JPH08211550A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To improve the coatability of a substrate made of syndiotactic polystyrene very excellent in dimensional stability and the adhesiveness of photographic constituent layers to the substrate. CONSTITUTION: This silver halide photographic sensitive material has hydrophilic photographic constituent layers on the substrate made of a styrene polymer whose principal chain is chiefly a racemic chain through a layer contg. a polymer compsn. contg. water-dispersible or water-soluble polyester and a styrene polymer as constituent elements and a compd. represented by the formula. In the formula, each of R1 and R2 is 1-18C straight chain or branched alkyl, M is a cation and (n) is an integer of 1-50.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention uses a support having excellent dimensional stability and is subjected to an undercoating process which is excellent in coating property when the support is used and adhesion of the photographic constituent layer to the support. The present invention relates to a silver halide photographic light-sensitive material thus obtained.

[0002]

2. Description of the Related Art The performance required of a photographic support is that it is optically transparent, that adhesion to a hydrophilic photographic emulsion layer is obtained by some processing, and that it has dimensional stability. , It is difficult to have a curl, etc.
The use of various synthetic resin sheets and films has been investigated.

In general, as a support for a photographic light-sensitive material, which is wound around a small-diameter core, cellulose triacetate (TAC), whose curl is eliminated by a developing process, is wound around a large-diameter core or is formed into a sheet. As the support for the photographic light-sensitive material used, polyethylene terephthalate (P
ET) is used.

In recent years, with the demand for increasing the recording density per unit area more than ever, the dimensional stability of photographic light-sensitive materials has been demanded. This is because the photosensitive material has many uses as an intermediate recording medium for obtaining a final image, and when an image is obtained by sequentially exposing using several types of recording media, it is clear if the dimensions are misaligned. This is because such an image cannot be obtained.

Such a dimensional deviation is caused by expansion and contraction due to environmental humidity and a PET or TAC support which supports it because the photographic constituent layer of the photographic light-sensitive material uses a hydrophilic binder mainly containing gelatin. Has a hydrophilic portion in the molecule, and is also affected by environmental humidity.

On the other hand, there is known a technique of providing a support with a waterproof layer made of polyvinylidene chloride, for example, but when it is stored for a long period of time, dechlorination gradually progresses and the entire film turns yellow. When the end part is collected and reused during film formation, it also turns yellow due to dechlorination.Vinylidene chloride becomes an impurity and the support resin cannot be reused, and if incinerated, chlorine is generated, which is harmful to the environment. , There is a problem.

[0007]

Generally, polystyrene is not crystalline and therefore has no dimensional stability against heat.
The so-called syndiotactic polystyrene described in JP-A-3-131843, in which the main chain of the main chain is a racemo chain, has a high degree of crystallinity and therefore has an advantage of being extremely excellent in dimensional stability.

On the contrary, this polystyrene is difficult to be surface-treated to give it easy adhesion due to its crystallinity, and its surface is highly hydrophobic, so that the coating property when applying the undercoat layer is poor and uneven. There is a problem that it will occur.

The present invention has been made in view of the above circumstances, and an object thereof is to use a support made of syndiotactic polystyrene, which is very excellent in dimensional stability, and to apply the coating property when the support is used. It is to improve the adhesion of the photographic constituent layer to the support.

[0010]

The above object of the present invention is to provide (a) a water-dispersible or water-soluble polyester and a styrene-based polymer on a support having a styrene-based polymer whose main chain is a racemo chain. A silver halide photographic light-sensitive material having a hydrophilic photographic constituent layer via a layer containing a polymer composition having a polymer as a constituent element and (b) a compound represented by the general formula [I] Obtaining a polymer composition of (a) by dispersion-polymerizing styrene or dispersion-polymerizing styrene and a monomer copolymerizable with styrene in the presence of a material, water-dispersible or water-soluble polyester, The polymer composition of 1) has a water-dispersible or water-soluble polyester as a backbone, and styrene or a polymer obtained by polymerizing styrene and a monomer copolymerizable with styrene, (a) water-dispersible or water-soluble Po A layer containing a polymer composition having an ester and a styrene polymer as constituent elements and (b) a compound represented by the general formula [I] further comprises (c) a water-soluble conductive compound and (d) poly. (A) a water-dispersible or water-soluble polyester and a styrene-based polymer as constituents on a resin film having a styrene-based polymer in which glycerin is contained and the main chain of the main chain is a racemo chain. The coating composition containing the combined composition and (b) the compound represented by the general formula [I] is applied, and then the resin film is stretched in at least one direction and subjected to heat treatment for crystal orientation. It is achieved by forming a hydrophilic photographic constituent layer on the side having a coating layer.

That is, the inventors of the present invention have found the optimum undercoat layer composition when using a syndiotactic polystyrene-based support having extremely excellent dimensional stability, and arrived at the present invention.

The present invention will be described in detail below.

In the present invention, a styrene polymer in which the main chain of the main chain is a racemo chain (hereinafter also referred to as the polymer of the present invention) is a so-called "syndiotactic polystyrene" (hereinafter also abbreviated as SPS). If it is a styrene homopolymer, it is disclosed in JP-A-62-11.
It can be obtained by the method described in JP-A-7708, and other polymers are described in JP-A-1-46912 and JP-A-1-17.
It can be obtained by the method described in No. 8505. The racemo chain is preferably 75 mol% or more, more preferably 85 mol% or more in 2 chains (dyad),
Further, it is preferably 95 mol% or more. The racemo dyad preferably has the following structure.

[0014]

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Here, n represents an integer of 1 to 5, and examples of X include an alkyl group, an alkoxy group, COOM (M is an alkali metal, a hydrogen atom and the like), a halogen atom and the like.

Quantification of such racemo chain was determined by ¹³ C-NMR.
It can be performed with high accuracy by measuring the 1-position carbon of the benzene ring using.

Raw material monomers that can be used include styrene, alkylstyrene (methylstyrene, etc.), halogenated (alkyl) styrene (chloromethylstyrene, chlorostyrene, etc.), alkoxystyrene,
Examples thereof include vinyl benzoate, and when used as a copolymer of alkyl styrene and styrene, 50
It is preferable to obtain a film having a film thickness of μm or more.

The polymer of the present invention comprises, as raw material monomers selected from the above, those containing (a) a transition metal compound and an aluminoxane as main components described in JP-A-5-320448, pages 4 to 10, or ) It can be produced by polymerizing using a transition metal compound and a compound containing a compound capable of reacting with a transition metal compound to form an ionic complex as a main component as a catalyst.

In order to produce the polymer of the present invention, first, the styrene-based monomer is sufficiently purified and then in the presence of any of the above catalysts, about -50 to 200 ° C, preferably 30 to 100 ° C. Polymerization is carried out at the temperature of 1 second to 10 hours, preferably 1 minute to 6 hours. The polymerization method may be any of a slurry polymerization method, a solution polymerization method, a bulk polymerization method, a gas phase polymerization method, etc., and may be either continuous polymerization or discontinuous polymerization. The molecular weight can be controlled by hydrogen, temperature, monomer concentration and the like.

The molecular weight of the polymer of the present invention is not particularly limited as long as a film can be formed, but the weight average molecular weight is from 10,000 to 10,000.
It is preferably in the range of 3,000,000, particularly 30,000 to 1,500,000. The number average molecular weight / weight average molecular weight is preferably 1.5-8.
The molecular weight distribution can be adjusted by mixing different molecular weights.

Further, it does not matter if another monomer copolymerizable with the above-mentioned monomer is copolymerized within a range that does not impair the effects of the present invention.

<< Synthesis Example 1 >> Syndiotactic polystyrene pellets were prepared by the following method according to the method described in JP-A-3-131843. It should be noted that the process from the adjustment of the catalyst to the polymerization reaction was all performed in a stream of dry argon.

Copper sulfate 5 in a glass container with an internal volume of 500 ml
17.8 g (71 mmol) of water salt (CuSO ₄ .5H ₂ O), 200 ml of purified benzene and 24 ml of trimethylaluminum were added, and the mixture was stirred at 40 ° C. for 8 hours to adjust the catalyst. This is No. After filtering through 3 glass filters, the filtrate was freeze-dried. This was taken out and put in a 2 l stainless steel container, and tributylaluminum and pentacyclopentadiethyl titanium methoxide were further mixed therein, and heated to 90 ° C. 1 liter of purified styrene was put therein, and the polymerization reaction was continued for 8 hours while maintaining the temperature. After that, the mixture was cooled to room temperature, 1 liter of methylene chloride was added thereto, and a methanol solution of sodium methylate was added thereto with further stirring to deactivate the catalyst.

The product was slowly dropped into 20 l of methanol, filtered through a glass filter, washed with methanol three times, and dried. This was pelletized with an extruder and dried at 130 ° C.

The support of the present invention preferably comprises SPS alone, but in order to obtain strength of the support, a styrene polymer (IPS) having an isotactic structure in which the main chain is a meso chain is added to SPS. The crystallization rate may be controlled by mixing. The mixing ratio at the time of mixing SPS and IPS depends on the stereoregularity of each other, but the weight ratio is about 30:70 to 99: 1, preferably 50:50 to 9.
It is 8: 2.

Upon forming the SPS film, the SPS pellets are dried at 120 to 180 ° C. for about 1 to 24 hours under vacuum or atmospheric pressure in an air or nitrogen atmosphere to obtain a moisture content of 0.05% by weight. Below, preferably 0.01% by weight
Hereafter, it is desirable that the content be 0.005% by weight or less. This makes it possible to prevent a decrease in mechanical strength due to hydrolysis.

The film formation of SPS is preferably carried out by a melt biaxial stretching method using a T-die. Specifically, the process is as follows.

The dried SPS pellets were fed to an extruder for melt lamination, melted at 280 to 350 ° C., and slit-shaped T
It is extruded into a sheet form from a mold die and is cooled and solidified while being electrostatically applied on a casting roll to produce an unstretched film. This unstretched film is biaxially stretched sequentially or simultaneously to be biaxially oriented. As a stretching method, the longitudinal direction →
Sequential biaxial stretching in which stretching is performed in the width direction is preferable, and the stretching ratio in the length and width in this case is preferably 2.5 to 6 times.
The stretching temperature in the longitudinal direction depends on the glass transition temperature (Tg) of the polymer, and is usually (Tg + 10) to (Tg + 5).
0) ° C., 110 to 150 ° C. for SPS, and 115 to 160 ° C., which is slightly higher than the stretching temperature in the width direction, respectively. Next, draw the stretched film 150-2.
After heat treatment at 70 ° C. for about 1 second to 2 minutes, it is cooled and wound. In this case, it may be rapidly cooled and wound, but it may be gradually cooled between Tg and the heat treatment temperature for 0.1 minute to 1500 hours, wound into a large diameter core, and further cooled between 40 and Tg ° C.
It is preferable to cool the support at an average cooling rate of about 0.01 to −20 ° C./minute because the support is less likely to have a curl. Further, the heat treatment at 40 to Tg ° C. is preferably carried out in a constant temperature bath after the support is wound up and after the photographic constituent layer is formed and before cutting into a product.

Further, in order to impart various characteristics such as slipperiness, adhesiveness and antistatic performance, a laminate with an SPS film imparted with the characteristics can be used. Lamination is performed by laminating molten resin in a laminar flow and then extruding it from a die, or extruding and laminating molten SPS on a cooled / solidified unstretched SPS film or uniaxially stretched SPS film, and then stretching and heat fixing.

The thickness of the support of the present invention varies depending on the application, but is about 50 to 500 μm, preferably 70 to 250.
μm.

The support may contain inorganic fine particles, antioxidants, UV absorbers, antistatic agents, dyes and the like in order to impart desired functions to the support within the range not impeding the object of the present invention. it can.

Next, each component constituting the undercoat layer of the present invention will be explained.

In the present invention, the water-dispersible polyester means a polyester dispersed in water with a particle diameter of several tens to several hundreds of nm, and the water-soluble polyester is 0.1% by weight or more with respect to water at 25 ° C. It preferably has a solubility of 0.5 to 5% by weight.

The polyester in the present invention is a substantially linear polymer obtained by a polycondensation reaction of a polybasic acid or its ester-forming derivative with a polyol or its ester-forming derivative. The polybasic acid component of this polymer includes terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid,
1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, pyromellitic acid, dimer acid and the like can be mentioned. In addition to these, unsaturated polybasic acids such as maleic acid, fumaric acid and itaconic acid and hydroxycarboxylic acids such as p-hydroxybenzoic acid and p- (β-hydroxyethoxy) benzoic acid can be used at a small rate.

As the polyol component, ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, xylylene glycol, trimethylolpropane. , Poly (ethylene oxide) glycol, poly
(Tetramethylene oxide) glycol and the like can be mentioned.

The water-dispersible or water-soluble polyester used in the present invention is further effective to introduce a sulfonate, diethylene glycol, polyalkylene ether glycol or the like. In particular, it is preferable that the dicarboxylic acid component having a sulfonate (dicarboxylic acid having a sulfonate or an ester derivative thereof) is contained in an amount of 5 to 15 mol% with respect to the total dicarboxylic acid component in the polyester.

The sulfonic acid-containing dicarboxylic acid or its ester derivative used in the present invention is particularly preferably one having a sulfonic acid alkali metal salt group, such as 4-sulfoisophthalic acid, 5-sulfoisophthalic acid and sulfo. Examples thereof include alkali metal salts such as terephthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and 5- (4-sulfophenoxy) isophthalic acid, or ester-forming derivatives thereof. 5-sulfoisophthalic acid The sodium salt or its ester-forming derivative is particularly preferred. From the viewpoint of water dispersibility or water solubility and water resistance, it is particularly preferable to use 6 to 10 mol% of the total dicarboxylic acid component.

In order to improve water resistance and adhesiveness,
It is preferably modified with a styrene polymer. Examples of the styrene-based polymer that modifies the water-dispersible or water-soluble polyester include styrenes (styrene, methylstyrene, diethylstyrene, trimethylstyrene, ethylstyrene,
Isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, benzylstyrene, chloromethylstyrene, acetoxymethylstyrene, methoxystyrene, chlorostyrene, dichlorostyrene, 2
-Brom-4-trifluoromethylstyrene, vinyl benzoic acid, vinyl benzoic acid methyl ester, etc.) may be polymerized alone, or may be a copolymer.
Acrylic acids (acrylic acid, chloroacrylic acid, etc.), acrylates (ethyl acrylate, butyl acrylate, amyl acrylate, octyl acrylate, 2-
Butoxyethyl acrylate, chloroethyl acrylate, hydroxyethyl acrylate, cyanoethyl acrylate, dimethylaminoethyl acrylate, diethylene glycol monoacrylate, trimethylolpropane monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, etc.), methacrylic acids (methacrylic acid, etc.), Methacrylates (methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, cyanoacetoxyethyl methacrylate, chlorobenzyl methacrylate, ethylene glycol monomethacrylate, 3-hydroxypropyl methacrylate,
2,2-Dimethyl-3-hydroxypropyl methacrylate, diethylene glycol monomethacrylate, glycidyl methacrylate, dimethylaminophenoxyethyl methacrylate, phenyl methacrylate, etc., acrylamides (acrylamide, etc.), N-substituted acrylamides (methyl acrylamide, ethyl acrylamide, butyl acrylamide) , T-octylacrylamide, benzylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, hydroxyphenylacrylamide, dimethylacrylamide, dibutylacrylamide, etc.), methacrylamides (methacrylamide, etc.), N-substituted methacrylamides (methylmethacrylamide, t-). Butylmethacrylamide, t-octylmethacrylamide De, benzyl methacrylamide,
Cyclohexyl methacrylamide, etc.), allyl compounds (allyl acetates, allyl caproates, allyl caprylates, allyl esters; allyl exciethanol, allyl butyl ether, allyl glycidyl ether, allyl phenyl ether, etc.), vinyl ethers (methyl vinyl ether, butyl vinyl ether) , Hexyl vinyl ether, octyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, chloroethyl vinyl ether, 2-ethylbutyl ether, hydroxyethyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, Vinyl dimethyl propionate, vinyl ethyl butyrate, vinyl parerate,
Vinyl caproate, vinyl chloroacetate, etc.), vinyl heterocyclic compound (N-vinyl oxazolidone, vinyl pyridine, N-vinyl imidazole, N-vinyl pyrrolidone, N-vinyl carbazole, N-vinyl ethyl acetamide, etc.), crotonic acids (Crotonic acid, crotonic acid amide, crotonic acid esters such as butyl crotonic acid), vinyl ketones (methyl vinyl ketone, phenyl vinyl ketone, etc.), olefins (dichloropentadiene, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, etc.),
Itaconic acids (itaconic acid, itaconic anhydride, methyl itaconic acid, etc.), sorbic acid, cinnamic acid, methyl sorbate, glycidyl sorbate, citraconic acid, mesaconic acid, maleic acid, fumaric acid, ethacrylic acid, unsaturated nitriles ( Acrylonitrile, methacrylonitrile, etc.)
Etc. may be introduced as a copolymerization component.

The method of dispersion-polymerizing the styrene or the styrene and a monomer copolymerizable with the styrene in the presence of the water-dispersible or water-soluble polyester is, specifically, a solution containing the water-dispersible or water-soluble polyester. Disperse the above-mentioned monomer in, and use ammonium persulfate, potassium persulfate, cerium ammonium nitrate, cesium ammonium sulfate, hydrogen peroxide, azobisisobutyronitrile, benzoyl peroxide, etc. as an initiator,
Polymerization is performed at a temperature of 50 ° C, preferably 50 to 80 ° C. In this case, a surfactant is not particularly required and the reaction can be carried out soap-free, but for the purpose of improving the polymerization stability, general nonionic and anionic surfactants can be used as an emulsifier in the system.

Further, a graft polymer of a copolymer of water-dispersible or water-soluble polyester and styrene or a monomer copolymerizable with styrene and styrene is prepared by introducing an addition-polymerizable group into the terminal of the polyester. A method of copolymerizing the monomer by the above-mentioned method, or polymerizing the styrene-based polymer, and introducing a reactive group such as a carboxylic acid group, a glycidyl group or an amino group by a copolymerization component, and the copolymer is a polyester. It can be obtained by the method introduced during condensation. Further, after the completion of the polymerization of styrene using the catalyst used for the polymerization of the support of the present invention, while the terminal group is active, a hydroxyl group, an amino group, a carboxyl group and 4-bromophenethyl alcohol that can react with the polyester are obtained. , 4-chlorophenol, 3-bromo-1-
Halogenated alcohols such as propanol, α-bromo-
Using a compound having a halogen atom such as a halogenated carboxylic acid such as p-toluic acid, p-bromobenzoic acid, 2-bromopropionic acid, etc., in a reaction vessel subsequent to polymerization, at a temperature of 30 to 80 ° C. In, the compound obtained by reacting for about 1 hour can be obtained by putting it in a system for condensing a polyester.

The copolymerization ratio is polyester: styrene = 99: 1 to 5:95, preferably 97: 3 to 5 by weight.
It is 0:50, especially 95: 5 to 80:20.

The compound represented by the general formula [I] used in the present invention is an alkylaryl polyether sulphate compound, which has the carbon number of the alkyl group introduced into the aryl group and the polymerization degree of the polyether structure. According to the above balance, desired surface activity and emulsion stability are obtained, and a smooth and uniform film forming property of the undercoat layer composition of the present invention is ensured.

As the alkyl group represented by R ₁ and R ₂ in the formula, those having a branched alkyl group are preferable, and those having two branched alkyl groups are particularly effective.

The cation represented by M may be any as long as it does not impair the surface activity and water solubility of the compound, but potassium, sodium and ammonium ions are usually used.

N is preferably 1 to 30, more preferably 1 to 13.

The typical examples of the compounds represented by the general formula [I] are shown below, but the invention is not limited thereto.

[0047]

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[0048]

[Chemical 4]

Examples of the water-soluble conductive compound that can be contained in the undercoat layer composition of the present invention include polymers or copolymers having the following structural units in the molecule.

[0050]

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[In the formula, m and n represent integers, M represents a hydrogen atom, an alkali metal, an alkaline earth metal or ammonium, and X represents a copolymerizable monomer. Other copolymerizable monomers include styrene-based compounds such as styrene, α-methylstyrene, vinyltoluene and p-methylstyrene; methyl acrylate, ethyl acrylate, butyl acrylate, acrylate-2- Acrylic acid or acrylic ester of methacrylic acid such as ethylhexyl, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate; mono- or acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, etc. Dicarboxylic acids or anhydrides of dicarboxylic acids; aliphatic conjugated dienes such as butadiene, isoprene, 2-chloro-1,3-butadiene, 1-chloro-1,3-butadiene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; vinyl,
Vinylidene chloride, vinyl ethyl ketone, vinyl methyl ether, vinyl acetate, vinyl formate, allyl acetate,
Examples thereof include methallyl acetate, acrylamide, N-methylol acrylamide, glycidyl acrylate, glycidyl methacrylate, acrolein, and allyl alcohol.

In the present invention, antistatic property, transparency,
From the viewpoint of adhesiveness, the water-soluble conductive polymer compound preferably contains 10 to 50% of the copolymerizable monomer in the structural unit. The number average molecular weight of the polymer compound is not particularly limited, but is 500 to 500 from the viewpoint of transparency after biaxial stretching.
It is preferably in the range of 1,000,000, and particularly in the range of 1,000 to 10,000.

Examples of the counter ion of sulfonic acid in the structural unit include H ⁺ , Na ⁺ , K ⁺ , NH ₄ ⁺ , Li ⁺ , 1 / 2Ca ^{2+ and the} like. Among them, H ⁺ and NH ₄ ⁺ ions are mentioned. It is preferable in terms of antistatic property and transparency.

The polyglycerin to be contained in the undercoat layer composition of the present invention is preferably a compound represented by the following general formula.

HO (CH ₂ CH (OH) CH ₂ O) _n H
(2 ≦ n ≦ 20) In the present invention, the amount of polyglycerin used is such that the water-soluble conductive compound: a polymer composition having water-dispersible or water-soluble polyester and a styrene-based polymer as constituent elements = 70.
It is preferably 0.01 to 50% by weight, and more preferably 5 to 40% by weight, based on the total solid content in the undercoat layer composition prepared in a weight ratio of -15: 30 to 85. By including polyglycerin in the undercoat layer composition, aggregation or gelation of the composition can be prevented and transparency can be maintained.

The subbing layer composition of the present invention further contains an anionic surfactant, a nonionic surfactant, an aliphatic polyhydroxy compound, a natural water-soluble polymer compound as long as the effect of the present invention is not impaired. Sulfonation, carboxylation,
Phosphorylated, sulfoalkylenated, alkylphosphorylated and salts thereof, antiblocking agents, organic or inorganic fillers, pigments, ultraviolet absorbers and the like may be added.

When the undercoat layer is applied, the support is subjected to chemical treatment, mechanical roughening treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment or laser treatment. Etc., the surface tension of the surface is 50
It is preferably dyne / cm or more.

The coating of the undercoat layer may be carried out after the film for the support is formed, but if the composition of the undercoat layer is stretchable, it may be stretched before or during the longitudinal stretching during film formation. It can be performed at any time during the transverse stretching, such as after the transverse stretching and before the heat treatment.

The subbing layer composition preferably has a film-hardening agent to enhance film strength.
Isoxazole type, epoxy type, vinyl sulfone type,
Acryloyl-based, carbodiimide-based, triazine-based, polymer-based, maleimide-based, acetylene-based, methanesulfonic acid ester-based hardening agents can be used.

As the method of applying the undercoat layer, various known methods such as roll coating method, gravure roll coating method, spray coating method, air knife coating method, bar coating method, impregnation method and curtain coating method can be applied. .

The light-sensitive material of the present invention is for radiography.
It can be used for various purposes such as printing plate making, general photography, and direct viewing.

The crystal form of silver halide used in the light-sensitive material of the present invention may be any of a tetradecahedron, an octahedron, an irregular plate and a cubic crystal, but a high-sensitivity tabular grain or a high-hardness cubic crystal grain is preferable. The silver halide composition is AgBr,
AgCl, AgClBr, AgClBrI, AgBr
I, AgClBrI and the like can be optionally used, but AgBrI rich in AgBrI is preferable for a high speed emulsion. For rapid processing, a silver chloroiodobromide emulsion rich in AgCl and low in iodine is preferable. When used as a medical sensitive material, the silver halide grain size is preferably 0.01 μm to 1 μm,
0.05μ to 0.5μ is commonly used. For printing materials,
0.05μ to 0.2μ is often used.

Tabular grains are described in US Pat. No. 4,439,5
No. 20, No. 4,425, 425, No. 4,414,
No. 304 etc., the target tabular grain can be easily obtained. The tabular grains can be formed by epitaxially growing silver halide having a different composition on a specific surface site or by shelling. Further, in order to control the photosensitive nuclei, it is preferable to provide a transition line on the surface or inside of the tabular grains. In order to have a transition line, fine grains of silver iodide can be present during chemical sensitization or can be formed by adding iodide ions.

When tabular grains are used in the present invention, the tabular grains are preferably 50% or more of the total projected area of all grains of the emulsion layer in which the tabular grains are used or have an aspect ratio of 2 or more. . In particular, the proportion of tabular grains is 60% to 7
It is preferable to increase to 0%, further 80%. The aspect ratio represents the ratio of the diameter of a circle having the same area as the projected area of tabular grains and the distance between two parallel planes. In the case of medical sensitive material, the aspect ratio is preferably 3 or more and less than 20, and in the case of printing sensitive material, the aspect ratio is 1.5 to 8.
Is preferred. For the tabular grains having a large amount of silver chloride component, the method described in US Pat. No. 5,320,938 can be referred to.

The presence of 0.001 mol% or more and less than 10% high silver iodide sites or the presence of silver nuclei inside the silver halide grains is preferable for improving the pressure resistance of the grains. The thickness of the tabular grains is preferably 0.01 to 0.5 μm, but can be arbitrarily selected by setting the aspect ratio and the average volume grain size. In addition, the distribution of tabular grain diameters is often 30% when the variation coefficient (100 times the value S / D obtained by dividing the standard deviation S when the projected area is approximated by a circle by the diameter D) is used.
The monodispersed emulsion having a content of 20% or less is particularly preferable. Further, two or more kinds of tabular grains and normal crystal grains can be mixed. For the preparation of particles, an acidic method, an intermediate method, an ammonia method, or the like can be appropriately selected. When doping the metal, it is preferable to form particles under acidic conditions of pH 2 to 4.

In order to control the growth of tabular grains during grain formation, silver halide solvents such as ammonia, thioethers, thiourea compounds and thione compounds can be used. As a thioether compound, 3,6,9, described in German Patent 1,147,845
15,18,21-Hexoxa-12-thiatricosane, 3,9,15-trioxa-6,12-dithiaheptadecane; 1,17-dioxy-3,9-15-trioxa-6,12-dithiahepta Decane-4,14-dione; 1,20-dioxy-3,9,12,18-tetroxa-6,15, -dithiaeicosane-4,17-dione; 7,10-dioxa4,13-dithiahexadecane- 2,15-Dicarboxamide; JP-A-56-9434
7, oxathioether compounds described in JP-A-1-121847, and cyclic oxathioether compounds described in JP-A Nos. 63-259653 and 63-301939. Especially as thiourea, JP-A-53-53
Those described in the specification of No. 82408 are useful. Specifically, tetramethylthiourea, tetraethylthiourea, dimethylpiperidinothiourea, dimorpholinothiourea; 1,3-dimethylimidazole-2-thione; 1,3-dimethylimidazole-4-phenyl-2
-Thion; tetrapropylthiourea and the like can be mentioned.

During physical aging and chemical aging, zinc, lead,
Metal salts such as thallium, iridium, rhodium, ruthenium, osmium, palladium and platinum can coexist. Doping iridium in an amount of 10 ^-9 to 10 ^-3 mol per mol of silver halide in order to obtain high illuminance characteristics, and similarly doping rhodium to obtain a high-contrast emulsion having γ = 10 or more, silver halide is used. Commonly used in emulsions. Ruthenium, osmium and rhenium doping can be used instead of rhodium doping. The ruthenium, osmium and rhenium compounds are preferably added during the formation of silver halide grains. As the addition position, there are a method of uniformly distributing in the particles, and a method of forming a core-shell structure and localizing a lot in the core portion or the shell portion. It is often better to have more in the shell. Further, in addition to localizing in a discontinuous layer structure, a method of increasing the existing amount may be used as it continuously becomes outside of the particles. The addition amount can be appropriately selected within the range of 10 ⁻⁹ to 10 ⁻³ mol per mol of silver halide.

Specific examples of the compound used are shown below, but the invention is not limited thereto.

[Ru (NO) Cl ₅ ] ^-2 , [Ru (NO) Br ₅ ] ^-2 [Ru (NO) I ₅ ] ^-2 , [Ru (NO) F ₅ ] ^-2 [Ru (CN) Cl ₅ ] ^-2 , [Ru (CN) Br ₅ ] ^-2 [Ru (CN) I ₅ ] ^-2 , [Ru (CN) F ₅ ] ^-2 [Ru (SCN) Cl ₅ ] ^-2 , [Ru (SCN) Br ₅ ] ^-2 [Ru (SCN) I ₅ ] ^-2 , [Ru (SCN) F ₅ ] ^-2 [Ru (SeCN) Cl ₅ ] ^-2 , [Ru (SeCN) Br ₅ ] ^-2 [Ru (SeCN) I ₅ ] ^-2 , [Ru (SeCN) F ₅ ] ^-2 [Ru (TeCN) Cl ₅ ] ^-2 , [Ru (TeCN) Br ₅ ] ^-2 [Ru (TeCN) I ₅ ]. ^-2, [Ru (TeCN) F _5] ^-2 [Ru (CO) Cl _5] ^-2, [Ru (CO) Br _5] ^-2 [Ru (CO) I _5] ^-2, [Ru (CO) F ₅ ] ^-2 [Ru (N H ₃₎ Cl _5] ^-2, [Ru (NH ₃₎ Br _5] ^-2 [Ru (NH ₃₎ I _5] ^-2, [Ru (NH ₃₎ F _5] ^-2 [RuCl _6] ^-2, [RuBr _6] ^-2 [RuI _6] ^-2, [RuF _6] ^-2 _{[Ru (NO) Cl 2 (H} 2 O) 2 ] ^-1, _{[Ru (NO) Br 2 (H} 2 O) 2 ] ^-1 _{[Ru (NO) F 2 (H} 2 O) 2 ] ^-1, _{[Ru (NO) I 2 (H} 2 O) 2 ] ^-1 _{[Ru (NO) Cl 4 (CN} ) ] ^-2, [ Ru (NO) Br ₄ (SCN)] ^-2 [Ru (NO) Cl ₄ (SeCN)] ^-2 , [Ru (NO) Br ₄ (SeCN)] ^-2 [Ru (NO) Cl ₃ (CN) ₂ ] ^-2, _{[Ru (NO) Br 3 (CN} ) 2 ] ^-2 [Ru (NO) Cl _5] ^-4, [Ru (NO) Br _5] ^-4 [Ru (NO) I _5] ^-4, [Ru (NO) F ₅ ] ^-4 [Ru (CN) Cl ₅ ] ^-4 , [Ru ( CN) Br _5] ^-4 [Ru (CN) I _5] ^-4, [Ru (CN) F _5] ^-4 [Ru (SCN) Cl _5] ^-4, [Ru (SCN) Br _5] ^-4 [ Ru (SCN) I ₅ ] ^-4 , [Ru (SCN) F ₅ ] ^-4 [Ru (SeCN) Cl ₅ ] ^-4 , [Ru (SeCN) Br ₅ ] ^-4 [Ru (SeCN) I ₅ ] ^{- 4,} [Ru (SeCN) F _5] ^-4 [Ru (TeCN) Cl _5] ^-4, [Ru (TeCN) Br _5] ^-4 [Ru (TeCN) I _5] ^-4, [Ru (TeCN) F _5] ^-4 [Ru (CO) Cl _5] ^-4, [Ru (CO) Br _5] ^-4 [Ru (CO) I _5] ^-4, [Ru (CO) F _5] ^-4 [Ru (NH ₃ ) Cl ₅ ] ^-4 , [Ru (NH ₃ ) Br ₅ ] ^-4 [Ru (NH ₃ ) I ₅ ] ^-4 , [Ru (NH ₃ ) F ₅ ] ^-4 [RuCl ₆ ] ^-4 , [ RuBr _6] ^-4 [RuI _6] ^-4, RuF _6] ^-4 _{[Ru (NO) Cl 4 (CN} ) ] ^-4, _{[Ru (NO) Cl 4 (SCN} ) ] ^-4 _{[Ru (NO) Cl 4 (SeCN} ) ] ^-4, [Ru (NO ) Br ₄ (SeCN)]
^-4 _{[Ru (NO) Cl 3 (CN} ) 2 ] ^-4 _{[Ru (NO) Br 3 (CN} ) 2 ] ^-4 [Ru (NH _{3) 6]} Cl _3, [Ru (NH _{3) 6]} Other metals such as Br ₃ osmium and rhenium as well as rhodium, iridium, palladium and platinum can be represented by substituting Os, Re, Rh, Ir, Pa and Pt for the Ru part. The bidentate transition metal compound is disclosed in JP-A-2-2082 and JP-A-2-2085.
No. 3, No. 2-20854, No. 2-20855 specifications can be referred to. Also, as the alkali complex salt, general sodium salt and potassium salt can be selected,
Other than this, primary, secondary, and tertiary amine salts may be used.
For example, K ₂ [RuCl ₆ ], (NH ₄ ) ₂ [RuC
l ₆ ], K ₄ [Ru ₂ Cl ₁₀ O] XH ₂ O, K ₂ [RuCl ₅
(H ₂ O)] and the like.

The silver halide can be sensitized with a noble metal salt such as a sulfur compound or a gold salt. Further, selenium sensitization or reduction sensitization can be performed, and these methods can be combined for sensitization. When sensitizing with a noble metal salt, the presence of a sensitizing dye described below can enhance the sensitizing effect. When these are added to the emulsion, the sensitizing effect can be further enhanced by adding them in the form of fine particles and dispersing them. Further, when AgI fine particles are dispersed and added during chemical sensitization, AgI is formed on the grain surface, and the effect of dye sensitization can be enhanced. When forming tabular grains of AgI, the contribution of the transition line portion ranging from 0 to 1000 is often utilized.

As the sensitizing dye, cyanine, carbocyanine, merocyanine, hemicyanine, etc. are used.
As the merocyanine, those having an oxazole ring and a thiohydantoin ring of JP-B-4-73860 are preferable.

The silver halide is applied by being dispersed in a hydrophilic colloid medium, for example, gelatin.

Crosslinking of hydrophilic colloidal medium such as gelatin or carboxylic acid, polymer having hydroxy group or amino group can be carried out by aldehydes such as glyoxal or mucochloric acid, sodium 2,4, -dichloro-6-hydroxy-s-triazinate. Cyanuric chlorides of salts, aziridines such as bis (aziridineacetamido) hexane and bis (aziridineacetamido) butane, or 1,2
-Vinylsulfone hardeners such as bis (sulfonylacetamido) ethane, 1,3-bis (vinylsulfonyl) -2-propanol and bis (vinylsulfonyl) methyl ether can be used.

Particularly preferred hardeners are represented by the general formula R ₁ -N (R ₂ ) -CO-pyridinium, where the pyridinium ring is R ₃ and / or L-X-S.
It is substituted with O ₃ H.

In the formula, R ₁ and R ₂ represent an alkyl group or an aryl group, and R ₁ and R ₂ may form a ring. R ₃ represents a hydrogen atom or a substituent. L represents a single bond or a divalent group. X represents a single bond or _{-O -, - N (R 4} ) - represents,
R ₄ represents a hydrogen atom, an alkyl group or an aryl group.

When the light-sensitive material of the present invention is applied for printing plate making, a hydrazine compound as a contrast-increasing agent, an amine compound as a contrast-increasing aid, or a redox compound releasing a development inhibitor by oxidation can be used. .

When the light-sensitive material of the present invention is applied to a light-sensitive material for printing, a desensitizing dye can be used for controlling sensitivity and safelight property.

The light-sensitive material of the present invention has at least one light-sensitive emulsion layer on a support. A protective layer can be provided on the photosensitive emulsion layer. The emulsion layer and the protective layer can be further divided into two or more layers. Further, by disposing an intermediate layer between the protective layer and the emulsion layer, it is possible to control the diffusion of additives and the transmission of light, and to suppress the chemical or physical influence of the adjacent layers. A filter dye may be fixed to the protective layer to block out safety light. For immobilization, fine particles can be used, an anion-cation ionic bond can be used, or a redox reaction that decomposes by oxidation or reduction can be used. Fixing the dye in the lower layer of the emulsion layer or on the side opposite to the support for preventing halation is good for improving image quality. The antihalation layer is preferably provided below the emulsion layer. In the case of X-ray silver halide photographic elements with emulsions on both sides, the filter dye is fixed as a transverse light blocking layer. When two or more emulsion layers are provided, the emulsion having high photosensitivity and development may be provided closer to the support side or may be provided farther. Since light reaching the side closer to the support is less and the penetration of the developing solution is delayed, providing an emulsion layer with high sensitivity and high developability improves the image quality, so it is preferably applied to medical and printing sensitive materials. You can Since the difference in developability becomes large in the latter stage of development, a redox compound releasing a development inhibitor can be used for speed control. In order to enhance the effect of the development inhibitor released from the redox compound, it is preferable that the layer in which the redox compound is present is adjacent to the emulsion layer via the intermediate layer. The specific layer structure is from the support / adhesive layer / transverse light blocking layer or antihalation layer / emulsion layer / intermediate layer /
The order is redox-containing layer / protective layer. Also, from the support / adhesive layer / transverse light blocking layer or antihalation layer /
It can also be used in the order of redox-containing layer / intermediate layer / emulsion layer / protective layer. The gelatin used in these layers can be swollen with a known cross-linking agent, but in order to cross-link each layer, it is preferable to adjust the molecular weight or use a cross-linking accelerator.
The amount of gelatin used in each layer is 0.1 g to 2.0 g.
/ M ² . Crosslinking agent is 0.01 per gram gelatin
It is preferable to use from 1 to 1 mmol. In addition to gelatin, a hydrophilic polymer such as dextrin, starch, grape or the like or a hydrophobic latex can be introduced into each layer to control the degree of swelling. The degree of swelling is 120 to 200
Up to rank is common. For drying each layer, the temperature and time are adjusted according to the evaporation rate of water. 25 ℃ -2 as temperature
Generally, 00 ° C. and time of 0.1 second to 200 seconds are applied. The degree of swelling can be measured by immersing in water and measuring with a microscope, or by a swelling degree meter. As the degree of swelling,
Dry film thickness = Ld (film thickness after humidity conditioning at 23 ° C. and 50% relative humidity for 24 hours), and swollen thickness L in water at 23 ° C.
A value obtained by multiplying the ratio of w (Lw / Ld) by 100 can be used as an index.

In order to accelerate development, at least one layer of the hydrophilic colloid layer may contain the following developing agent used in the developing solution. Further, as a fungicide, N-methyl-isothiazol-3-one, N-methyl-isothiazol-5-chloro-3-one, N-methyl-isothiazol-4,5-dichloro-3-one, 2 -Nitro-2
-Brom-3-hydroxypropanol, 2-methyl-
4-chlorophenol and the like can be used.

To simultaneously coat a plurality of constituent layers of 3 to 10 layers at a high speed of 30 to 1000 meters per minute, the methods described in US Pat. Nos. 3,636,374 and 3,508,947 are described. Known slide hopper type or curtain coating can be used. In order to reduce unevenness during coating, it is preferable to use a hydrophilic polymer capable of lowering the surface tension of the coating liquid and imparting thixotropic properties in which the viscosity is reduced by shearing force.

The silver halide photographic light-sensitive material of the present invention may have a backing layer. When a backing layer is provided, it is common to provide an adhesive layer / antistatic layer / dye-containing layer / protective layer on a support.

The backing layer contains an inorganic filler such as colloidal silica for dimensional stability, silica for preventing adhesion, a methyl methacrylate matting agent, a silicone-based slipping agent or a release agent for controlling transportability, and the like. Can be made. As the backing dye, a benzylidene dye or an oxonol dye is used. These alkali-soluble or decomposable dyes can be fixed in the form of fine particles. The concentration for preventing halation is preferably 0.1 to 2.0 at each photosensitive wavelength.

The light-sensitive material of the present invention is preferably dried at a moisture content of 300% or less based on the dry weight of the binder at 25 ° C. under a relative humidity condition of 50% or less.
It is desirable to be in an atmosphere having a water content of 5 ° C. and a relative humidity of 50% or less.

The processing solution for developing the light-sensitive material is hydroquinone such as hydroquinone, sodium hydroquinone sulfonate and chlorohydroquinone as a developing agent, as well as 1-phenyl-3-pyrazolidone and 1-phenyl-4,4-dimethyl-. Super-additivity such as pyrazolidones such as 3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and 1-phenyl-4-methyl-3-pyrazolidone and N-methylparaaminophenol sulfate It can be used in combination with a developing agent. Further, ascorbic acid or isoascorbic acid may be used in combination with the above-mentioned super-additive developing agent without using hydroquinone. Sodium sulfite or potassium sulfite as a preservative, sodium carbonate or potassium carbonate as a buffer, and EDTA or EDTA as a chelating agent.
-2Na, EDTA-4Na, etc. 5-methylbenzotriazole, 2-mercaptobenzothiazole, 1-phenyl-as a fog inhibitor or silver sludge inhibitor
5-Mercaptotetrazole, 6-Nitrobenzimidazole, 1- (Phenylcarboxylate) -5-mercaptotetrazole, 1- (Phenylsulfonate)-
5-mercaptotetrazole, 2-mercaptobenzimidazole, 2-mercapto-5-sulfonic acid-benzimidazole, diethanolamine as a development accelerator,
It may include triethanolamine, diethylaminopropanediol and the like. The antifoggant can be added to photographic element layers such as an emulsion layer and an emulsion protective layer to improve not only fog suppression but also sharpness and bright reproducibility. The developer can be adjusted to a pH range of 9 to 12 with an alkaline agent such as sodium hydroxide or potassium hydroxide. The pH is generally adjusted within a range of 10 ± 0.5, which has good storage stability, but it can be used at a pH of 11 ± 0.5 for rapid processing. The development treatment can be carried out under processing conditions of 20 ° C. to 40 ° C. and 1 second to 90 seconds. Also, the replenishment amount of the developing solution and the fixing solution is 5 cc per 1 m ² by using a development accelerator and a sensitizer.
It can be in the range of ˜216 cc or less. Replenishment amount reduction is particularly effective by reducing the amount of silver halide grains used by the emulsion sensitization technique, and can be achieved in combination with the development acceleration technique.

[0085]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

<< Preparation of Modified Polyester A-1 >> 800 g of a polyester copolymer (WD size manufactured by Eastman Kodak Company) is dissolved in 5600 g of hot water at 95 ° C. for 5 hours with stirring. 200 g of styrene and 1.0 g of ammonium persulfate are added to this solution and reacted at 80 ° C. for 8 hours to obtain a polymer.

<Preparation of modified polyester A-2> Modification was carried out in the same manner as preparation of A-1 except that the same amount of a mixture of styrene / methyl methacrylate / acrylic acid = 6/2/2 was added instead of styrene. Polyester A-2 was obtained.

<< Preparation of Modified Polyester A-3 >> Instead of styrene, styrene / glycidyl methacrylate = 8 /
A modified polyester A-3 was obtained in the same manner as in the preparation of A-1 except that the same amount of the mixture of 2 was added.

<Preparation of modified polyester A-4> A modified polyester was prepared in the same manner as preparation of A-1 except that the same amount of a mixture of styrene / acrylamide / glycidyl methacrylate = 7/2/1 was added instead of styrene. A-4 was obtained.

<< Preparation of Support 1 >> S obtained in Synthesis Example 1
The PS pellets were melted at 330 ° C., and the molten polymer was extruded through a pipe while applying static electricity to a cooled casting drum through a die slit of a die, and then cooled to obtain a 1000 μm SPS unstretched sheet. The unstretched sheet was preheated at 115 ° C., stretched 3.3 times in the longitudinal direction, and further stretched 3.3 times in the width direction at 130 ° C.
Next, heat-fix at 225 ° C while relaxing a little in the width direction, and then heat-relax at 170 ° C for about 5 minutes to 1
The support was cooled to 00 ° C. and further heat treated at 80 ° C. for about 10 minutes to obtain a support.

Corona discharge was applied to both sides of the obtained support, the following composition was applied so that the dry film thickness was 0.7 μm, and then dried at 140 ° C. for 3 minutes to obtain support 1. .

Modified Polyester A-1 66 g Compound I-7 of the present invention (1.0% aqueous solution) 3 g 2,4-dichloro-6-hydroxy-s-triazine sodium (1.5% aqueous solution) 2 g Pure water 100 g To finish.

<< Preparation of Support 2 >> A modified polyester was used as A.
In the same manner as in the production of the support 1 except that the number 2 was changed to -2,
I got

<< Preparation of Support 3 >> 66 g of the modified polyester A-3 and 2.5 g of the compound I-3 of the present invention (1.0% aqueous solution) were mixed and purified to 100 g with pure water.

The SPS pellets obtained in Synthesis Example 1 were mixed with 33
Melt at 0 ° C, extrude the molten polymer through the pipe from the die slit of the extrusion die while applying static electricity to the cooled casting drum, and cool to 1000 μm SP.
An S unstretched sheet was obtained. The unstretched sheet was preheated at 115 ° C. and then stretched 3.3 times in the longitudinal direction. After subjecting both surfaces to corona discharge, the composition containing A-3 above was applied to both surfaces with an extrusion coater, and 100
It was dried while being preheated at ℃, and further stretched 3.3 times in the width direction at 130 ℃. Next, heat set at 225 ° C while relaxing a little in the width direction, heat relaxed at 170 ° C for about 5 minutes, cooled to 100 ° C, and further 80 ° C.
Then, the support 3 was obtained by heat treatment for about 10 minutes.

<< Preparation of Support 4 >> Modified Polyester A--
4 and the water-soluble conductive compound C in a weight ratio of A-4: C = 5
The mixture was mixed at 5:35 to adjust the solid content to 10% by weight. The compound I- of the present invention was added to 100 parts by weight of this adjusting solution.
5 parts by weight and polyglycerin D by 2 parts by weight with respect to the total solid content were added to obtain an undercoat processing liquid.

[0097]

[Chemical 6]

A support 4 was obtained in the same manner as the preparation of the support 3 using the obtained undercoating processing liquid.

<< Preparation of Support 5 >> JP-A-3-13184
According to the method described in No. 3, a gelatin aqueous solution (5% by weight) and a formalin aqueous solution (4% by weight) in a weight ratio of 7: 1.
To 100 parts by weight with pure water, and applied to an SPS sheet prepared in the same manner as the preparation of the support 1 so that the dry film thickness becomes 0.7 μm, and dried.

After applying an antistatic layer and an antihalation layer to each of the obtained supports, a photographic constituent layer and a backing layer having the following constitution were formed by a curtain coater. here,
As the emulsion, tabular grains composed of silver chlorobromide having a silver chloride content of 60 mol% and doped with iridium and rhodium in an amount of 10 ^-6 mol per mol of silver were used. Sodium sulfate pentahydrate 8.
Sensitization was carried out using 2 mg, 163 mg of potassium thiocyanate, 5.4 mg of chloroauric acid, and 2.0 mg of diphenylpentafluorophenyl selenide. The emulsion of the high-sensitivity emulsion layer has an average grain size of 0.13 μm and the aspect ratio = 1.5. The emulsion of the low-sensitivity emulsion layer has an average grain size of 0.14 μm and the aspect ratio =
2. The difference in sensitivity between the high speed emulsion and the low speed emulsion was 32%.

<< Photographic Layer >> First Layer Reflected Light Absorption Layer (Absorbance at 500 nm = 0.36) Gelatin 0.3 g / m ² Matting Agent (Average Particle Size 2 μm) 0.02 g / m ² Solid Disperse Dye B ( Average particle size 0.06 μm) 0.03 g / m ²

[0102]

[Chemical 7]

Thickener to polystyrene sulfonic acid (MW = 500,000) 0.1 g / m ² styrene-maleic acid copolymer 0.1 g / m ² polyvinylpyrrolidone 0.1 g / m ² second layer High-sensitivity emulsion layer Silver halide (silver equivalent) 1.5 g / m ² Gelatin 1.0 g / m ² Poly (ethyl methacrylate-butyl acrylate) copolymer latex 0.5 g / m ² Solid dispersion Hardening agent (average grain Diameter 0.12 μm) to 1-formyl-2- {4- [2- (2,4-di-tert-pentylphenoxy) butyramide] phenyl} hydrazine 0.02 g / silver 1 mol Sensitizing dye-5- [ 3- (4-sulfobutyl) -5-chloro-2- Okisazoriji Den] -1-hydroxyethyl-3- (2-pyridyl) -2-thiohydantoin potassium salt 1 × 10 ^-3 mol / silver model Thickener - polystyrene sulfonic acid (M.W. = 500,000) 0.1g / m 2 Styrene - maleic acid copolymer 0.1 g / m ² Polyvinyl pyrrolidone 0.1 g / m ² The third layer intermediate layer Gelatin 0.3 g / m ² thickener to polystyrene sulfonic acid (MW = 500,000) 0.1 g / m ² 4th layer Low-sensitivity emulsion layer Silver halide (silver conversion) 1.5 g / m ² gelatin 1.0 g / m ² poly (ethyl methacrylate-butyl acrylate) copolymer latex 0.5 g / m ² solid dispersion-hardening agent (average particle size 0.12 μm) to 1-formyl-2- {4- [2- (2,4-di-tert-pentylphenoxy) butylamido] phenyl} hydrazine 0.02 g / silver 1 mol Solid dispersion redox compound (average particle size 0.12 μm) to 1- (5-nitroindazole) 1-yl) -2- {4- [2,4-di-tert-pentylphenoxy) butylamido] phenyl} hydrazine 0.02 g / silver 1 mol Hardening agent-bis (1-piperidinotriethylene oxide) Thioether 0.2 g / silver 1 mol Nonylphenoxidecosaethylene oxide sulfonate / sodium salt 0.2 g / silver 1 mol Antifoggant hydroquinone monosulfonate 12 mg / silver 1 mol Hydroquinone aldoxime 12 mg / silver 1 mol 1- (p-carboxyphenyl ) -5-Mercaptotetrazole 12 mg / silver 1 mol Benzotriazole 12 mg / silver 1 mol 1-butanesulfonic acid-2,3-dithiacyclohexane 12 mg / silver 1 mol Adenine 12 mg / silver 1 mol Butyl gallate 12 mg / silver 1 mol Sensitizing dye-5- [3- (4-Sulfobutyl) -5-chloro-2-oxazolididene] -1-hydroxyethyl-3- (2-pyridyl) -2-thiohydantoin potassium salt 1 × 10 ⁻³ mol / silver 1 mol Thickener to polystyrene Sulfonic acid (M. W. = 500,000) 0.1 g / m ² Styrene-maleic acid copolymer 0.1 g / m ² Polyvinylpyrrolidone 0.1 g / m ² Fifth layer Protective layer lower layer Gelatin 0.5 g / m ² Thickener-polystyrene Sulfonic acid (MW = 500,000) 0.1 g / m ² Styrene-maleic acid copolymer 0.1 g / m ² Polyvinylpyrrolidone 0.1 g / m ² Ethyl methacrylate-butyl acrylate copolymer latex 0. 2 g / m ² matting agent to silicon dioxide (average particle size 4 μm) 0.03 g / m ² solid dispersion safelite dye (average particle size 0.06 μm) 4,4′-bis [1- (4-carboxyphenyl)- 3-carboxyethyl pin Razoru-5-one] heptamethine 60 mg / m ² alkali-soluble solid dispersion development inhibitor (average particle size 0.07 .mu.m) 4-nitroindazole 0 mg / m ² Layer 6 upper protective layer Gelatin 0.5 g / m ² thickener - polystyrene sulfonic acid (M.W. = 500,000) 0.1g / m 2 Styrene - maleic acid copolymer 0.1g / M ² Polyvinylpyrrolidone 0.1 g / m ² Ethyl methacrylate-butyl acrylate copolymer latex 0.2 g / m ² Matting agent to silicon dioxide (average particle size 4 μm) 0.03 g / m ² Solid dispersion safelight dye (average Particle size 0.06 μm) 4,4′-bis [1- (4-carboxyphenyl) -3-carboxyethylpyrazol-5-one] heptamethine 60 mg / m ² Alkali-soluble solid dispersion development inhibitor (average particle size 0 .07μm) 4--nitroindazole 60 mg / m ² in addition, Ze of the pyrrolidinopyridine carbamoyl pyridine ethanesulfonic acid hardener to reflected light absorbing layer all layers 0 for Chin.
3 mmol / g gelatin was added and coated.

<< Preparation of Backing Layer Coating Liquid >> The following compositions were mixed and then adjusted with pure water to a total amount of 895 ml to prepare a backing layer coating liquid.

Gelatin 32.4 g Pure water 696 ml Dye C 6% (W / V) aqueous solution 64 ml Dye D 5% (W / V) aqueous solution 24 ml Saponin 33% (W / V) aqueous solution 6.6 ml Polymer latex 20% (W / V) aqueous solution 33.6 ml (copolymer of cyclohexyl methacrylate, isononyl acrylate, glycidyl acrylate and styrene-isoprene sulfonic acid having an average particle size of 0.10 μm) 10% (W / V) solid fine particle dispersion of zinc oxide ( Average particle size 0.15 μm) 10 ml 6% (W / V) solid fine particle dispersion of compound N (average particle size 0.1 μm) 10 ml Citric acid 7% (W / V) aqueous solution 3.8 ml Sodium styrenesulfonate 4% (W / V) Aqueous solution 23 ml << Preparation of coating liquid for backing protective film layer >> After mixing the following compositions, the total amount And a backing protective layer coating solution so adjusted with pure water becomes 711Ml.

Gelatin 24.9 g Pure water 605 ml 2% (W / V) aqueous solution of methyl methacrylate (average particle size 7 μm) 72 ml 1-decyl-2- (3-isopentyl) succinate-2-sodium sulfonate 4% ( W / V) aqueous solution 11 ml Glyoxal 4% (W / V) aqueous solution 4 ml The hardener solution having the following composition was added to the coating solution for the backing protective film layer immediately before the application, and the amount of gelatin applied to the backing layer was 2.
5 g / m ² , coating amount of gelatin on backing protective film layer 0.5
Both of them were simultaneously coated so as to be g / m ² .

Pure water 27.22 ml Methanol 1.5 ml Hardener H1 1.28 ml Sodium chloride 0.005 g

[0108]

Embedded image

Each characteristic was measured by the following method.

<< Adhesiveness of Coating Film >> A coating film (primer layer) obtained by coating on the upper surface of the SPS film was cut with a razor at an angle of 45 °, and a cellophane tape was pressure-bonded to be rapidly peeled off. The peeled area of the primer layer was evaluated in 5 levels.

Evaluation Criteria 1 Adhesive strength is very weak and 100% or more of the area is completely peeled off 2 50% or more and less than 100% of the area is peeled off 3 10% or more and less than 50% of the area is peeled off 4 Adhesive strength 5% or more and less than 10% of the area peels off 5 Adhesion is very strong, peeling area is less than 5% or no peeling <Presence of cracks in coating film> After coating primer layer, methylene blue After dyeing, the state of cracks on the primer layer surface was observed with an optical microscope and evaluated according to the following evaluation criteria.

1 with large cracks (50 μm or more) 2 with fine cracks (less than 50 μm) 3 with no cracks << Adhesiveness of photosensitive material >> Silver halide above the SPS film having a primer layer A sample provided with an emulsion layer is provided with a film in a dry state before development (hereinafter referred to as a raw film), with a wet film during development, and with a film in a dry state after development (hereinafter referred to as a dry film). It was evaluated by the following method.

After coating the emulsion layer (with a biofilm), the surface of the silver halide emulsion layer side of the dried sample was scratched in a grid pattern with a razor until it reached the SPS film, and a cellophane tape was pressure-bonded to it. The peeled area of the peeled silver halide emulsion layer was evaluated on a 5-point scale.

1 Adhesive strength is very weak and completely 100%
The above area is peeled off 2 50% or more and less than 100% area is peeled off 3 20% or more and less than 50% area is peeled off 4 Adhesive strength is strong 5% or more and less than 20% area is peeled off 5 Adhesive strength Is very strong, and the peeled area is less than 5% or is not peeled at all. If the evaluation is 4 or more, it can be considered that the film adhesion is sufficiently strong in practical use.

(With wet film) It is dipped in each developing, fixing, and rinsing developing solution in sequence, and after rinsing with water, the emulsion layer that is still wet is rubbed vigorously for 10 seconds with a hand wearing rubber gloves. The area of the silver halide emulsion layer peeled at this time was compared with the lattice area, and the peeled areas were compared in five steps. The evaluation criteria are the same as those with a raw film and with a dry film.

<Photographic performance-actual image quality> A line drawing original was photographed on a sample provided with a silver halide emulsion layer above an SPS film having a primer layer and developed using an automatic processor (28 ° C., 6 seconds). ), Fixing (28 ° C., 6 seconds), washing with water (25 ° C., 6 seconds), and drying (60 ° C., 6 seconds), and the obtained image was evaluated by visual observation in 5 grades.

1 Practical Impossible 2 Practical range but not preferable 3 Practical acceptable 4 Good 5 Very good However, comprehensive evaluation including sensitivity, line drawing reproducibility and graininess was performed for actual shooting evaluation. It was The results are shown below.

Sample No. Support Adhesiveness of photosensitive material in coating film Photographic performance Adhesiveness With or without cracks Wet 1 1 1 5 3 5 4 4 2 2 2 5 3 5 4 4 3 3 3 5 3 4 5 5 4 4 5 5 5 5 5 5 5 3 2 2 1 2

[0119]

INDUSTRIAL APPLICABILITY According to the present invention, a support made of syndiotactic polystyrene, which is very excellent in dimensional stability, can be effectively applied to a photographic light-sensitive material.

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Claims (5)

[Claims] 1. A polymer composition comprising (a) a water-dispersible or water-soluble polyester and a styrene polymer as a constituent on a support having a styrene polymer whose main chain is a racemo chain. And (b) a silver photographic light-sensitive material having a hydrophilic photographic constituent layer via a layer containing a compound represented by the following general formula [I]. Embedded image [In the formula, R ₁ and R ₂ each represent a linear or branched alkyl group having 1 to 18 carbon atoms, M is a cation, and n is 1 to
Represents an integer of 50. ] 2. In the presence of water-dispersible or water-soluble polyester, styrene is dispersion-polymerized or styrene and a monomer copolymerizable with styrene are dispersion-polymerized (a).
2. The silver halide photographic light-sensitive material according to claim 1, wherein the polymer composition is obtained. 3. The polymer composition of (a) comprises a polymer obtained by polymerizing styrene or styrene and a monomer copolymerizable with styrene with a water-dispersible or water-soluble polyester as a backbone. The silver halide photographic light-sensitive material according to claim 2. 4. A layer containing (a) a polymer composition having a water-dispersible or water-soluble polyester and a styrenic polymer as constituent elements, and (b) a compound represented by the above general formula [I]. 4. The silver halide photographic light-sensitive material according to claim 1, 2 or 3, further comprising (c) a water-soluble conductive compound and (d) polyglycerin. 5. A polymer composition comprising (a) a water-dispersible or water-soluble polyester and a styrene polymer on a resin film having a styrene polymer whose main chain is a racemo chain. And (b) a coating composition containing the compound represented by the general formula [I] is applied, and then the resin film is stretched in at least one direction and heat-treated to crystallize the coating film. 5. The silver halide photographic light-sensitive material according to claim 1, 2, 3 or 4, wherein a hydrophilic photographic constituent layer is formed on the side having the.