sample was left at 23°C and 25% relative humidity for 24 hours, the backing layer was rubbed with a rubber roller and a
Development was carried out in the usual manner using a developer for rays, and the occurrence of static marks was examined. The results are shown in Table-1. As can be seen from the results in Table 1, the sample of the present invention containing sodium tripolyphosphate ([compound of group 13) in the lower layer of the backing layer and the exemplary compound represented by the general formula Cn) in the upper layer, The antistatic property was significantly improved compared to the sample that did not contain sodium tripolyphosphate in the lower layer of the backing layer and the sample that did not contain the exemplified compound in the upper layer. Again, same 7! As a result of thermo-processing the samples, exposing them to light with a KS-1 line photometer (manufactured by Konishi Roku Photo Industry Co., Ltd.), and performing sensitometry, no differences in photographic properties were observed among these seven samples. It has been found that the compounds according to the present invention have no adverse effect on the photographic properties of light-sensitive materials. Example-2 Gelatin and ethylenediaminetetraacetic acid (
EDTA), saponin as a coating aid, styrene-sodium maleate copolymer as a thickener, and formalin as a hardening agent. ,
A 4% aqueous solution of Exemplary Compounds 10.18 and 24.30 was used as the lower layer so that EDTA was o, tg/-''.
A 5% gelatin aqueous solution containing 70 si2 per IQ was added to the pubking layer coating solution, and one exemplified compound was added to the lower layer of the two legs.
It was coated to a thickness of 20 m to 97 m" and dried to form the upper layer. On the opposite side of these backing layers, the same indirect radiographic emulsion as in Example-■ was coated, and then a protective layer was coated to form X-ray film samples (8) to (14). The surface resistivity of the bubbling layer and the generation of static marks due to development after triboelectric charging were measured for each sample in the same manner as in Example 1.The results are shown in Table 2.The results in Table 2 also reflect the present invention. It is shown that the sample having the backing layer according to the above significantly improves the antistatic property compared to the comparative sample. Example-3 Same as Example-■ except that the two-layer backing layer was changed to a single-layer structure. When an X-ray film was prepared and tested in the same manner as in Example-1, antistatic effects equivalent to those in Example-1 were observed.

Claims (1)

[Scope of Claims] A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on one side of a support and a backing layer on the other side, the backing layer comprising the following [
A gelatin layer containing at least one compound selected from group [I] and at least one compound represented by the following general formula [II], or a gelatin layer containing at least one compound selected from group [I] 1. A silver halide photographic material comprising a gelatin layer containing at least one compound represented by the general formula [II] on a gelatin layer. [I] Alkali metal salts of ethylenediaminetetraacetic acid derivatives, pyrophosphoric acid, metaphosphoric acid, tripolyphosphoric acid, hexametaphosphoric acid, oxalic acid, silicic acid, tartaric acid, molybdic acid, chromic acid, and tungstic acid. General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1, R_2 and R_3 each represent an alkyl group, an aralkyl group, or a group derived from these,
R_4 represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, a heterocyclic group, or a group derived therefrom. X^■ represents an anion. ]