JPH0215859B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to photographic materials, and more particularly to photographic materials in which a photographic layer consisting of a hydrophilic organic colloid is provided on a plastic film support having a hydrophobic surface. Conventionally, polyethylene terephthalate, cellulose triacetate, polystyrene, polycarbonate, and the like have been widely used as photographic supports because of their excellent transparency and flexibility. However, when using these polymers as supports,
Since all of the supports have hydrophobic surfaces, photographic layers (for example, photosensitive silver halide emulsion layers, intermediate layers, filter layers, etc.) consisting of protective colloids mainly made of gelatin can be firmly adhered to these supports. It is very difficult to do so. Surface treatments of hydrophobic supports in conventional techniques attempted to overcome these difficulties include (1) chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge; (2) After surface activation treatments such as active plasma treatment, lazy treatment, mixed acid treatment, and ozone oxidation treatment, a photographic emulsion is applied directly to obtain adhesive strength. There are two methods, one is to provide an undercoat layer and then coat the photographic emulsion layer thereon. (e.g. U.S. Pat. No. 2,698,241,
No. 2764520, No. 2864755, No. 3462335, 3475193
Among these, method (2) is more effective and widely practiced. All of these surface treatments are
This is thought to be due to the creation of polar groups on the surface of the support, which was originally hydrophobic, and the increase in the crosslinking density on the surface.As a result, the polar groups of the components contained in the undercoating liquid This may be due to an increase in the affinity with the adhesive, or an increase in the fastness of the adhesive surface. In addition, various ideas have been made for the structure of the undercoat layer. A layer that adheres well to the support (hereinafter referred to as the first undercoat layer) is provided as the first layer, and a photographic layer is placed on top of it as the second layer. The so-called multi-layer method involves applying a hydrophilic resin layer that adheres well to the base coat (hereinafter referred to as the second undercoat layer), and the single-layer method involves applying only one resin layer containing both hydrophobic and hydrophilic groups. There is. All of these methods are well researched;
The first layer of the undercoat in the multilayer method uses a copolymer starting from a monomer selected from vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, etc. As such, a number of resins such as polyethyleneimine, epoxy resin, grafted gelatin, and nitrocellulose have been investigated, and the suitability of gelatin, mainly, for the second undercoat layer has been investigated.
These methods have a certain degree of sufficient adhesive strength compared to conventional gelatin/silver halide photographic emulsions. However, in recent years, there has been a move to reduce the amount of coated silver in silver halide photographic materials from the perspective of resource conservation, and in order to prevent the accompanying decrease in image density, the photographic layer swells during the development process. Therefore, it has become necessary to reduce the amount of hardening agent in the photographic layer. When the amount of the hardening agent decreases in this way, an unprecedented problem arises in that the adhesive strength between the photographic layer and the second undercoat layer is insufficient, particularly in the development process. Also, the first undercoat
The undercoating liquid for the layer contains an aldehyde-based, activated vinyl-based, active halogen-based curing agent, or the like. Such a curing agent is often contained in a large amount in order to ensure strong adhesion between the plastic film support and the first undercoat layer. However, as the amount of curing agent increases, the adhesive strength between the second undercoat layer and the photographic layer becomes insufficient. Furthermore, an undercoat layer containing a large amount of a hardening agent had an adverse effect on photographic performance, such as lowering image density. The present invention has been developed to overcome the above-mentioned drawbacks. The first object of the present invention is to provide a photographic material that has strong adhesive strength between the second undercoat layer and the photographic layer even if the amount of curing agent in the photographic layer is reduced in order to adjust the photographic properties. It is something to do. Second, support and undercoat first.
The first undercoat is applied to provide strong adhesion between the layers.
The object of the present invention is to provide a photographic material having strong adhesive strength between the second undercoat layer and the photographic layer even if the layer contains a large amount of curing agent. Thirdly, the present invention provides an undercoating liquid that is less likely to have an adverse effect on photographic properties. Fourthly, it provides a primer liquid that is less irritating to the skin. These objects of the invention provide at least one subbing layer (first subbing layer) on the support;
In a photographic light-sensitive material having a light-sensitive emulsion layer,
A photographic light-sensitive material characterized in that it has a layer (second undercoat layer) containing a gelatin derivative derived by a reaction between a compound without a vinyl group and gelatin, between the undercoat layer and the photosensitive emulsion layer. It was finally achieved. The gelatin derivatives used in the present invention are those in which the amino group, imino group, carboxyl group and/or hydroxyl group contained in the polar or hydrophilic residues among the various amino acid residues constituting the gelatin molecule are Refers to chemically modified gelatin produced as a result of treatment with reactive monofunctional reagents. The term gelatin used herein as a starting material for the gelatin derivatives according to the present invention represents the scientific name for a protein material derived from collagen. It is also intended to include any other product substantially equivalent thereto, such as when such product is synthesized. Normally, gelatin includes so-called alkali-treated gelatin, which is treated with lime etc. in the process of deriving collagen, so-called acid-treated gelatin, which is also treated with hydrochloric acid, etc., so-called enzyme-treated gelatin, which is treated with hydrolytic enzymes, etc., and each of these gelatins. Low-molecular-weight gelatin obtained by further hydrolysis of can. The monofunctional reagent necessary for preparing the gelatin derivative used in the present invention may be a compound having one functional group in the molecule that can react with the amino group, imino group, carboxyl group, and/or hydroxyl group in the gelatin molecule. Representative functional groups, which can be used to prepare gelatin derivatives that are almost equally useful in the practice of this invention, include the following. −NCO, −NCS, −NH・CO・SO ₃ M, −NH・
CS・SO ₃ M (M represents an alkali metal atom, such as a sodium atom or a potassium atom)

【formula】

[Formula] (R ¹ and R ² represent a hydrogen atom or an alkyl group, such as a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, etc., and X represents a halogen atom, such as a chlorine atom, a bromine atom, or a fluorine atom. ) -SO ₂ X (X has the same meaning as above), -COX (X has the same meaning as above),

【formula】

[Formula] (R ¹ has the same meaning as above),

[Formula] (X has the same meaning as above), -CH ₂ X (X has the same meaning as above), -
COOR ³ (R ³ is an aryl group having an electron-withdrawing group at the ortho or para position, such as an o-nitrophenyl group, a p-nitrophenyl group, a p-carboxylphenyl group), and the like. Representative examples of reagents having the above-mentioned functional groups suitable for preparing the gelatin derivatives used in the present invention are shown below. Phenyl isocyanate, p-tolyl isocyanate, 4-bromophenyl isocyanate, 2
- Isocyanates such as nitrophenyl isocyanate, 4-ethoxycarbonyl phenyl isocyanate, 1-naphthyl isocyanate, phenyl isocyanate bisulfite adduct, 4-biphenyl isocyanate, bisulfite adduct or their precursors; phenylthio Isocyanate, p-tolyl isothiocyanate, phenyl isothiocyanate
Thioisocyanates such as bisulfite adduct or their precursors; N-pentanoyl-2-ethyl-1-aziridine, 1-phenylcarbamoylaziridine, 2-
methyl-1-phenylcarbamoylaziridine,
1-dimethylaminosulfonylaziridine, 1-
Benzoylaziridine, 4-nitrobenzoyl-
1-Aziridine, 1-(2-chlorophenyl)carbamoyl-1-aziridine, 1-(3-methylphenyl)carbamoylaziridine, 1-(n-
butylsulfonyl)aziridine, 1-(phenylsulfonyl)-2-methylaziridine, 2-(1-
aziridinyl)-4,6-bis(ethylamino)-
1,3,5-triazine, 1-phenyl-3-
Aziridines such as (2-chloroethyl)urea or their precursors; N-vinylsulfonyl-p-toluidine, vinylsulfonylbenzene, 1-methyl-4-vinylsulfonylbenzene, acrylonitrile, 1-
Active vinyl compounds or precursors thereof such as (hydroxysulfonyloxy)-2-(4-methoxyphenylsulfonyl)ethane, 2-phenylcarbamoylethyl bromide; benzenesulfonyl chloride, 4-methoxybenzenesulfonyl chloride, 4-phenoxylene Cybenzenesulfonyl chloride, 4-chlorobenzenesulfonyl chloride, 4-bromobenzenesulfonyl chloride, 4-methylbenzenesulfonyl chloride, 3-nitrobenzenesulfonyl chloride, 3-carboxybenzenesulfonyl chloride, 2-naphthalenesulfonyl chloride, 4-aminobenzenesulfonyl chloride 3,4-diaminobenzenesulfonyl fluoride, 3-carboxybenzenesulfonyl fluoride; carboxylic acid halides such as 4-nitrobenzoyl chloride, 4-carboxybenzoyl bromide; succinic anhydride, phthalic acid Anhydride, hexahydrophthalic anhydride, isatoic anhydride, monomethylsuccinic anhydride, glutaric anhydride, benzoic anhydride, trimellitic anhydride, 3,6-dichlorophthalic anhydride, diglycolic anhydride acid anhydrides such as nitrophthalic anhydride; 3-phenoxy-1,2-epoxypropane,
3-(3-methylphenoxy)-1,2-epoxypropane, 3-(2,4-dibromophenoxy)-
1,2-epoxypropane, 3-(4-acetylaminophenoxy)-1,2-epoxypropane,
3-(2-biphenyloxy)-1,2-epoxypropane, 3-(2,4-dinitro-1-naphthoxy)-1,2-epoxypropane, 1-chloro-2-hydroxy-3-phenoxypropane , epichlorohydrin, 1-bromo-2-hydroxy-3-(2-chlorophenyl)propane and other oxirane ring-containing compounds or their precursors; halomethyl compounds such as bromoacetic acid and chloroacetic acid; o-nitrophenyl benzoate , p-nitrophenyl acetate, p-nitrophenyl-1-
Active esters such as hydroxynaphthoate; etc. These reagents have the function of chemically modifying gelatin by the method described below, and the gelatin derivative obtained as a result can be used as a material for the undercoat layer of the photographic material of the present invention, as described above. In addition, it has a great effect on adhesion between the second undercoat layer and the hydrophilic organic colloid layer. Among these reagents, reagents that increase carboxyl groups in gelatin side chains, such as succinic anhydride, phthalic anhydride, and trimellitic anhydride, are preferably used. The preparation of gelatin derivatives necessary for carrying out the present invention is carried out by treating gelatin with a monofunctional reagent (a compound having one functional group in the molecule that can react with a reactive group in the gelatin molecule) as described above. water or dimethyl sulfoxide, which can be used as a solvent;
A base or acid as a PH regulator in an organic solvent such as N,N-dimethylformamide, N,N-dimethylacetamide, tetramethylurea, tetramethylene sulfone, acetic acid, or a mixed solvent of these organic solvents and water. This is achieved by a general method of reacting in the presence of. In the gelatin derivative according to the present invention, at least one functional group among an amino group, an imino group, a carboxyl group, or a hydroxyl group in a gelatin molecule is chemically modified, and the substitution rate is 50% or more for one functional group. Among the functional groups, amino groups are most preferably modified, and the substitution rate is preferably 70% or more of the amino groups, more preferably 90% or more of the amino groups. The coating amount of the gelatin derivative according to the present invention is from 0.01 to 1 square meter of the support as a solid content.
Preferably it is 2.00g, especially 0.05-0.50g. The binder of the second undercoat layer applied to the photographic material of the present invention may be composed only of the above-mentioned gelatin derivative, or may be composed of a mixture of the gelatin derivative and other polymeric substances. As other polymeric substances, for example, polymers having repeating units represented by the following general formulas [] and [] can be preferably used. In addition, lime-treated gelatin, acid-treated gelatin, enzyme-treated gelatin, proteins such as colloidal albumin and casein, cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose, agar, sodium alginate, sugar derivatives such as starch derivatives, and synthetic hydrophilic colloids. ,
For example, it may contain polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide, or derivatives and partial hydrolysates thereof. When using derivative gelatin and non-derivative gelatin together, with respect to one functional group (for example, an amino group), the ratio should be such that 50% or more is substituted based on the total number of functional groups for both. It is preferable to adjust the usage ratio of both. R: hydrogen atom, alkyl group having 1 to 6 carbon atoms, or halogen atom M: hydrogen atom, alkali metal atom, alkaline earth metal atom, or organic base (e.g. trimethylamine, triethylamine) X: alkyl group having 1 to 6 carbon atoms, Alkoxy group, alkylamino group or halogen atom m: 0, 1 or 2 n: 1 or 2 R′: Hydrogen atom or alkyl group X′: Hydrogen atom, halogen atom, nitro group, cyano group, alkyl group, alkoxy group, alkoxycarbonyl group, alkylsulfonyl group,
Aryloxy group, acyl group, acyloxy group or acylamido group m': 0, 1 or 2 n': 1 or 2 The substituents in the general formulas [] and [] may be any of those listed above, but Among them, the following are particularly preferably used. R is a hydrogen atom,
M is a sodium atom or a potassium atom, m is 0, n is 1, R' is a hydrogen atom, m' is 0,
n′ is 1. A polymer having a repeating unit of the general formula [] is a homopolymer obtained by polymerizing a monomer represented by the following general formula [], or a polymer having at least one addition-polymerizable unsaturated bond with the monomer represented by the general formula []. It includes copolymers obtained by polymerizing monomers having the same, polymers obtained by introducing sulfinic acid groups into side chains after polymerization, and derivatives of these polymers. General formula [] However, R, M, X, m and n have the same meanings as in the general formula []. The monomer represented by the general formula []
It can be synthesized according to the synthesis method described in Chemistry Letters pp419-420 (1976), but is not necessarily limited to this synthesis method. The synthesis of other monomers is basically as simple as synthesizing the corresponding sulfonic acid chloride, and then following the above Chemistry procedure.
It may be reduced in the same manner as Letters or with a reducing agent such as sodium sulfite, and converted into vinyl if necessary. As monomers that can be copolymerized with the monomer represented by the general formula [], any monomer having at least one addition-polymerizable unsaturated bond can be used. Such addition polymerizable unsaturated compounds include styrenes (e.g. styrene, methylstyrene, styrenesulfonic acid, chloromethylstyrene, chlorostyrene, etc.);
Vinyl heterocyclic compounds (e.g. N-vinyloxazolidone, N-vinylpyrrolidone, N-vinylimidazole, etc.), vinyl ethers (e.g. methyl vinyl ether, butyl vinyl ether, etc.), vinyl esters (e.g. vinyl acetate, vinyl butyrate, etc.) vinyl chloroacetate, vinyl salicylate, etc.), and olefins (e.g. dicyclopentadiene, ethylene, 1-
butene, etc.) are preferably used. In the present invention, the polymer having repeating units of general formula [] must contain at least 0.1 mol% of repeating units represented by general formula [],
It is necessary to contain preferably 1 mol% or more, more preferably 10 mol% or more. 0.01% to 99% by weight, preferably 0.1% to 50% by weight of the solid content of the gelatin in the second layer of undercoat containing one or more of these polymers;
More preferably, if it is added in an amount of 1% to 20% by weight, the desired effect will be further enhanced. Examples of polymer compounds having repeating units represented by the general formula [] that can be used in the second undercoat layer in the present invention are shown below. All composition ratios are shown in molar ratios. Compound example In the present invention, a polymer having a repeating unit represented by the general formula [ ] is defined as
At least 0.1 mol%, preferably 1 mol% or more of repeating units represented by the general formula [], especially
It is a homopolymer or copolymer containing 10 mol% or more. Examples of compounds are shown below. Compound example Synthetic methods for compounds (8) to (13) are known, for example, as described in Journal of Organic Chemistry, Vol. 23, No. 544.
(1958), etc., using monomers for which the synthesis method is known, Journal of Polymer Science, A.
It can be easily synthesized by the polymerization method described in Vol. 1, Vol. 7, pp. 2175 and 2405 (1969). Some of the above compounds are also available as commercial products. For example, the polymer shown in Compound Example (8) is sold by Maruzen Sekiyu Co., Ltd. under the trade name "Resin M," and the polymer shown in Compound Example (9) is sold by Maruzen Oil Co., Ltd. under the trade name "Resin MB." Therefore, the object of the present invention can be achieved using such commercially available products. One or more of these polymers is coated with 0.01 solids content of gelatin in the second layer.
If it is added in an amount of 99% to 99% by weight, preferably 0.1% to 50% by weight, more preferably 1% to 20% by weight, the desired effect will be further enhanced. The undercoat liquid for the second undercoat layer used in the present invention can contain various additives as necessary. For example, matting agents, surfactants, antistatic agents,
Antihalation agents, coloring dyes, pigments, coating aids, antifoggants, etc. The matting agent is an inorganic or organic fine powder with an average particle size of 1 to 5μ, and inorganic matting agents include silica (silicon dioxide), magnesium oxide, titanium dioxide,
Organic matting agents such as calcium carbonate include polymethyl methacrylate, cellulose acetate propionate, polystyrene, etc., and silica and polymethyl methacrylate, particularly polymethyl methacrylate, are preferably used. The first undercoat layer according to the present invention contains various polymeric substances in order to achieve good adhesion to the plastic film support. The polymeric substances contained in the first undercoat layer include vinyl chloride, vinylidene chloride, methacrylic acid, acrylic acid, methacrylic ester, acrylic ester, itaconic acid, maleic anhydride, vinyl acetate, butadiene, styrene, etc. as starting materials. Copolymers can be mentioned. Among these copolymers, those using butadiene, styrene, or vinylidene chloride as a starting material are preferably used. Examples of synthesis or use of these copolymers are given in Japanese Patent Publications No. 35-13092 and No. 36-11779.
No. 47-28324, JP-A No. 50-43911, No. 51-
No. 114120, No. 50-131516, No. 51-135526, No.
No. 51-135-971, No. 52-49019, No. 51-120214
No. 51-58469, No. 51-117617, No. 51-
No. 121323, No. 51-123139, No. 51-139320, No.
No. 52-65422, No. 52-96016, No. 52-108114,
It is described in detail in No. 52-109923, No. 51-114121, etc. It is preferable to use a curing agent in the first layer of the undercoat,
Examples of curing agents include aldehyde compounds such as formaldehyde and glyoxazole, and ethyleneimino groups such as mucochloric acid, tetramethylene-1,4-bis (ethylene urea), and hexamethylene-1,4-bis (ethylene urea). methanesulfonic acid esters such as trimethylene bismethane sulfonic acid ester, active vinyl compounds such as bisacroyl urea and metaxine divinyl sulfone, and compounds containing active halogens such as 2-methoxy-4,6-dichlorotriazine. , compounds having epoxy groups such as bisphenol glycidyl ether, isocyanates, and the like. Among these, active halogen compounds, particularly 2-4 dichloro-6-hydroxy-S-triazine sodium salt, are particularly effective. The undercoat liquid for the first undercoat layer used in the present invention can contain various additives as necessary. Examples include surfactants, antistatic agents, antihalation agents, coloring dyes, pigments, coating aids, antifoggants, and the like. When using the undercoat liquid for the first layer of undercoat according to the present invention, there is no need to include an etching agent such as resorcinol, chloral hydrate, chlorophenol, etc. in the undercoat liquid. However, if necessary, apply an etching agent as mentioned above to the base coat first.
There is no problem in containing it in the layer. When coating on a plastic film support with a conventional undercoat layer by reducing the amount of curing agent in the photographic layer in order to adjust the photographic properties, the adhesive strength between the second undercoat layer and the photographic layer decreases. It was insufficient. However, surprisingly, if derivative gelatin is used in the second undercoat layer as in the present invention, strong adhesion can be maintained between the photographic layer and the second undercoat layer even if the amount of hardening agent in the photographic layer is reduced. arise. Moreover, when the second undercoat layer contains a polymer having a repeating unit represented by the general formula [] and/or [], an even more surprisingly strong adhesive force is produced. The undercoat liquid according to the present invention can be applied by a generally well-known coating method, such as a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, or the specification of US Pat. No. 2,681,294. It can be coated by an extrusion coating method using a hopper as described in . as needed,
U.S. Patent No. 2761791, U.S. Patent No. 3508947, U.S. Patent No. 2941898
Two or more layers can be simultaneously coated by the method described in No. 3526528, Yuji Harasaki, "Coating Engineering", p. 253 (published by Asakura Shoten, 1973). Of course, each or either of the first undercoat layer and the second undercoat layer can be composed of a plurality of layers. The thus applied undercoating liquid is then dried in a drying process, the conditions of which are 120°C to 200°C.
The heating time is 30 seconds to 10 minutes, but the temperature and time can be determined as appropriate within this range. In the present invention, plastic film supports include, for example, cellulose esters (especially cellulose triacetate, cellulose diacetate, cellulose propionate), polyamides, polycarbonates, polyesters (especially polyethylene terephthalate, poly-1,4-cyclohexane diacetate), Methylene terephthalate, polyethylene 1,2-
It refers to films made of diphenoxyethane-4,4'-dicarboxylate), polystyrene, polypropylene, polyethylene, etc., and composite films made by coating or laminating these films on other supports such as paper. Among them, polyethylene terephthalate film is most preferably used, especially biaxially stretched and heat-set polyethylene terephthalate film.
It is also advantageously used in terms of stability, toughness, etc. There is no particular limit to the thickness of the plastic film support, but a thickness of about 15 to 500 microns, especially about 40 to 200 microns, is advantageous in terms of ease of handling and versatility. Further, the support may be transparent, may contain a dye, may contain a pigment such as titanium dioxide, and may further include silicon dioxide, alumina sol,
It may contain chromium salt, zirconium salt, etc. A photographic light-sensitive material is prepared by coating a photographic layer by a conventional coating method on a support provided with an undercoat layer according to the present invention. As the photographic layer, for example, a silver halide emulsion layer,
Examples include an intermediate layer, a filter layer, a surface protection layer, and a backing layer. These photographic layers are layers using hydrophilic colloid as a binder, but as a hydrophilic colloid,
Examples include gelatin, phthalated gelatin, maleated gelatin, carboxymethylcellulose, hydroxyethylcellulose, grafted gelatin, polyvinyl alcohol, polyhydroxyalkyl acrylate, polyvinylpyrrolidone, copolyvinylpyrrolidone-vinyl acetate, and the like. In addition to these hydrophilic colloids, a dispersion of a synthetic polymer that is insoluble or poorly soluble in water can also be included. For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate, (meth)
Acrylamide, vinyl esters (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or together with acrylic acid, methacrylic acid, α,β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl A polymer containing a combination of (meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used. For example, US Patent No. 2376005, US Patent No. 2739137,
No. 2853457, No. 3062674, No. 3411911, No.
No. 3488708, No. 3525620, No. 3607290, No.
No. 3635715, No. 3645740, British Patent No. 1186699,
The one described in No. 1307373 can be used. In addition to this, the photographic layer may contain silver halide grains, chemical sensitizers, antifoggants, stabilizers,
It can contain hardeners, antistatic agents, coating aids, matting agents, brighteners, spectral sensitizing dyes, dyes, color couplers, and the like. For information on these additives, see Research Disclosure, Volume 176, 22.
~31 pages (December 1978) can be referred to. The present invention will be further explained below with reference to Examples, but the present invention is not limited to these Examples. The method for synthesizing the gelatin derivative may be, for example, the method described in JP-A-49-107538. Note that the adhesion test in the examples was conducted by the following method. 1 Adhesion test during drying Use a razor blade to make a mesh pattern of approx.
Make scratches at mm intervals, apply adhesive tape (Scotchi Permacel Tape manufactured by Sumitomo 3M) on top of the scratches, and peel off instantly. In this method, if the peeled portion is 0 to less than 5%, it is graded A, if it is 5 to less than 30%, it is graded B, and if it is 30 to 100%, it is graded C. 2 Wet adhesion test At each stage of development, fixing, and washing, make two scratches on the emulsion side of the film in the processing solution using a metal pencil, and then scratch the scratched area in a direction perpendicular to the line. Rub it with your fingertips. Grade A if the emulsion layer does not peel off beyond scratches;
When the maximum peeling width is within 5mm, it is classified as B class, and when it is larger than this, it is classified as C class. Example 1 A first undercoat layer having the composition shown in Table 1 was applied to a biaxially stretched and oriented crystallized polyethylene terephthalate film, and the film was dried at 180°C for 1 minute. Next, a second undercoat layer with the composition shown in Table 1 was provided on the first undercoat layer, dried at 120°C for 1 minute, and then dried at 140°C for 5 minutes.
Heat treated for minutes. Silver halide emulsion for X-rays (AgBrI, I = 2.5 mol%) was added to this undercoated base.
Samples (11) to (19) were obtained by applying 3 g of silver and 3.5 g of gelatin per square meter, and changing the amount of hardening agent as shown in Table 1.

[Table] The adhesive strength of the sample thus obtained when dry and wet was as shown in Table-2.

[Table] From the results in Table 2, it can be seen that reducing the amount of curing agent in the photographic layer deteriorates the adhesion. In addition, samples (15) to (19) using derivative gelatin are
It can be seen that good adhesion is exhibited even when the amount of curing agent in the photographic layer is reduced. Among these, phthalated gelatin,
It can be seen that samples using trimellitated gelatin and succinated gelatin exhibit particularly good adhesion. Example 2 A polyethylene terephthalate film coated with the same first layer of undercoat as in Example 1 was coated with a second undercoat layer consisting of phthalated gelatin with various amino group substitution ratios as shown in Table 3. It was dried at 140°C for 1 minute and then heat treated at 140°C for 5 minutes.
Next, a silver halide emulsion for X-rays was applied in the same manner as in Example 1 to obtain Samples (21) to (26).

[Table] The adhesive strength of the sample thus obtained when dry and wet was as shown in Table 4.

[Table] From the results in Table 4, it can be seen that the higher the substitution rate of the gelatin derivative contained in the second undercoat layer, the better the adhesion. Example 3 A second undercoat layer having the composition shown in Table 5 was applied to a polyethylene terephthalate film provided with a first undercoat layer similar to that in Example 1, and dried at 120°C for 1 minute, and then at 140°C for 5 minutes. Heat treatment was performed. Next, a silver halide emulsion for X-rays was applied in the same manner as in Example 1 to obtain Samples (31) to (37).

[Table] The dry and wet adhesive strengths of the samples thus obtained were as shown in Table 6.

[Table] From the results in Table 6, examples of compounds for gelatin derivatives
It can be seen that even better adhesion can be obtained by adding the polymers shown in (2) and (8). Example 4 A second undercoat layer having the composition shown in Table 7 was applied to a polyethylene terephthalate film coated with the same first undercoat layer as in Example 1, dried at 120°C for 1 minute, and then heat treated at 140°C for 5 minutes. I went there. Next, a silver halide emulsion for X-rays was applied in the same manner as in Example 1 to obtain Samples (41) to (46).

[Table] The dry and wet adhesive strengths of the samples thus obtained were as shown in Table 8.

[Table] From the results in Table 8, it can be seen that samples with a high content of phthalated gelatin in the second undercoat layer exhibit good adhesion. Example 5 A first undercoat layer having the composition shown in Table 9 was provided on a biaxially stretched and oriented crystallized polyethylene terephthalate film, and dried at 120°C for 3 minutes. Next, a second undercoat layer with the composition shown in Table 9 was provided on the first undercoat layer, dried at 120°C for 1 minute, and then dried at 140°C for 5 minutes.
Processed for minutes. Next, silver halide emulsions for X-rays were coated in the same manner as in Example 1, with the amount of curing agent changed as shown in Table 9, to obtain Samples (51) to (59).

【table】

[Table] The adhesive strength of the samples thus obtained when dry and wet was as shown in Table 10.

[Table] From the results in Table 10, it can be seen that Samples (55) to (59) using derivative gelatin exhibit good adhesion even if the amount of hardening agent in the photographic layer is reduced. Among these, it can be seen that samples using phthalated gelatin, trimellitated gelatin, and succinated gelatin exhibit particularly good adhesion. Preferred embodiments of the invention are as follows. 1. In the claims, the substitution rate of functional groups in the gelatin derivative is 50% or more for one functional group. 2 In Embodiment-1, the functional group is an amino group. 3. In the claims, gelatin derivatives are modified with reagents that add carboxyl groups to gelatin side chains. 4 In Embodiment-3, the reagent is an acid anhydride. 5 In -4, the acid anhydride is succinic anhydride, phthalic anhydride or trimellitic anhydride. 6. In the claims, a layer containing a gelatin derivative contains the gelatin derivative in an amount of 60% by weight or more of the total gelatin in the layer. 7 In the claims, the layer containing the gelatin derivative further contains a polymer having repeating units represented by the general formula () or (). 8. In the claims, the thickness of the layer containing derivative gelatin is 0.05 to 0.5μ.

Claims (1)

[Claims] 1. In a photographic light-sensitive material having at least one undercoat layer and at least one light-sensitive emulsion layer on a support, a compound having no vinyl group is present between the undercoat layer and the light-sensitive emulsion layer. 1. A photographic light-sensitive material, comprising a layer containing a gelatin derivative derived from a reaction between a gelatin and a gelatin derivative.