JPS62201431A - Silver halide photographic sensitive material having subbing layer superior in adhesiveness - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material having a subbing layer superior in adhesiveness to both of a hydrophilic colloidal layer and a synthetic resin film by incorporating a specified block and/or graft polymer in a polymer made from a polymer latex. CONSTITUTION:The silver halide photographic sensitive material has the subbing layer formed by coating a synthetic resin film base with a polymer latex containing a polymer A capable of forming a polymer latex and a block polymer B having block units compatible with the polymer A and/or a graft copolymer B having graft units compatible with the polymer A in an amount of 10-99wt%, preferably, 20-95wt%, and the sum of A and B is added, preferably, in an amount of >=90wt% of the total polymers contained in the polymer latex grains.

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 having a subbing layer with excellent adhesiveness.

[Background of the Invention] Synthetic resin films have excellent physical properties as supports for silver halide photographic materials and the like, so their demand has increased in recent years and they have been widely used.

However, synthetic resin films are extremely hydrophobic;
It is often difficult to create strong adhesion between such supports and hydrophilic colloid layers, such as photographic gelatin layers, with materials such as gelatin as the binder.

Conventionally, in photographic materials using synthetic resin films, many subbing methods have been known for adhering the support and the hydrophilic colloid layer. To firmly bond the layers,
In either method, it is often necessary to use a swelling or dissolving agent for the synthetic resin film. However, when a subbing composition containing this swelling agent or dissolving agent is applied to a synthetic resin film, the flatness of the support is impaired during the subbing process, and the swelling agent or dissolving agent is - Because most of them use harmful organic solvents,
It had many drawbacks such as compromising work safety.

For this reason, it has been proposed to undercoat synthetic resin films without using swelling or dissolving agents.

One technology is to create a synthetic resin film whose surface has been chemically or physically treated, such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, activated plasma treatment, laser treatment, etc. Supports that have been subjected to surface activation treatments such as treatment, mixed acid treatment, and ozone oxidation treatment have been proposed. This technology is covered by U.S. Patent No. 2,943.
, No. 937, No. 3.475, 193, No. 3,61
5,557, British Patent No. 1.215,234, U.S. Patent No. 3,590,107, and Japanese Patent Application Laid-Open No. 1983-1
This method has been proposed in No. 3672, Japanese Patent No. 55-18469, and the like. However, these surface-treated synthetic resin films have some copolar groups on the film surface, which was originally hydrophobic, and the thin layer that is a negative factor for surface adhesion has been removed. Although the adhesive force with the hydrophilic protective colloid layer for copying pages increased, sufficient adhesive strength was not obtained.

Furthermore, in order to increase the adhesion to a photographic hydrophilic colloid layer, a synthetic resin film has been proposed in which a hydrophilic coating composition layer is provided on a surface-treated layer.

The subbing layer made of this hydrophilic coating composition must have sufficient adhesion to both the synthetic resin film and the photographic hydrophilic colloid layer.

In particular, in order to ensure sufficient adhesion between the subbing layer and the photographic hydrophilic colloid layer, hydrophilic groups or reactive groups are generally included in the resin component of the subbing layer (hereinafter referred to as subcoating resin). It is. Examples of the hydrophilic group or reactive group include acids (e.g., acrylic acid, itaconic acid, semi-alkyl esters of itaconic acid, etc.), epoxy groups (e.g., glycidyl acrylate, glycidyl methacrylate, etc.),
N-alkanol groups [e.g. N-methylolacrylamide, hydroxymethyl-N-(1,1-dimethyl-3
-oxobutyl) acrylamide, etc.], and hydroxyl groups (e.g., hydroxyethyl methacrylate, hydroxyethyl acrylate, etc.).

Among the above, examples in which the undercoating resin containing an acid component is included in the undercoat layer include Japanese Patent Publication No. 48-3546, Japanese Patent Publication No. 1123-1983, Japanese Patent Publication No. 50-1718, and European Patent No. 1484 Specification N1 No. 54-61518, No. 50-39536
It is disclosed in the specification publication, US Patent No. 3,545,972, etc.

However, in a synthetic resin film having an undercoat layer containing an acid component in the undercoating resin, the adhesiveness of the photographic hydrophilic protective colloid layer during development processing was insufficient.

An example in which the undercoat layer contains an undercoat resin containing an epoxy group component is as follows:
Japanese Patent Publication No. 34-9629, Japanese Patent Publication No. 51-58469,
No. 52-104913, No. 51-27918, No. 52-19786, No. 54-30121, No. 51-
121323 specification, British Patent No. 1.168j71 specification, Japanese Patent Application Laid-open No. 55-69138, etc. However, epoxy group components such as glycidyl methacrylate or glycidyl acrylate,
It has self-crosslinking properties and easily decomposes, and its quality deteriorates during the synthesis of the Shimoki resin or during the storage of the synthetic solution. (referred to as liquid withdrawal) had insufficient stability.

Examples in which the undercoat layer contains an undercoat resin containing an N-alkanol group component are disclosed in French Painting Patent No. 140,408 and JP-A No. 5
Publication No. 1-131516, British Patent No. 1,178,59
It is disclosed in Japanese Patent Publication No. 57-3054. However, the N-alkanol acryl 7amides described in these documents have strong self-crosslinking properties, and crosslinking occurs during the synthesis of the lower-citing resin or during storage of the synthetic solution, resulting in insufficient stability of the synthetic solution and the lower-compound solution. Met.

In this way, the hydrophilic composition containing the lower resin (hereinafter referred to as lower latex) must adhere not only to the hydrophilic colloid layer but also to the synthetic resin film, despite its hydrophilicity. Until now, improvements have been made mainly by changing the components of the polymer that forms the latex cited below. However, most of the versatile, high-performance, and inexpensive monomers have already been researched, and we have reached the point where no further performance improvement can be expected. Latex for undercoating that is sexually satisfactory has not been obtained.

[Object of the Invention] Therefore, an object of the present invention is to provide a silver halide photographic light-sensitive material having a subbing layer having excellent adhesion to both a hydrophilic colloid layer and a synthetic resin film.

[Structure of the Invention] The above-mentioned object of the present invention is to provide a synthetic resin film support with:
In a silver halide photographic material having a polymer latex layer formed by film formation, the polymer latex layer is
This was achieved using a silver halide photographic light-sensitive material containing a block polymer having block units compatible with the polymer latex-forming polymer and/or a graft polymer having compatible graft units.

[Specific Structure of the Invention] The latex-forming polymer used in the present invention may be any polymer that forms latex in water, which is a dispersion medium, but preferably has a glass transition point (T!7). is a polymer in the range of 40 to 150°C.

Examples of the polymer latex-forming polymer of the present invention include acrylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate, and glycidyl acrylate; methacrylic esters such as methyl methacrylate, ethyl methacrylate, hydroxyl methacrylate, and glycidyl methacrylate; Acrylic acid amide derivatives such as dimethylacrylamide, N,N-diethylacrylamide, methacrylic acid amide derivatives such as N,N-dimethylmethacrylamide, vinyl esters such as vinyl acetate, vinyl halides, vinylidene halides, styrene derivatives, butadiene, Homo or copolymers obtained by polymerizing heptamers such as isoprene and acrylonitrile can be mentioned.

Particularly preferred are homo- or copolymers formed by polymerizing at least one member selected from acrylic esters, methacrylic esters, vinyl halides, vinylidene halides, vinyl acetate, butadiene, and styrene.

Methods for producing these polymer latexes are known and can be easily produced by those skilled in the art. Production methods include an emulsion polymerization method and a method in which a polymer synthesized by solution polymerization or bulk polymerization is dissolved in a water-insoluble solvent and dispersed in water (abbreviated as redispersion method), but emulsion polymerization is preferred.

The molecular weight of the polymer latex-forming polymer of the present invention was measured using gel permeation chromatography (hereinafter referred to as GPC) to determine the number average molecular weight in terms of styrene.
The range of ~1oo, ooo is preferable.

The latex-forming polymer of the present invention [hereinafter simply referred to as polymer]
A) is used in combination with a block polymer having a block unit compatible with the polymer (A) and/or a graft polymer E having a graft unit compatible with the polymer (A), hereinafter simply referred to as polymer (B).

In the polymer (B), the block unit or graft unit that is compatible with the polymer (A) is a polymer chain, and preferably the difference in solubility parameter between the polymer (B) and the polymer (A) is within ±2, or more. Preferably it is within ±1.

In addition, the content of block units or graft units in polymer (B) that is 11% and compatible with polymer (A) is preferably in the range of 10 to 99% by weight, and preferably in the range of 20 to 95% by weight. preferable.

The polymer (B) of the present invention contains a polymer (
Macro that can have various linking groups (for example, thio group, oxy group, carbonyloxy group, etc.) and terminal groups introduced during the synthesis of B) and into which the above units are derived within the range that does not impede the purpose of the present invention. There is no problem even if it contains a component derived from a monomer that can be copolymerized with a hexamer or the like.

The molecular weight of the polymer (B) of the present invention is 2,000 to 200.000 as a number average molecular weight in terms of styrene using GPC.
A range of is preferred.

Methods for synthesizing the graft polymer, which is the polymer (8) having graft units compatible with the polymer (A) of the present invention, include conventionally known chain transfer methods, radiation grafting methods, mechanical methods, and chemical methods. Although any of the chemical reaction method, polymer initiator method, prepolymer bonding method, macromonomer method, etc. can be preferably used, the most effective graft polymer of the present invention can be obtained especially by synthesis by the macromonomer method.

The above-mentioned method for synthesizing the graft polymer includes, for example, radical polymerization of monomer (for example, hydroxyethyl methacrylate) in the coexistence of thioglycolic acid with a molecular weight of 300 to 10,
A single-terminated carboxylic acid prepolymer of 000 is obtained, and this is reacted with glycidyl methacrylate to produce a macromonomer having a methacrylic acid ester type terminal group.

If, for example, methyl methacrylate is used as a copolymerization component for this macromonomer, a graft polymer having a methyl methacrylate trunk and a portion of polyhydroxyethyl methacrylate anchors as branches can be obtained. Moreover, the opposite graft polymer can also be easily obtained.

Methods for synthesizing the block polymer, which is the polymer (B) having block units compatible with the polymer (A) of the present invention, include conventionally known anionic living polymerization methods, linking of both anionic and cationic living polymers, Both the terminal functional group method and the condensation method can be preferably used.

Vinyl monomers, such as methyl methacrylate, are radically polymerized in the coexistence of thioglycolic acid, and the molecular weight is 300 to 10.
,000 one-terminal carboxylic acid polymer, and also, for example, lauroyl methacrylate was radically polymerized in the coexistence of mercaptoethanol to obtain a polymer with molecules of 111,000 to 10
,000 of a single-terminated hydroxy polymer is obtained. By condensing this one-end carboxylic acid polymer and one-end hydroxy polymer, the desired block polymer can be obtained.

In the polymer (B), which is at least one polymer selected from the above-mentioned graft polymers and block polymers of the present invention, a vinyl monomer having a hydrophilic component is used to form a portion compatible with a synthetic resin film or a hydrophilic colloid. It is preferable to use, as the vinyl monomer, a vinyl monomer having -803M1, a vinyl monomer having a -000M group, a vinyl monomer having a polyalkylene oxide chain, and after forming a macromonomer, a graft polymer or a block polymer. Examples of monomers capable of introducing -803M groups or -000M groups include nyl monomers (hereinafter abbreviated as -803M group-introducing monomers and -C00M group-introducing monomers, respectively).

Here, M is a hydrogen atom or a cation, and has the same meaning below.

Examples of the vinyl monomer having 18 OaM groups include p-styrenesulfonic acid, sodium 2-acrylamido-2-methylpropanesulfonate, sodium acryloyloxyethylsulfonate, sodium 3-methacryloyloxypropylsulfonate, and the like.

Examples of the vinyl monomer having -COOMM include acrylic acid, methacrylic acid, itaconic acid, and maleic acid.

Examples of the vinyl monomer having a polyalkylene oxide chain include monomers represented by the following general formula [I].

General formula [I] CH2-C+X) (A O key R': H or CHa A knee C2H now- or -C3Hs- Q: H or an alkyl group having 1 to 9 carbon atoms n: integer from 1 to 50 Specifically, the following compounds may be mentioned.

CH3 CH2=C C-0-C2H40H Ha CH2-C Ha CH2-C ■ Ha CH2-C C-N H-(-Ca Hs Osu1πC Hs
(t) 18 when using a 1-3O3 group-introducing monomer
Taking hydroxyethyl methacrylate as an example, the method for introducing hydroxyethyl methacrylate may be to form a macrohetamine of hydroxyethyl methacrylate and then react it with propane sultone or the like using sodium carbonate or the like as a catalyst.

The 18 OaM group may be introduced after the graft polymer or block polymer is formed.

When using a -COOM group-introduced monomer,
When introducing a -COOM group into a macromonomer using the macromonomer method, if the -COOM group of the branch polymer must be protected, maleic anhydride, acrylic ester, or methacrylic acid can be used as the -COOM group-introducing monomer. Examples include esters. These may be hydrolyzed by a known method after forming a graft polymer or block polymer.

The vinyl monomer having a hydrophilic component is the polymer (
Considering the compatibility with A) and the compatibility with hydrophilic colloids, it is preferable to copolymerize the vinyl monomer with other vinyl monomers so that the amount of the vinyl monomer is 30% by weight or more.

Examples of other vinyl monomers to be copolymerized with the vinyl monomer having a hydrophilic component include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate, and sulfopropyl methacrylate. Methacrylate ester:
Vinyl esters such as vinyl acetate and vinyl pionate; Vinyl ethers such as methyl vinyl ether and butyl vinyl ether; Vinyl ketones such as methyl vinyl ketone and ethyl vinyl ketone; Styrenes such as styrene, methylstyrene, and polymethylstyrene. : Acrylonitrile, vinyl chloride, vinylidene chloride, butadiene, isoprene, etc.

Some of the graft polymers and block polymers, which are the polymer (B) of the present invention, are commercially available as Aron G (manufactured by Toagosei Chemical Industry Co., Ltd.) and Modiva H (manufactured by NOF vA), respectively.

As a method for containing the polymer (A> and polymer (B) of the present invention in the form of a polymer latex, the polymer (B) is dissolved in a monomer from which the polymer (A) is derived during emulsion polymerization, and then polymerized. Methods include a method in which polymer (A) and polymer (B) are simultaneously dissolved and dispersed using a redispersion method, and a method in which polymer (B) dissolved in an organic solvent is added to a latex of polymer (A).

The polymers contained in the latex particles of the present invention mainly consist of the above-mentioned polymer (A) and polymer (B), and polymers other than these may also be present as long as they do not impede the purpose of the present invention. No, but polymer (
Preferably, it consists essentially of polymer A) and polymer CB), and most preferably consists only of both of these polymers. Specifically, the total ratio of polymer (A) and polymer (8) to the polymers contained in the latex particles is preferably 90% or more.

In the latex particles of the present invention, the polymer (A) and the polymer (B) are present in a mixed state as a so-called polymer blend.

The mixing ratio of both polymers is such that polymer (B) is polymer (A).
>0.001 to 10% by weight, particularly preferably 0.01 to 5% by weight.

The particle size of the latex particles of the present invention is 0.01 to 5.0μ
m is preferable, and more preferably 0.05 to 1.0 μm.

The latex particles of the present invention may contain compounding agents (for example, a plasticizer such as dioctyl phthalate, a fluorine-containing surfactant, etc.) in addition to the polymers (A) and (B).

Examples of producing a latex containing polymer (A) and polymer (B) used in the polymer latex layer of the present invention will be shown below, but the present invention is not limited thereto.

Production Example 1 A surfactant of 10σ is mixed with water 11 that has been degassed with N2 gas, and the temperature is raised to 80°C. Next, ammonium perfaate oy
ysg and while stirring, add Aron G■C-10 (l
I! Monomer mixture (n-butyl acrylate 10% by weight, t-
Butyl acrylate 35% by weight, styrene 27% by weight,
Hydroxyethyl methacrylate 28% by weight) 250
Add Q dropwise over 1 hour. After the dropwise addition was completed, the reaction was continued for another 4 hours, and steam distillation was performed for 1 hour to remove some residual monomer, thereby obtaining the desired latex (1).

Production Example 2 Monomer mixture (n-butyl acrylate 10% by weight,
Polymer 80 which is prepared by prepolymerizing 35% by weight of t-butyl acrylate, 27% by weight of styrene, and 28% by weight of hydroxyethyl methacrylate! ] and Aron G”C-100,
8Q and ethyl acetate-1-butanol (1:1)
It was dissolved in 190g.

Further, 1.0 g of sodium dodecylbenzenesulfonate was dissolved in 40Q water. Furthermore, 40 g of gelatin was placed in a 500°C beaker, and 320 g of water was added to the gelatin, which was swelled for 30 minutes and then dissolved at 60°C.

Next, the dissolved gelatin solution and the aqueous sodium dodecylbenzenesulfonate solution were placed in a three-bottle flask having an internal volume of 11, and then heated to 35°C. Pour the above pre-dissolved solution into it and rotate it for 20 minutes at a speed of 1000 revolutions per minute.
After stirring for a minute, latex (1') was obtained.

Production example 3 a. a. ■C-1077),,A. ,. 0H-20(
Latex (2) was obtained in the same manner as in Production Example 1 using Toagosei Chemical Co., Ltd.).

Production Example 4 Latex (3) was obtained in the same manner as in Production Example 1, using Modiva-HM-18 (manufactured by NOF Corporation) in place of Aron G■C-10.

Production Example 5 7o) G"C-1 (1) Substance 1) C7[]:,zG■H-
20 (manufactured by Toagosei Kagaku Kogyo ■) in the same manner as in Production Example 2 to obtain latex (2').

Production Example 6 Latex (3') was obtained in the same manner as in Production Example 2, using Modiva-HM-18 (manufactured by NOF Corporation) in place of Aron G'C-10.

Production Example 7 Ingredient A Styrene 50g Butadiene 50g Aron G■C-105q Water 200
gB acid component Sodium laurate 0.5g Potassium persulfate o, s g Water
In an autoclave containing 100 gB acid component 1Q at 60°C, while stirring, component A is added over 6 to 8 hours at a rate such that the internal temperature becomes 65 to 70°C. Continue the reaction for another 2 to 4 hours with latex (
4) was obtained.

Production Example 8 Component A Vinylidene chloride 40 j7 ethyl acrylate 60g Aron G"C-105g Water 200
gB ingredients Sodium laurate 0.5g Ammonium persulfate 0.5g Water 100
While stirring in the autoclave of gB acid component 11 at 60°C, component A is added over 6 to 8 hours at a rate such that the internal temperature becomes 65 to 70°C. After further reaction for 2 to 4 hours, latex (5) was obtained.

Production Example 9 In Production Example 1, 2.5 g of Aron G C-10 dissolved in 50 d of ethyl acetate was added to the latex obtained by removing and polymerizing Aron G C-10, and the mixture was heated at 60°C for 2. Stir for hours. After 2 hours, ethyl acetate was distilled off under reduced pressure to obtain latex (6).

The coating solution cited below using a latex containing the polymer (A) and polymer (B) of the present invention contains the resin component of the latex consisting of the polymer (A) and polymer (B) of the present invention in an aqueous dispersion medium at 0.00%. It contains 1 to 40% by weight, and may contain other additives such as a surfactant, a hydrophilic colloid, a matting agent, a lubricant, and a crosslinking agent added immediately before coating, as necessary.

Examples of crosslinking agents include photographic hardening agents, such as aldehyde compounds such as formaldehyde, ethylene urea compounds,
Examples include triazine compounds.

Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants.

The coating solution cited below is coated onto a synthetic resin film support.

In the present invention, examples of the synthetic resin film used as a support include cellulose triacetate film, polyester film, polystyrene film, polycarbonate film, etc., and polyester film is particularly preferred.

The synthetic resin film used in the present invention only needs to have a support surface made of synthetic resin, and may be one in which a synthetic resin is supported on another support such as a laminate film.

There is no particular limit to the thickness of the synthetic resin film, but it is about 12μffi to 500μ, preferably 40μI1.
A material having a diameter of about 1 to 200 μm is advantageous in terms of ease of handling and versatility. In particular, a biaxially stretched and crystallized polyester film is advantageous in terms of stability, strength, and the like.

Before applying the coating solution cited below onto a synthetic resin film, it is preferable to subject the surface of the synthetic resin film to various surface activation treatments to make it hydrophilic. Examples of the surface activation treatment include oxidizing agent solution treatment as described in U.S. Pat. No. 2,943,937, etc., and U.S. Pat. No. 3,475,193.
Ultraviolet absorption treatment as described in the specification of No. 1, etc., electrical discharge treatment of corona discharge as described in the specification of U.S. Pat. Examples include active gas irradiation treatment as described in , and flame treatment as described in US Pat. No. 3,590,107.

The coating liquid cited below is applied onto the synthetic resin film by any method. For example, the synthetic resin film can be coated by curtain coating, reverse roll coating, fountain air doctor coating, slide hopper coating, extrusion coating, dip coating, etc. Here, the resin component of the latex of the present invention is preferably 0.01 to
513/v2, particularly preferably 0.03 to 2 (J/f). Drying after the coating solution cited below can be carried out by a known method.

For example, hot air drying, infrared heat drying, heater roll drying, microwave drying, etc. can be used.

In the present invention, preferably, an upper layer is further applied on top of the undercoat layer. The upper layer may contain known natural hydrophilic organic colloids such as gelatin, kaze, and in, synthetic hydrophilic organic colloids, and antistatic agents, such as Japanese Patent Publication No. 46-24159.
Publication No. 48-93165 and Japanese Patent Application Publication No. 1987-93165
An aqueous solution of a hydrophilic polymer or the like as described in Japanese Patent No. 9-23828 can be applied.

This upper layer liquid may contain a matting agent, a hardening agent, a surfactant, etc. For coating and drying the upper layer liquid, any known method can be used as in the case of processing the lower layer. After drying these subbing liquids and the upper layer coating liquid provided as necessary, flame radiation treatment is performed as necessary.
Known surface treatments such as plasma treatment, corona discharge treatment, glow discharge treatment, and ultraviolet irradiation treatment may be performed.

The subbing layer of the present invention may be provided not only on one side of the synthetic resin film support but also on both sides.

A photographic hydrophilic colloid layer can be coated on the subbing layer of the synthetic resin film support provided with the subbing layer by a commonly used method. Specifically, various compositions for forming photographic light-sensitive layers, such as silver halide photographic emulsions, diazo light-sensitive compositions, gelatin compositions containing antihalation agents, or gelatin backing compositions for adjusting the curl balance of support films. Can cover objects etc.

The present invention can be applied to various photographic materials having a hydrophilic colloid layer, but typically includes photographic materials that use halogen silver as a photosensitive component, such as general negative photosensitive materials, general reversal photosensitive materials, It can be used in general positive light-sensitive materials, direct positive light-sensitive materials, special purpose (for example, printing, X-ray, high resolution, infrared, ultraviolet, etc.) silver halide photographic materials, and the like.

[Specific Effects of the Invention] The silver halide photographic material having the structure of the present invention as described above has excellent adhesion between the support and hydrophilic colloid layers such as various photographic light-sensitive layers, and is resistant to development processing. The photosensitive layer does not peel off from the support even after photographic processing.

[Specific Examples of the Invention] Hereinafter, the present invention will be specifically explained using Examples. Mr. g is not limited to these.

Example 1 30 (W/n2IIlin
) was subjected to corona discharge treatment. Next, 10 cc of the latex (1) of Production Example 1, 20 ma of surfactant having the following structural formula, and 30 ml of hexamethylene-1,6-bis(ethylene urea)
No, add 20 μl of subtraction liquid consisting of 90 cc of pure water to I! !
It was applied thickly and dried at 100°C for 1 minute. Next, an upper layer coating solution consisting of 1 g of gelatin, 20 mA of saponin, and 100 cc of pure water was further applied to a thickness of 20 μm and dried at 100° C. for 1 minute. The above operations were performed on both sides of the film, and a silver halide emulsion for X-rays shown below was coated on both sides of the obtained polyethylene film as an undercoat layer, and a protective layer (gelatin 1 G/m') was further coated on top of the silver halide emulsion for X-rays. Sample 1
I got it.

In addition, sample 2 was prepared in the same manner as in sample 1 except that the latex (1) above was replaced with the latex shown in Table 1 below.
I got ~10.

Silver halide emulsion for x-rays> A silver iodobromide gelatin high-sensitivity emulsion containing 98.5 mol% silver bromide and 1.5 mol% silver iodide was added with 1.2 g of 4- hydroxy-6-methyl-1,3
, 3a, 7-titrazyden, 10(+) diethylene glycol was added, and polyethyl acrylate was added as a binder latex at 1.0 g per 1 g of gelatin.
After addition of 2-hydroxy-4,6-dichloro-6-triazine sodium salt, silver was coated on both sides of the support so as to give silver la, oO/f.

The obtained samples 1 to 10 were exposed and processed with the following developer.

[Developer solution (undiluted solution)] Potassium bromide 2.5 g Disodium ethylenediaminetetraacetate 19 Potassium sulfite (
55% aqueous solution > 90d potassium carbonate
25 a Hydroquinone
10! J5-Methylbenzotriazole
100100II1 Nitrobenzotriazole
100mg 1-phenyl-5-mercaptotetrazole 30mg 5-ditroimidazole 50mg 1-phenyl-
4-Methyl-4- and droxymethyl-3-pyrazolidone o, s g Diethylene glycol 60 (1 Add water to make up to 500 tN, and adjust the pH to 10 with sodium hydroxide.
．． Adjusted to 6.

When used, the above stock solution is diluted 2 times with water.

The following adhesion tests were conducted on samples during and after treatment with developer. The results are shown in Table-1.

(1) Adhesion test and dry film test> On the emulsion surface of the sample that had dried after the development process, shallow scratches were made with a razor in the shape of the substrate, and after pressing cellophane adhesive tape on top of the scratches, the The residual rate of the emulsion film relative to the adhesive area of the cellophane tape when it was suddenly peeled off was expressed as a percentage.

Treatment film test> In a processing bath, the emulsion surface of the sample was scratched in the shape of a substrate with a sharp end, and the surface was rubbed, and the residual rate of the emulsion film was expressed as a percentage.

Table-1 *Comparison is made with Aron G using latex (1) used in Sample-1.
■ Same composition except for C-10.

As is clear from the results in Table 1, the silver halide photographic material having a subbing layer containing the latex of the present invention has excellent adhesion both during and after processing with a developing solution. I understand that.

Example 2 In Samples 1 to 10 of Example 1, a subbing layer was provided on one side of the polyethylene terephthalate film support, and on top of the subbing layer, a silver halide emulsion for printing shown below was applied, Samples 11 to 20 were provided with the same protective layer as in Example 1.
I got it.

(Silver halide for printing - A silver chloroiodobromide gelatin emulsion containing 75 mol % silver chloride, 24 mol % silver bromide and 1 mol % silver iodide was added to a silver chloride iodobromide gelatin emulsion containing 0.6 g of 4-chloride per mol silver halide). hydroxy-6-methyl-
1, 3, 3a, Fuchtrazyden was added, polyethyl acrylate was added as a binder latex at a concentration of 1.0 g per 1 g of gelatin, an anionic surfactant was added at a concentration of 401 nMf, and mucochloric acid was added. After adding silver amount 4. Coating was performed to achieve OQ/f.

The obtained samples 11 to 20 were exposed and processed with the following developer.

The composition of the developer is as follows.

Phenidone 0.4g Metol 5g Hydroquinone
1g anhydrous sodium sulfite
60 (1 hydrated sodium carbonate
54 G5-nitroimidazole
100 (J potassium bromide 2
．． Add 5g of water to make 1000d and make pi-110,20.

During and after the development process, an adhesion test was conducted in the same manner as in Example 1. The results are shown in Table-2.

Table-2 *Synonymous with Table-1.

As is clear from the results in Table 2, it can be seen that the samples of the present invention, like Example 1, had excellent adhesive properties both during and after the development process.

Procedural amendment (voluntary) August 8, 1985 Patent application No. 44682 2, Title of invention Silver halide photographic light-sensitive material having a subbing layer with excellent adhesion 3, Case made by the person making the amendment Relationship Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (1
27) Konishi Roku Photo Industry Co., Ltd. Representative Director Keio Benko 4 Agent 102 Address Kudan-Rosaka Building, 4-1-1 Kudankita, Chiyoda-ku, Tokyo Telephone 263-9524 Name (7614) Patent Attorney Li Miyao Ichinose
d, , , 7 Column ``3. Detailed Description of the Invention'' in the specification (1) [Plus transition point (T
g) is in the range of 40 to 150°C” is corrected to read “the positive transition point (Tg) is in the range of -40 to 150°C”.

(2) In lines 7 and 8 of page 27 of the specification, the phrase ``by a commonly used method'' is amended to read ``by a commonly used method.''

(3) In the 7th to 6th lines from the bottom of No. 33 of the specification, the phrase "tetrazydene is added," is amended to read "tetrazydene is added."

More than °°"'1°"3 ,",-1)i',...,6
1 missing-N ・

Claims (1)

[Claims] In a silver halide photographic material having a polymer latex layer formed on a synthetic resin film support, the polymer latex layer comprises a block polymer having a block unit compatible with the polymer latex-forming polymer and/or a polymer latex layer. Alternatively, a silver halide photographic material containing a graft polymer having compatible graft units.