JPS59214850A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To enhance physical properties during manufacturing process, storage, and development process by incorporating a specified org. silane compd. in a hydrophilic colloidal laver. CONSTITUTION:A hydrophilic colloid layer contains an org. silane compd. represented by the formula shown here which R<1> is lower alkyl or alkenyl optionally sustd. by epoxy, amino, vinyl, or the like, and R<2>-R<4> are each lower alkyl, alkoxy, alkylcarboxy, or the like, and at least one of R<1>-R<4> has an epoxy, vinyl, or amino group at the terminal, and at least one of them has none of said groups. As a result, the obtained material is prevented from deterioration of photographic characteristics and increase of viscosity during the waiting time after coating, and also progress of film hardening during the lapse of time, and occurrence of peeling phenomena and surface damages are decreased.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for producing a silver halide photographic light-sensitive material (hereinafter abbreviated as light-sensitive material). The present invention relates to a photosensitive material having a hydrophilic colloid layer on the surface of a support.

(Prior art) A variety of supports have been used for photosensitive materials in the past, depending on the purpose and use. For example, a paper support coated on the entire surface of a polyolefin layer such as polyethylene, or a synthetic resin film such as polyethylene terephthalate. It is considered to be representative.

These photosensitive materials generally have multiple layers of various hydrophilic colloids coated on a support.

The hydrophilic colloid layer to be coated is mainly made of gelatin, which generally has extremely low mechanical strength, and the coating film is easily damaged by handling after coating, including development.

Therefore, a hardening agent is added to the hydrophilic colloid layer to strengthen the physical properties of the coating film, and the surface of the support is corona discharged in order to strengthen the adhesion between the support and the coating film.

Currently, preliminary treatments such as ultraviolet irradiation or flame treatment are performed.

However, in recent years, the manufacturing process for coating and drying photosensitive materials has been significantly speeded up for the purpose of mass production and cost reduction, for example, 100 to 200 cIrL per second.
High-speed continuous coating and drying are performed. For this reason, the applied hydrophilic colloid layer often expands and softens due to high temperature and rapid drying, and in some cases melts or flows.

Similarly, in the development process after production, in recent years, it has been common practice to mechanically perform rapid processing before and after adding seconds in a high-temperature bath starting at 30°C.

As a result, the coating film swells and softens, its physical properties deteriorate, and it often suffers from fatal damage such as scratches or peeling of the film. Therefore, there is a strong demand for silver halide photographic materials to have sufficient adhesion to the support and strong film properties immediately after coating production, and to maintain these properties stably even after production. It is in.

It has also been known to improve adhesiveness by applying corona discharge treatment to the surface of a paper support coated with polyethylene on both sides.

Adhesive strength usually decreases over time after corona discharge treatment.

As described above, if the adhesive is applied after a period of time after the corona discharge treatment, the adhesion will inevitably deteriorate, so it is most preferable to apply the corona treatment immediately before application, which is a constraint on the production process. Various methods have been investigated to provide sufficient physical properties that can be applied to such situations, but photosensitive silver halide is extremely selectively sensitive to chemical factors, and has various photographic properties. It is built on the balance of chemical reactions and has a complex interplay of constituent factors, or when a hardening agent is added to gelatin, which is used as the main ingredient, the viscosity changes drastically after addition, making it difficult to apply the same batch of coating solution. It becomes difficult to apply uniformly from the beginning to the end, resulting in intra-batch variations in finished photographic properties.Furthermore, after coating and drying, the degree of hardness progresses over time, resulting in so-called post-hardening, which changes developability and deteriorates photographic properties over time. In severe cases, the PL between the processing baths may deteriorate, and in severe cases, it may become impossible to develop.In addition, the PL between the processing baths during the processing process may be unsuitable for drastic changes, or may combine with processing waste products and cause failure. Due to the problems peculiar to photosensitive gelatino silver halide, such as the occurrence of problems, it has not been possible to easily introduce techniques used for the same purpose in other technical fields, and the process has remained unsatisfactory.

(Object of the Invention) The object of the present invention is to provide a photosensitive material in which a hydrophilic colloid layer is provided on the surface of a support having a plastic surface. Our goal is to provide all kinds of photosensitive materials that are of good quality.

(Structure of the Invention) The present invention provides a photosensitive material in which a hydrophilic colloid layer is provided on the surface of a support having a plastic surface, in which the hydrophilic colloid layer contains a compound represented by the following general formula [I]. This is achieved by using a photosensitive material that is wettable.

In addition, in the present invention, a more preferred embodiment is achieved by subjecting the plastic surface to a corona discharge treatment.

General formula CI) 2 R"-5i-R" 4 In the formula, R1 represents a substituted or unsubstituted lower alkyl group, lower alkenyl group or Ryl group,
Examples of the substituent include an epoxy group, an amino group, and a vinyl group that have the ability to bond with a reactive group of a hydrophilic colloid.

Further, R', R'' and R4 represent a lower alkyl group, an alkoxy group, an alkylcarboxy group, an epoxyalkoxy group, an alkenyl group or an aryl group.

However, at least one of RI, B2, R3, and R4, which is centered on a silicon atom, has an epoxy group, vinyl group, or amine group at the end. Among the remainder, specific examples of at least the -rane compound will be given. Of course, the present invention is not limited to this.

(Exemplary compound) 7°, [2] HzCCI(CHtO(CHJaSj (O
C*Hs)s[3] HsC*Sshi(OCHtH
C”CHs)+[6] HzC=CI(-8*-
→0COCHs)aHC/CF(.

[:9] HtC=CHCH+++1Si+0Ct
ffi) + [10] HtNCHtCHJH(CH
z )s S t + 0C) Is )1 These compounds are commercially available and readily available. For example, S
I (series compounds (manufactured by Toray Silicone ■), silane coupling agents (manufactured by Chisso ■), etc.

The hardener used in the present invention can be arbitrarily selected depending on the purpose, and is contained in at least one layer of the light-sensitive material such as the silver halide emulsion layer and antihalation layer. be able to.

The amount used may be in the range of 0.001 to 1 og per 1 g of dry gelatin as a hydrophilic colloid (binder),
Preferably, the amount is in the range of 0.019 to 1.0 g. When used, it may be dissolved and dispersed in water or a hydrophilic intoxicant such as methanol, and if necessary, it may be added in the form of a dispersion in an aqueous solution such as gelatin. You can also do it.

Further, an acid or alkaline agent can be used to adjust the pH of the aqueous solution to an appropriate value.

It may be added to the constituent layer coating solution at any time during the coating solution manufacturing process, but preferably immediately before coating.

Of course, the hardeners of the present invention may be used alone, or two or more of the hardeners of the present invention may be mixed.

Further, there is no problem in using it in combination with a known hardening agent other than the one of the present invention.

Known hardening agents include, for example, aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclobentanedione, bis(2-chloroethylurea), and 2-hydroxy-4,6-
Dichloro-1,3,5) riazine, and other U.S. patents 3
, 288,775, 2,732,303, British Patent No. 974,723, British Patent No. 1,167.207, divinylsulfone, 5-acetyl- 1,3-diacryloylhexahydro-1,3,5-) riazine, and other reactivities described in U.S. Pat. No. 3,635,718, U.S. Pat. olefin-containing compounds, N-hydroxymethylphthalimide, and other U.S. Pat. Nos. 2,732,316 and 2
．． N-methylol compounds described in US Pat. No. 586,168, incyanates described in US Pat. No. 3,103,437, US Pat. No. 3,017,280, etc.
Aziridine compounds described in U.S. Pat. No. 2,725,294, U.S. Pat.
Acid derivatives described in US Pat. No. 725,295 etc., carbodiimide compounds described in US Pat. No. 3,100,704 etc., epoxy compounds described in US Pat. No. 3,091,537 etc. US Patent 3,32
Inoxazole compounds described in No. 1,313 and No. 3,543,292, halogenocarboxialdehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane and dichlorodioxane, or inorganic hardening agents. As chrome light pan, zirconium sulfate etc. Also, instead of the above compound, a breaker
It may be used in combination with those in the form P, such as alkali metal bisulfite aldehyde adducts, methylol derivatives of hydantoin, etc. When the hardener of the present invention is used in combination with other hardeners, the proportion of the hardener of the present invention can be selected at any rate depending on the purpose and effect.

Hydrophilic binders advantageously used in the light-sensitive material of the present invention include lime-treated gelatin, acid-treated gelatin, and gelatin derivatives (for example, Japanese Patent Publication No. 38-4854, 439-
No. 5514, No. 40-12237, No. 42-2684
No. 5, U.S. Patent No. 2,525,753, l'ffi 2
, No. 594,293, No. 2,614,928, No. 2,
No. 763,639, No. 3,118,766.

No. 5 13,132,945, No. 3,186,846,
No. 3,312,553, British Patent No. 861.414,
Gelatin derivatives described in 1,033,189 etc.)
, proteins such as albumin and casein, cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose, 5! Synthetic hydrophilic binders include natural polymers such as natural polymers, sodium alginate, polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymers, polyacrylamide or their derivatives, and partial hydrolysates. The binders can be used individually or in combination. These hydrophilic binders can also be advantageously used to prepare constituent layers of photosensitive materials that do not contain silver halide, such as antihalation layers, intermediate layers, and protective layers.

The support having a plastic surface to which the present invention is applied is an α-olefin polymer, particularly a raw material coated or laminated with an α-olefin polymer having 2 to 10 carbon atoms, such as polyethylene, polypropylene, or ethylene butene copolymer. The boat may have roughened surfaces.

In addition, cellulose nitrate, cellulose acetate, cellulose acetate butyrate, cellulose acetate globionate, polystyrene, polyethylene terephthalate, polycarbonate F, which are commonly used in photosensitive materials.
Films such as

These supports may be transparent or transparent depending on the purpose of the photosensitive material.
Choose something opaque. In addition, when it is transparent, it is not only colorless and transparent, but also dyes and pigments can be added to make it colored and transparent. This has been done for a long time with X-ray films, etc., and also according to J, SMPTE 672.
Also known as c+6 (t95g).

Opaque supports include opaque materials such as paper, transparent films with pigments such as dyes and titanium oxide added, surface-treated plastic films, and even carbon black dyes added to make them completely light-shielding. Also includes paper, plastic film, etc. When the adhesive strength between the support and the photographic emulsion layer is insufficient, it is possible to provide a layer having adhesive properties to both as an undercoat layer.

Further, in order to further improve the adhesion, the surface of the support may be subjected to preliminary treatment such as corona discharge, ultraviolet irradiation, flame treatment, etc.

When using the hardener of the present invention, each layer of the photosensitive material can be coated by dip coating, air knife coating, curtain coating, spray coating, or exdolsion coating using a hopper as described in U.S. Pat. No. 2,681,294. It can be applied by a variety of coating methods including.

If necessary, see US Pat. No. 2,761,791 and US Pat. No. 3.
It is also possible to apply two or more layers simultaneously by the methods described in US Pat. No. 508,947 and US Pat.

Next, as the type of silver halide (according to the present invention), silver chloride, silver bromide, silver chlorobromide, silver iodobromide complex, silver chloroiodobromide, etc. can be used.

The shape of these silver halide grains may be cubic, octahedral, or a mixed crystal form thereof. The particle diameter and average particle size distribution do not need to be limited to K, and may be of any value.

These silver halogenide grains are produced according to known and commonly used methods. Of course, it is also useful to use the so-called single or double jet method, controlled double jet method, or the like.

Furthermore, two or more kinds of silver halogenide photographic emulsions formed separately may be mixed.

Furthermore, even if the crystal structure of silver halide grains is uniform throughout the interior, there are also those with a layered structure with different interior and exterior structures, British Patent No. 635,841, U.S. Patent No. 3,622,
It may also be of a so-called conversion type as described in No. 318. Further, either a type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the particle may be used. These photographic emulsions are from ``The Theory of Photogr'' by 1dees (Glass).
aphic Process' (The Φ Theory of Fist Photography Process), Mac Mill
Published by an-sha: P, Grafikid@s ” Ch1mi@Photographiqu
e” (Shimmy Fist Photography), Paul
Such silver halide grains can be prepared by various methods such as the generally accepted ammonia method, neutral method, acidic method, etc., which are described in Go's bottom book published by Mont@1sha (1957). After its formation, it is washed with water to remove by-product water-soluble salts (e.g., silver nitrate and bromide; potassium nitrate when silver bromide was made using J ram) from the system, followed by heat treatment and chemical amplification. Sensitizers, such as sulfuric acid) IJium, N,N,N'-trimethylthiourea, -side thiocyanate lead acid, thiosulfate lead acid,
This is done in the presence of stannous chloride, hexamethylenetetramine, etc. to increase sensitivity without coarsening the particles. These dosage methods are described above.

The above silver halide emulsion can also be chemically sensitized by conventional methods.

Photographic emulsions using the hardener according to the present invention can be spectral sensitized or enhanced by using cyanine dyes such as cyanine, merocyanine, and carbocyanine alone or in combination, or in combination with styryl dyes, etc., as necessary. Sensitization can be performed.

The selection can be arbitrarily determined depending on the wavelength range to be sensitized, sensitivity, etc., and the purpose and use of the photosensitive material.

Various compounds can be added to the above-mentioned photographic emulsion in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the light-sensitive material. These compounds are 4-hydroxy-6-methyl-1,3゜3a, 7-chitrazaindene, 3-methyl-benzothiazole, l-phenyl-
A large number of compounds have been known for a long time, including 5-mercaptotetrazole, many heterocyclic compounds, mercury-containing compounds, mercapto compounds, and metal salts.

An example of a compound that can be used is "The
Theory of Photographic Pr
cess ll (3rd edition, 1966) 344-34
The original documents are listed on page 9.

When the hardener according to the present invention is used in a photosensitive material, it can be used together with a matting agent. The matting agent is preferably fine particles of a water-insoluble organic or inorganic compound with an average particle size of 0.2μ to 10μ. Examples of the organic compound include water-dispersible vinyl polymers such as polymethyl acrylate, Examples of cellulose derivatives include polymethyl methacrylate, polyacrylonitrile, acrylonitrile-α-methylstyrene copolymer, polystyrene, styrene-divinylbenzene copolymer, polyvinyl acetate, polyethylene carbonate, polytetrafluoroethylene, and cellulose derivatives such as methyl cellulose and ethyl cellulose. , cellulose acetate, cellulose acetate glopionate, etc. Examples of starch derivatives include carboxy starch, carboxynitrophenyl starch, urea-formaldehyde-starch reactants, etc. Gelatin and coacervate hardened with known hardening agents to form microcapsules. Hardened gelatin or the like can be preferably used. Examples of inorganic compounds that can preferably be used include silicon dioxide, titanium dioxide, magnesium dioxide, silver chloride desensitized by a method known in the art, such as silicon dioxide, titanium dioxide, magnesium dioxide, di[tS aluminum, barium sulfate, calcium carbonate, and known methods], bromide, and glass. .

The above-mentioned matting agents can be used by mixing different types of substances as necessary.

When the hardener according to the present invention is used in a photographic material, the photographic emulsion layer and its rib layers may also contain a synthetic polymer compound, such as a latex-like water-dispersed vinyl compound polymer, particularly for improving the dimensional stability of the photographic material. Compounds that increase the
(of different types of polymers) or in combination with hydrophilic water-permeable colloids. There are many types of polymers, such as U.S. Pat. No. 2,736,005;
No. 2,739,137, No. 2,853,457, No. 3,062,674, No. 3,411,911, No. 3
, No. 488,708, No. 3,525,620, No. 3,
635,715, 3.607,290, 3.6
No. 45,740, British Patent No. 1,186,699, No. 1
, No. 307, 373, etc. Among these descriptions are alkyl acrylate, alkyl methacrylate, acrylic acid, methacrylic acid, sulfoalkyl acrylate, sulfoalkyl methacrylate,
Copolymers and homopolymers selected from glycidyl acrylate, glycidyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, alkoxyalkyl acrylate, alkoxy methacrylate, styrene, butadiene, vinyl chloride, vinylidene chloride, maleic anhydride and itaconic anhydride. is commonly used. In some cases, when these vinyl compounds are subjected to emulsion polymerization, a so-called graft-type emulsion polymerization latex carried out in the coexistence of a hydrophilic protective colloid polymeric substance may be used.

A surfactant may be added alone or in combination to the emulsion used in the light-sensitive material to which the hardener according to the present invention is applied. Although they are used as coating aids, they are sometimes applied for other purposes, such as emulsifying and dispersing, sensitizing, improving photographic properties, antistatic, antiadhesive, etc.

nonionic surfactants, higher alkylamines,
Quaternary ammonium salts, pyridine and other heterocycles,
Cationic surfactants such as phosphonium or sulfoniums, anionic surfactants containing acidic groups such as carboxylic acid, sulfonic acid, phosphoric acid, and sulfuric acid ester groups, amino acids, aminosulfonic acids, and sulfuric or phosphoric acid esters of amino alcohols. Divided into amphoteric active agents.

Regarding these active agents, see Ryohei Oda et al., "Synthesis of Surfactants and Their Applications" (Maki Shoten, 1964 edition) and A. W. Berry, "Surface Active Agents" (Interscience Bubbles Incorporated, 1958), J. , P. Sisley [Encyclopedia op.
1964 M) etc. are listed in neglect.

The method of the present invention can be used for light-sensitive materials containing color couplers. The coupler used is 2-equivalent type or 11t4-equivalent type diketomethylene type coupler x-o-Jy.
Used are 7'5-14 weight type or 2-equivalent type pyrazolone type and indacylon type magenta couplers, as well as α-su7tole type cyan couplers and phenol type cyan couplers.

The types of photosensitive materials to which the method of the present invention can be applied include general-purpose black and white photosensitive materials, printing photosensitive materials, printing plates, X-ray photosensitive materials, color films, color papers, diffusion transfer photosensitive materials, and other photosensitive materials. It can be advantageously applied to a wide range of photosensitive materials having a hydrophilic layer coated on water-resistant base paper or plastic film, such as image-receiving layers and heat-developable photosensitive materials. Of course, there is no problem even if these photosensitive materials contain a developer.

Further, the hardening agent according to the present invention can be used not only by being added to a light-sensitive material, but also into a processing bath depending on the case.

(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example-1 A silver iodobromide emulsion consisting of 2.0 moles of silver iodide and the remaining 98 moles of silver bromide was subjected to gold-sulfur sensitization, chemically ripened, and then treated with stabilizers and coating aids according to conventional methods. An emulsion was prepared by adding an appropriate amount of .

This emulsion was divided into parts, and a hardener according to the present invention as well as comparative (a) mucochloric acid and (b) formaldehyde were added thereto as shown in Table 1, and uniformly coated and dried on a subbed polyethylene terephthalate film base. A sample was obtained. The conditions for the corona discharge treatment are a high frequency output of 6K.
W, frequency 110±5 KH2s voltage 60V, grid current 100mA, distance from discharge surface 0.7±0.1 ttm
The treatment was carried out approximately 10 seconds before coating using an online force method under the conditions of an anode current of 0.3 A.

The amount of gelatin applied to the sample was 5. ! i'/m, and the amount of silver halide is 1.5% by weight with gelatin in terms of silver. : Adjusted to be I Vc. These samples were incubated at 50'C 180% RH for 2 days, 3 days and 4 days.
Table 1 shows the hardness of the samples that were stored for 1 day and those that were allowed to stand for 4 days.

The degree of hardness in the table is determined by immersing the sample in pure water at (9)°C for 1 minute, then attaching a needle with a steel ball with a radius of 0.21111E to the tip of the sample and moving it over the film surface at a speed of 5 disks per second. Continuously operate so that a load of 0 to 200 g is applied to the needle,
It is expressed as the weight at which scratches occur on the sample surface.

Table 1 As is clear from Table 1 above, compared to the conventionally known representative hardener (comparison) K, the hardener of the present invention has excellent film surface strength on a polyethylene terephthalate support in a short period of time. The obtained result was obtained by calculating the water/soil ÷ Example-2 135y/m polyethylene-coated paper treated with online corona discharge treatment just before application in the same manner as in Example-I, and two water-resistant thick sheets treated one month ago. Prepared.

Next, appropriate amounts of stabilizers and coating aids were added to the ortho-sensitized high-contrast jJ silver bromide emulsion, and after addition of comparative and inventive hardeners as shown in Table 2 below, the emulsion was coated on the base paper. A sample was prepared by uniformly coating and drying.

The coating amount of the emulsion layer was such that gelatin was 2.0 g/m and the silver amount calculated as silver nitrate FC was 1.59/rrl. After this sample was allowed to stand for 3 days under the humidity control condition of 45° C. and RH5096, an adhesive cellophane tape (Tsuba Cellotape manufactured by Nichiban) was directly applied and pressed onto the emulsion layer, and then an adhesion test was conducted in which it was strongly peeled off. .

Adhesion evaluation in Table 2 is based on the following criteria.

2) White rating ◎: Complete adhesion; tearing and peeling occurs due to destruction of the polyethylene layer.

○: Adhesion on the entire surface; there is some lifting of the emulsion layer, but no peeling of the emulsion layer is observed.

Δ: Partial adhesion; the emulsion layer is partially peeled off from the polyethylene layer.

×: Non-adhesion: The emulsion layer is completely peeled off from the polyethylene layer.

Table 2 Table 2 shows that both the samples of the present invention that were subjected to corona discharge treatment immediately before coating and those that were treated one month ago had good adhesion to the support.

Example-3 2-(1-benzyl-2,4-dioxyimidazolidin-3-yl)-2-pino(Clue 2'-chloro-5'
-(4-(2,4-ditardial milk enoxy)
butanamide] acetanilide
A yellow coupler dispersion was prepared by dissolving it with hexyl and ethyl acetate and dispersing it in a gelatin solution using sodium cetyl sulfate. This coupler emulsion was added to a Hanawa silver bromide emulsion for full color printing to obtain a color emulsion.

Divide this emulsion and add the hardener according to the present invention and the comparative hardeners (e) and (d) as shown in Table 3 below,
Example-1 on 180 g/m'' polyethylene coated base paper
The coating was uniformly coated and dried using the same online corona discharge treatment.

The coating amount of the emulsion is 2g of gelatin and 0g of Shio coupler.
, s9/rl and the amount of silver converted to silver nitrate is 0.15 g/
It was configured to be d.

Comparative hardener (C); hexamethylene-1,6-bis[aziridinylcarbamide] Comparative hardener (a); bis(vinylsulfonylmethyl) ether The obtained sample was stored at 45°C and RH6096. Table 3 below shows the measured film surface strength.

Table 3 As is clear from Table 4, compared to the comparative sample 1, the sample according to the present invention had less posterior dura and had excellent hardening properties, and had mechanical strength that could withstand harsh treatments. It is accompanied by being.

(Effects of the Invention) According to the method of the present invention, there is no deterioration of photographic properties seen with conventional hardeners, no increase in viscosity when the coating solution stagnates, and there is no progress in hardness over time, which is called post-hardening. The adhesive properties and physical properties of the film are good, and the occurrence of peeling and scratches is significantly reduced.

In addition, since the follow-up effect of corona discharge treatment can be fully utilized, good adhesion is always obtained, and since the corona discharge treatment and coating process can be separated, there is no risk of light leakage fogging during emulsion coating, and dust adhesion due to charging. Accidents such as this can be avoided. In addition, the above-mentioned follow-up effect can be fully utilized for easily one month.

Claims (1)

[Claims] (1) A photosensitive material in which a hydrophilic colloid layer is provided on the surface of a support having a plastic surface, characterized in that the hydrophilic colloid layer contains a compound represented by the following general formula [I]. Silver chemical photographic material. General 2〇) R"R' -St -R," 4 [In the formula, R1 represents a substituted or unsubstituted lower alkyl group, lower alkenyl group or aryl group. Further, R2 Ha and R4 represent a lower alkyl group, an alkoxy group, an alkylcarboxy group, an epoxyalkoxy group, an alkenyl group or a haryyl group. However, at least one of R"*R2*R" and R4, which is centered on a silicon atom, has an epoxy group, a vinyl group, or an amine group at its terminal, and at least one of the remainder has an epoxy group, a vinyl group, or an amine group at its terminal. It does not have a group of (2) The silver halide photographic material according to claim 1, wherein the plastic surface is subjected to a corona discharge treatment.