JPH0968775A - Silver halide photographic sensitive material and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure superior optical characteristics and dimensional stability, satisfactory adhesion of a film and superior productivity by using a syndiotactic polystyrene substrate and specifying the angle of contact of the substrate with water after the substrate is surface-treated before imparting an undercoat layer. SOLUTION: The substrate of this sensitive material is a syndiotactic polystyrene substrate and the angle of contact of the substrate with water is 39-65 deg. after the substrate is surface-treated before imparting an undercoat layer. The substrate is a film based on syndiotactic polystyrene and its stereoregular structure (tacticity) chiefly has a syndiotactic structure, that is, a steric structure in which phenyl groups or substd. phenyl groups as side chains are alternately positioned in the opposite directions to the principal chain consisting of carbon - carbon bonds. The angle of contact of the substrate with water is 39-65 deg., preferably 39-55 deg.. In the case of <39 deg., effects on wettability and adhesiveness are not enhanced and severe conditions in surface treatment are required.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material and a method for producing the same.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material (hereinafter also referred to as a photographic light-sensitive material) is generally a cellulose fibrin polymer such as triacetyl cellulose (hereinafter referred to as "TAC") or polyethylene. On a plastic film support made of polyester polymer represented by terephthalate (hereinafter referred to as "PET"),
It is manufactured by coating at least one photographic photosensitive layer. Generally, as a typical photographic light-sensitive material, a color or black-and-white negative film, which is stored in a cartridge with a width of 35 mm or less and is generally loaded in a camera for photographing, a bright room, a scanner,
An example is a black-and-white film for facsimiles. TAC is mainly used as a support for a roll film, and the greatest feature of this is that it has no optical anisotropy and high transparency. However, TA
The C film is inferior in mechanical strength, and is characterized by its molecular structure. As a plastic film, it has high water absorption and inferior dimensional stability due to humidity. It is considered that this is because, for example, water absorption during the development process causes the molecular chains to move, resulting in a large dimensional change.

On the other hand, PET film has excellent mechanical properties, dimensional stability, and high productivity, so that
It has been considered that AC could be substituted, but it is still considered to have insufficient dimensional stability due to water absorption during development processing, and improvements have been sought for photographic light-sensitive materials.

That is, a PET film is used as a support for a photographic light-sensitive material, but it is used after being subjected to a development treatment and then dried at room temperature. Therefore, a small humidity expansion coefficient is required for a printing photosensitive material application that requires particularly dimensional stability. When used at room temperature, elongation due to temperature does not occur, but dimensional change (elongation due to moisture absorption) is large due to moisture absorption due to development. In order to suppress the moisture absorption of the support during development and to perform the work within a limited short time after development, measures such as applying vinylidene chloride undercoat to both sides of the support have been made. Due to pollution problems and the like, there is a demand for the development of a support having a small dimensional change due to moisture absorption even without carrying out vinylidene chloride subbing or the like.

By the way, a syndiotactic polystyrene (hereinafter referred to as "SPS") support has all the thermal, mechanical, physical, chemical and optical properties of a PET support, and especially optical. It has excellent characteristics (light transmittance, haze, etc.) and dimensional stability, and its coefficient of hygroscopic expansion is about 1/10 or less that of PET, which is extremely excellent in dimensional stability under high humidity. Therefore, the SPS support is usefully used in the above-mentioned applications, and is particularly suitable for a printing photosensitive material application where dimensional stability is required.

Generally, in order to use a support as a photographic light-sensitive material, one side is coated with an emulsion layer and the other side is coated with a back coat layer. In order to adhere the emulsion layer or back coat layer to the support well, an undercoat layer is provided between the two layers. However, in the case of an SPS support, there is a problem in both quality and production that the film is not attached well and the wettability at the time of applying the undercoat layer is poor, and the production speed does not increase.

[0007]

Therefore, the object of the present invention is to have excellent thermal, mechanical, physical, chemical and optical properties, and in particular optical properties (light transmittance, haze, etc.). , Excellent in dimensional stability (small coefficient of hygroscopic expansion),
An object of the present invention is to provide a silver halide photographic light-sensitive material excellent in productivity with a film.

[0008]

The above object of the present invention has been achieved by the following constitution.

(1). A photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the support is a syndiotactic polystyrene support, and water after surface treatment applied before applying an undercoat layer And a contact angle of 39 to 65 °.

(2). The contact angle with water after the surface treatment of the support is 39 to 55 ° (1)
The silver halide photographic light-sensitive material described in.

(3). The silver halide photographic light-sensitive material as described in (1) or (2), wherein the coating rate of the undercoat layer after the surface treatment of the support is 80 m / min or more.

(4). The silver halide photographic light-sensitive material as described in (1) or (2), wherein the coating rate of the undercoat layer after the surface treatment of the support is 100 m / min or more.

(5). The method for producing a silver halide photographic light-sensitive material according to any one of (1) to (4) above.

The present invention will be described in detail below.

The present invention relates to a photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the support is an SPS type support, and a surface treatment is carried out before applying an undercoat layer. A silver halide photographic light-sensitive material which has been achieved by a silver halide photographic light-sensitive material and a method for producing the same, which has good film formation, good wettability when applied to an undercoat layer, and excellent productivity. And the manufacturing method thereof was achieved by subjecting the SPS-based support to a surface treatment before applying the undercoat layer. That is, although the reason is not clear by etching the surface of the SPS support, the SPS polymer crystal chain is cleaved, and the generated polymer crystal terminal amorphous chain and the carboxyl group improve the wettability. It can be presumed that the coating performance of the undercoat layer is improved, the productivity is increased, and the adhesive property is significantly improved by incorporating a polymer amorphous chain into the undercoat layer and chemically bonding with the undercoat layer.

By applying such a surface treatment,
The support surface is activated, and its wettability and adhesiveness are measured by measuring the contact angle with water after the surface treatment of the support,
It can be easily quantitatively evaluated.

By the way, the contact angle with water can be reduced by subjecting the SPS-based support to a surface treatment before applying the undercoat layer. The smaller the contact angle, the better the wettability. At the same time, it also shows that the smaller the contact angle, the better the adhesion. Of course, by making the surface treatment conditions strict (stronger and harder), the contact angle becomes smaller, but it is obvious that there is a limit.

The contact angle between the SPS-based support and water is 39.
It is preferably ˜65 °. More preferably 39-
It is good that it is 55 °. The lower limit of the contact angle is 39 °. If it is less than 39 °, the effect on wettability and adhesiveness will reach a ceiling and extremely strong surface treatment conditions will be required.

In the present invention, the syndiotactic polystyrene support means a film containing syndiotactic polystyrene (SPS) as a main component, and its stereoregular structure (tacticity) is mainly a syndiotactic structure. That is, it has a three-dimensional structure in which phenyl groups and substituted phenyl groups, which are side chains, are alternately located in opposite directions with respect to the main chain formed by carbon-carbon bonds, and the main chain of the main chain is a racemo chain. A styrene-based polymer or a composition containing the styrene-based polymer, and a styrene homopolymer can be polymerized by the method described in JP-A-62-117708. JP-A-1-46912 and 1-17.
It can be obtained by polymerization according to the method described in No. 8505.

The tacticity is quantified by a nuclear magnetic resonance method ( ¹³ C-NMR method) using isotope carbon. ^The tacticity measured by the ¹³ C-NMR method can be indicated by the abundance ratio of a plurality of continuous constitutional units, for example, diad in the case of 2 units, triad in the case of 3 units, and pentad in the case of 5 units. However, the styrene-based polymer having a predominantly syndiotactic structure as used in the present invention is usually a racemic diad of 75% or more, preferably 85% or more, or racemic triad 60% or more, preferably 75% or more, or a racemic pen. It is preferable that the tod is 30% or more, preferably 50% or more.

Specific monomers of the polymer constituting the syndiotactic polystyrene-based composition include styrene, alkylstyrene such as methylstyrene, halogenated (alkyl) styrene such as chloromethylstyrene and chlorostyrene, alkoxystyrene, A single or a mixture containing vinyl benzoate as a main component.

The polystyrene-based resin having a syndiotactic structure of the present invention uses (a) (a) (a) described in JP-A-5-320448, pages 4 to 10 as a catalyst for polymerization using the above raw material monomers. ) Those containing a transition metal compound and (b) aluminoxane as main components, or (b)
It can be produced by polymerization using a compound containing as a main component a compound capable of reacting with (a) a transition metal compound and (c) a transition metal compound to form an ionic complex.

To produce the styrenic polymer used in the film of the present invention, first, the styrenic monomer is sufficiently purified and then polymerized in the presence of any of the above catalysts. At this time, the polymerization method, polymerization conditions (polymerization temperature, polymerization time), solvent, etc. may be appropriately selected. Usually from -50
At a temperature of 200 ° C, preferably 30-100 ° C,
Polymerization is carried out for 1 second to 10 hours, preferably 1 minute to 6 hours. As the polymerization method, any of a slurry polymerization method, a solution polymerization method, a bulk polymerization method, a gas phase polymerization method and the like can be used, and either continuous polymerization or discontinuous polymerization may be used. Here, in solution polymerization, as a solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, and aliphatic hydrocarbons such as cyclopentane, hexane, heptane, and octane are used alone or in combination of two or more. It can be used in combination. In this case, the monomer / solvent (volume ratio) can be arbitrarily selected. The molecular weight and composition of the polymer may be controlled by a commonly used method. The molecular weight can be controlled by, for example, hydrogen, temperature, monomer concentration and the like.

The molecular weight of the SPS film of the present invention is not limited as long as it is formed, but the weight average molecular weight is preferably 10,000 to 3,000,000, and particularly preferably 30,000 to. It is preferably 1,500,000. The molecular weight distribution (number average molecular weight / weight average molecular weight) at this time is preferably 1.5 to 8. This molecular weight distribution can be adjusted by mixing different molecular weights. In addition, other monomers copolymerizable with these may be copolymerized to the extent that the effects of the present invention are not impaired.

The SPS film of the present invention is preferably SPS made alone from styrene, but as a film further containing SPS, SPS has a styrene-based heavy chain having an isotactic structure in which the main chain is a meso chain. The crystallization rate can be controlled by mixing the coalescence (IPS), and a stronger film can be obtained. When SPS and IPS are mixed, the ratio depends on their stereoregularity,
30:70 to 99: 1, preferably 50:50 to 98:
2.

The support may contain inorganic fine particles, an antioxidant, a UV absorber, an antistatic agent, a dye, a pigment, a dye, etc., in order to impart functionality, within a range not impeding the object of the present invention. Is possible.

The polymer used to form the SPS has a weight average molecular weight of 10,000 or more, more preferably 30,
It is more than 000. If the weight average molecular weight is less than 10,000, a film having excellent strength characteristics and heat resistance cannot be obtained. The upper limit of the weight average molecular weight is not particularly limited, but if the weight average molecular weight is 1,500,000 or more, rupture may occur due to an increase in stretching tension, which is not preferable. Furthermore, the SPS film of the present invention is
The SPS-based pellets are dried at 120 to 180 ° C. for 1 to 24 hours under vacuum or normal pressure under an atmosphere of inert gas such as air or nitrogen. The target moisture content is not particularly limited, but is 0.05% or less, preferably 0.01% or less from the viewpoint of preventing reduction in mechanical strength and the like due to hydrolysis.
Hereafter, 0.005% or less is more preferable. However, these methods are not particularly limited as long as the purpose is achieved.

A known method can be applied to the method of extrusion during film formation, but it is preferable to extrude using a T die, for example.
Melt and extrude SPS pellets at 280-350 ° C,
An unstretched film is prepared by cooling and solidifying while applying static electricity on a casting roll.

Next, this unstretched film is biaxially stretched to obtain 2
Orient the axis. As a stretching method, a known method, for example, a sequential biaxial stretching method in which longitudinal stretching and transverse stretching are sequentially performed, a sequential biaxial stretching method of transverse stretching / longitudinal stretching, a transverse / longitudinal / longitudinal stretching method, a longitudinal / transverse stretching method. -A longitudinal stretching method, a longitudinal-longitudinal-transverse stretching method, a simultaneous biaxial stretching method or the like can be adopted and can be appropriately selected according to various characteristics such as required mechanical strength and dimensional stability. . In general, a sequential biaxial stretching method in which stretching is first performed in the longitudinal direction and then in the width direction is preferable. In this case, the stretching ratio in the longitudinal and transverse directions is 1.5 to 6 times, and the longitudinal stretching temperature is Depending on the glass transition temperature (Tg),
Stretching is usually performed in a temperature range of (Tg + 10) ° C. to (Tg + 50) ° C. 110-150 for SPS film
It is preferably carried out at a temperature of ° C. The stretching temperature in the width direction is preferably slightly higher than that in the longitudinal direction and is preferably 115 to 160 ° C.

Next, this stretched film is heat-treated.
The heat treatment temperature in this case can be appropriately changed depending on the application. 1 for shrink wrapping applications that require high shrinkage
15 ° C or higher and 175 ° C or lower, 175 ° C to 175 ° C depending on the purpose for photography, printing, and medical applications requiring dimensional stability.
A temperature of 270 ° C is adopted. The heat treatment time is not particularly limited, but is usually 3 seconds to 100 seconds. It goes without saying that vertical heat relaxation, horizontal heat relaxation treatment and the like may be performed as necessary.

After this, the film may be rapidly cooled and wound, but it is 0.1 minute to 1500 at a temperature between Tg and the heat treatment temperature.
Slowly cool over time and wind on a large diameter core 40 ℃ ～ T
It is preferable to cool at an average cooling rate of −0.01 to −50 ° C./min between g ° C. because it has an effect of making it difficult to wind the support. Of course, the heat treatment between 40 ° C. and Tg ° C. may be carried out by putting the support in a constant temperature bath for 0.1 to 1500 hours after the emulsion is coated and after the emulsion is coated.

Such heat treatment is carried out immediately after film formation on the SPS support, after the surface treatment step of the support, after coating the undercoat layer,
It is also possible to carry out after coating the emulsion layer. The method of improving the curling due to heat treatment loses its effect when exposed to a temperature of Tg or higher, so it is necessary to prevent the temperature from becoming higher than Tg. At the same time, it is fatal for a photographic light-sensitive material that a blocking phenomenon occurs or the emulsion layer deteriorates by performing heat treatment, and measures such as setting the heat treatment temperature as low as possible are taken. You must avoid it. The heat treatment temperature is 40 ° C. or higher and Tg ° C. or lower. Although the Tg of the SPS support varies depending on the proportion of the copolymerization component, essentially no significant difference can be found in mechanical, physical and chemical properties from the SPS homopolymer support. However, the Tg of the SPS support containing some copolymerization components is about 95 to 100 ° C. Therefore, the temperature when the heat treatment for reducing the winding around the SPS support itself is performed is 40 ° C. or higher and Tg or lower, in other words, 95 to
It is preferably 100 ° C or lower. When heat-treating after the subbing treatment, 70 ° C. or less from the viewpoint of avoiding the blocking phenomenon 4
It is preferably 0 ° C or higher. Similarly, when heat treatment is performed after coating the emulsion, the temperature is preferably 65 ° C. or lower and 40 ° C. or higher.

In addition to the above film forming method, slipperiness, adhesiveness,
In order to impart various properties such as antistatic performance, it is also possible to produce an SPS laminated film in which an SPS support having the above-mentioned properties is laminated on at least one surface of the SPS support. The lamination method is such that the resin is melted in a laminar flow and then extruded from a die or cooled and solidified S.
Molten S is added to PS unstretched support or SPS uniaxially stretched support.
It is obtained by extrusion-laminating PS, then stretching in both the longitudinal and transverse directions or in the direction perpendicular to the uniaxial stretching direction and heat setting. Extrusion conditions, stretching temperature, stretching ratio, heat setting temperature, etc. of the SPS resin are slightly different depending on the combination of the SPS laminated support, but may be finely adjusted to select the optimum conditions.
Not a major change. Needless to say, the lamination is composed of a combination of two or more layers, and may be a combination of the same kind of polymers (including a combination of copolymerization polymers) or a combination of different kinds of polymers.

In addition to the above, surface coating (giving a gas barrier property by coating vinylidene chloride, imparting slipperiness and adhesiveness by in-line coating, etc.) may be carried out in the same manner. That is, it can be produced by in-line coating on an SPS unstretched film, after SPS uniaxial stretching, or after SPS biaxial stretching.

The above-mentioned film forming method can be appropriately changed according to its use and purpose, and the present invention is not limited to these methods for any reason.

The thickness of the SPS-based stretched film thus obtained varies depending on the application of the photographic light-sensitive material, but is 60 to 122 μm for color light-sensitive materials, and 1 for medical and printing light-sensitive materials.
The thickness is 00 μm, the thickness is 175 μm for X rays, and the film forming conditions described above are effective for the thickness of 50 to 250 μm.

Next, the subbing treatment of the support before coating the hydrophilic colloid layer for silver halide photographic light-sensitive materials will be described.
When applying the undercoat layer, chemical treatment, mechanical surface roughening treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation It is essential to apply surface treatment such as treatment. The surface treatment and coating of the undercoat layer may be carried out continuously or separately. By these surface treatments, the contact angle of water on the surface of the SPS support should be 65 ° or less and 39 ° or more, preferably 55 ° or less and 39 ° or more. If it is set to less than 39 °, it is necessary to make the treatment conditions considerably severe (strong and violent), and it is saturated at about 39 °, and there is not much point in setting it below this. If this condition is satisfied, both wettability and adhesiveness when applying the undercoat layer are good.

In the corona treatment, the discharge frequency is 50 Hz to
5000 KHz, preferably 5 KHz to several 100 KHz
Is appropriate. If the discharge frequency is too low, stable discharge cannot be obtained, and pinholes are generated in the object to be treated, which is not preferable. On the other hand, if the frequency is too high, a special device for impedance matching is required, which increases the cost of the device, which is not preferable. The processing strength of the object is SP
For the S support, 5 to 20 Watt · min / m ² , preferably 6 to 15 Watt · min / m ² are suitable. The treatment strength is not strictly defined depending on the type of device (gap clearance between electrode and dielectric roll, discharge shape, discharge frequency, waveform, etc.), so the contact angle between the treated surface of the support and water is specified in the claims. If the range is satisfied, it is not limited to these numerical values.

The ultraviolet treatment is preferably performed with a high-pressure mercury lamp or a low-pressure mercury lamp composed of a quartz tube and having a spectrum of 180 to 380 nm. The ultraviolet treatment is preferably performed in a film forming step (stretching process, heat setting, after heat setting), and particularly preferably in the latter half of the stretching step or heat setting. The method of UV irradiation is a high-pressure mercury lamp (generates a spectrum whose main wavelength is 365 nm)
If so, the irradiation light amount of 100 to 1500 (mJ / m ² ) is preferable. In the case of a low-pressure mercury lamp (generating a spectrum whose main wavelength is 254 nm), the irradiation light amount is 200 to 1500
(MJ / m ² ) is good, preferably 400 to 1300
(MJ / m ² ) is good. When it exceeds 1300 (mJ / m ² ), the effect is saturated. The treatment strength is not strictly defined depending on the type of the apparatus, so that the treatment angle is not limited to these values as long as the contact angle between the treated surface of the support and water satisfies the range defined in the claims of the present invention.

The subbing layer may be any of those used in the art. The undercoat layer is
Although it may be a single layer, it is preferably a multi-layer in order to obtain more functionality and increase the adhesive strength. The subbing multilayer method will be described below. In the multi-layer method, the first subbing
The layer preferably adheres well to the support, and as the material, unsaturated carboxylic acid such as methacrylic acid, acrylic acid or its ester, styrene, vinylidene chloride,
Polymer obtained from monomers such as vinyl chloride, or
Examples thereof include copolymers, water-dispersed polyesters, polyurethanes, polyethyleneimines, and epoxy resins. Of these, preferred are copolymers having a water-dispersible polyester and a styrene polymer as constituent elements. The copolymer or composition containing the water-dispersible polyester and the styrene polymer as constituent elements will be described.

The water-dispersible polyester is a substantially linear polymer obtained by a polycondensation reaction between a polybasic acid or its ester-forming derivative and 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,
Examples thereof include 4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, pyromellitic acid and dimer acid. Unsaturated polybasic acids such as maleic acid, fumaric acid, itaconic acid and p
A small proportion of hydroxycarboxylic acids such as -hydroxybenzoic acid and p- (β-hydroxyethoxy) benzoic acid can be used.

As the polyol component, ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, xylylene glycol, triglyceride, triethylene glycol, triethylene glycol, triethylene glycol, triethylene glycol, triethylene glycol, triethylene glycol, triethylene glycol, triethylene glycol, triethylene glycol, triethylene glycol, triethylene glycol, triethylene glycol, triethylene glycol, triethylene glycol, triethylene glycol, triethylene glycol, triglyceride, triethylene glycol, triethylene glycol, triethylene glycol, triethylene glycol, triethylene glycol, triethylene glycol, triethylene glycol, triethylene glycol, triethylene glycol, triethylene glycol, triethylene glycol, triethylene glycol, triethylene glycol, triethylene glycol, triethylene glycol, triethylene glycol, triethylene glycol, triethylene glycol, triethylene glycol. Methylolpropane, poly (ethylene oxide) glycol,
Examples thereof include poly (tetramethylene oxide) glycol.

In order to impart water dispersibility and water solubility to the water-dispersible polyester, introduction of a sulfonate, diethylene glycol, polyalkylene ether glycol or the like is an effective means. In particular, a dicarboxylic acid component having a sulfonic acid salt (a dicarboxylic acid having a sulfonic acid salt and / or
Or an ester-forming derivative thereof) in an amount of from 5 to 15 mol% based on all dicarboxylic acid components in the water-dispersible polyester.

In the present invention, the sulfonic acid salt-containing dicarboxylic acid and / or its ester-forming derivative used in the undercoat layer is particularly preferably one having a sulfonic acid alkali metal salt group, such as 4-sulfoisophthalic acid. , 5-sulfoisophthalic acid, sulfoterephthalic acid,
4-sulfophthalic acid, 4-sulfonaphthalene-2,7-
An alkali metal salt such as dicarboxylic acid or 5- (4-sulfophenoxy) isophthalic acid or an ester-forming derivative thereof is used, and 5-sulfoisophthalic acid sodium salt or an ester-forming derivative thereof is particularly preferable. The dicarboxylic acid having a sulfonic acid salt and / or an ester-forming derivative thereof is particularly preferably used in an amount of from 6 to 10 mol% based on all dicarboxylic acid components from the viewpoint of water solubility and water resistance.

In the present invention, the monomer of the styrene polymer used in the undercoat layer may be styrene alone or when it is copolymerized, for example, alkyl acrylate or alkyl methacrylate (wherein the alkyl group is a methyl group or an ethyl group). , N-propyl group, isopropyl group, n
-Butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, phenyl group, benzyl group, phenylethyl group, etc.); 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-
Hydroxy-containing monomers such as hydroxypropyl acrylate and 2-hydroxypropyl methacrylate; acrylamide, methacrylamide, N-methylmethacrylamide, N-methylacrylamide, N-methylolmethacrylamide, N-methylolacrylamide, N,
Amide group-containing monomers such as N-dimethylolacrylamide and N-methoxymethylacrylamide; amino group-containing monomers such as N, N-diethylaminoethyl acrylate and N, N-diethylaminomethacrylate; epoxy group-containing monomers such as glycidyl acrylate and glycidyl methacrylate; Acrylic acid, methacrylic acid and their salts (sodium salt, potassium salt, ammonium salt)
Monomers containing carboxyl groups or salts thereof such as;
Monomers containing sulfonic acid groups such as styrenesulfonic acid, vinylsulfonic acid and salts thereof (sodium salt, potassium salt, ammonium salt) or salts thereof; itaconic acid, maleic acid, fumaric acid and salts thereof (sodium salt) , A potassium salt, an ammonium salt) or the like, or a monomer containing a carboxyl group or a salt thereof; maleic anhydride,
Monomers containing acid anhydrides such as itaconic anhydride; vinyl isocyanate, allyl isocyanate, vinyl methyl ether, vinyl ethyl ether, acrylonitrile, vinyl chloride, vinyl acetate, vinylidene chloride and the like can be mentioned. The above-mentioned monomers can be copolymerized using one kind or two or more kinds.

In order to modify the water-dispersible polyester into a vinyl polymer, an addition-polymerizable group is introduced at the terminal of the water-dispersible polyester and copolymerized with a monomer of the vinyl copolymer for grafting. There are methods such as a method of polymerizing a vinyl-based copolymer and introducing a reactive group at the time of condensation polymerization of a water-dispersible polyester such as a carboxylic acid, a glycidyl group or an amino group as a monomer, and grafting.

The polymerization initiator includes ammonium persulfate, potassium persulfate, sodium persulfate, etc., and ammonium persulfate is preferably used.

Further, regarding the polymerization, a soap is not particularly required, and the reaction can be carried out soap-free. But,
For the purpose of improving the polymerization stability, a surfactant can be used as an emulsifier in the system, and any general nonionic and anionic surfactant can be used.

The modifying ratio of the above water-dispersible polyester and styrene copolymer is 99/1 to 5/95, preferably 97/3 to 50/50, and more preferably 95/5.
~ 80/20 is good.

In order to improve the coating property, it is preferable to add an activator or a cellulose compound such as methyl cellulose in the first subbing layer.

The subbing treatment may be carried out after the film formation, but if the subbing composition can be stretched, before the longitudinal stretching which is in the midst of the film formation, between the longitudinal stretching and the transverse stretching, It can be performed at any place such as after transverse stretching and before heat treatment.
When stretching is not possible For example, when a polymer having a hydrophilic group is used, it may not be possible to stretch due to strong interaction between hydrophilic polymers, but stretching under steam, polyglycerin as a stretching aid, etc. It becomes possible to stretch by adding.

Preferred among the monomers having a hydrophilic group are unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic anhydride. From the viewpoint of water resistance, the content is preferably 1 to 10% by weight,
More preferably 1 to 8% by weight, more preferably 1 to 6
%, Most preferably 1 to 4% by weight. Further, as the fourth component of this copolymer, other copolymerizable monomers may be copolymerized in the range of 0 to 15% by weight, preferably 0 to 10% by weight, if necessary. Examples of this include alkyl-substituted styrenes such as methylstyrene,
Chlorostyrene, chloromethyl styrene and other halogenated styrenes, acrylonitrile and other unsaturated nitrile compounds, methyl acrylate, methyl methacrylate, t-butyl acrylate and other aliphatic compounds, cyclohexyl methacrylate and other alicyclic compounds, and benzyl acrylate. And aromatic (meth) acrylic acid ester compounds, such as butadiene and isoprene, which are rubber-modified compounds.

The method for producing these copolymers is not particularly limited, and can be usually obtained by radical polymerization using a generally known radical initiator.

GP of a copolymer composed of these monomers
The weight average molecular weight in terms of standard polystyrene measured by the C method is preferably 1500 to 700,000, and more preferably 2000 to 500000.

The second subbing layer is preferably a hydrophilic resin layer which adheres well to the photographic emulsion layer. As a binder that constitutes the hydrophilic resin layer, gelatin, a gelatin derivative,
Casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer, carboxymethyl cellulose, water-soluble polymers such as hydroxyethyl cellulose, a combination of a polystyrene sulfonate sodium copolymer and a hydrophobic latex, and the like, Gelatin is preferred.

A hardener is preferably used in the undercoating second layer to increase the film strength. Examples of such hardener include aldehyde compounds such as formaldehyde and glutaraldehyde, and US Pat. , 732, 303
No. 3,288,775, British Patent 974,723.
No. 1,167,207, etc., compounds having a reactive halogen, ketone compounds such as diacetyl and cyclopentanedione, bis (2-chloroethyl)
Urea, 2-hydroxy-4,6-dichloro-1,3,5
-Triazine, divinyl sulfone, 5-acetyl-1,
3-Diacryloylhexahydro-1,3,5-triazine, U.S. Pat. Nos. 3,232,763 and 3,635.
718, compounds having reactive olefins described in British Patent 994,809, etc., US Pat. No. 3,539,64
No. 4, No. 3,642, 486, Japanese Patent Publication No. 49-1356
No. 8, No. 53-47271, No. 56-48860,
JP-A-53-57257, JP-A-61-128240,
No. 62-4275, No. 63-53541, No. 63-
Vinylsulfone compounds described in No. 264572, N-
Hydroxymethylphthalimide, US Patent 2,732
No. 316, 2,586,168, etc., N-methylol compounds, US Pat. No. 3,103,437, etc., isocyanate compounds, US Pat. No. 2,983,611.
And the aziridine compounds described in U.S. Pat. Nos. 2,725,294 and 2,725,2.
Acid derivatives described in US Pat. No. 3,100,7
No. 04, etc., carbodiimide compounds, U.S. Pat. No. 3,091,537, etc. epoxy compounds, U.S. Pat. Nos. 3,321,313, 3,543,292, etc. isoxazole compounds. , Organic hardeners such as halogenocarboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane and dichlorodioxane, and inorganic hardeners such as chromium alum, zirconium sulfate and chromium trichloride. Further, as a hardener having a relatively fast hardening effect on gelatin, compounds having a dihydroquinoline skeleton described in JP-A-50-38540, JP-A-51-59625 and JP-A-62-26 are mentioned.
No. 2854, No. 62-264044, No. 63-184.
No. 741 N-carbamoylpyridinium salts,
It has two or more acyl-imidazoles described in JP-B-55-38655, N-acyloxyimidazoles described in JP-B-53-22089, and two or more N-acyloxyimino groups described in JP-B-53-22089. Compounds, compounds having an N-sulfonyloxyimide group described in JP-A-52-93470, JP-A-58-113
A compound having a phosphorus-halogen bond described in No. 929,
JP-A-60-225148 and 61-240236.
Nos. 63-41580 and chloroformamidinium compounds are known.

The second subbing layer preferably contains, as a slip agent, inorganic fine particles such as silicon dioxide and titanium oxide, and an organic matting material (1 to 10 μm) such as polymethylmethacrylate. In addition to these, various additives such as an antistatic agent, an antihalation agent, a coloring dye, a pigment, and a coating aid may be contained, if necessary.

Among these, it is preferable to include an antistatic agent. Preferred antistatic agents include non-photosensitive conductors and / or semiconductor fine particles.

The non-photosensitive conductor and / or semiconductor fine particles used for the undercoat layer in the present invention include charge carriers existing in the particles, such as cations and anions.
It shows conductivity by electrons, holes, etc., organic materials,
It may be an inorganic material or a composite material of both. It is preferably a compound having electron conductivity, and examples of organic materials include polymer fine particles such as polyaniline, polypyrrole, and polyacetylene. Examples of inorganic materials include fine particles of metal oxides that easily form nonstoichiometric compounds such as oxygen-deficient oxides, metal-excess oxides, metal-deficient oxides, and oxygen-excess oxides. If it is a charge transfer complex or an organic-inorganic composite material, a phosphazene metal complex or the like can be mentioned. Among these, the most preferable compound for the undercoat layer of the present invention is metal oxide fine particles which can be manufactured by various methods. In the present invention, the volume resistivity of the conductor in the undercoat layer is 10 ³ Ω · cm.
The following are defined as a conductor and a semiconductor with respect to the semiconductor as 10 ¹² Ω · cm or less.

A preferred method for producing conductive fine particles will be described below.

<< Preparation of Semiconductor Fine Particle Solution >> 65 g of stannic chloride hydrate was dissolved in 2000 cc of a water / ethanol mixed solution to obtain a uniform solution. Then, this was boiled to obtain a coprecipitate. The formed precipitate is taken out by decantation, and the precipitate is washed with distilled water many times. Silver nitrate was dropped into distilled water in which the precipitate was washed, and after confirming that there was no reaction of chlorine ions, 1000 cc of distilled water was added to bring the total amount to 2
000 cc. 40c of 30% ammonia water
c, and heated in a water bath to obtain a colloidal gel dispersion.

<< Preparation of Semiconductor Fine Particle Powder >> 65 g of stannic chloride hydrate and 1.5 g of antimony trichloride were dissolved in 1000 g of ethanol to obtain a uniform solution. 1N- in this solution
A sodium hydroxide aqueous solution was added dropwise until the pH of the solution became 3, to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The obtained coprecipitate was left at 50 ° C. for 24 hours to obtain a reddish brown colloidal precipitate. The reddish brown colloidal precipitate was separated by centrifugation. To remove excess ions, water was added to the precipitate and washed by centrifugation. This operation was repeated three times to remove excess ions.
100 g of colloidal precipitate from which excess ions were removed was added with 50 g of barium sulfate having an average particle size of 0.3 μm and 1000 g of water.
It was mixed with g and sprayed in a firing furnace heated to 900 ° C. to obtain a bluish powder mixture of stannic oxide and barium sulfate having an average particle size of 0.1 μm.

The coating liquid concentration of the undercoat layer composition is usually 20% by weight or less, preferably 15% by weight or less. The coating amount is 1 to 30 g by weight of the coating liquid per 1 m ² of the film.
More preferably, it is 5 to 20 g.

As a coating method, various known methods can be applied. For example, a roll coating method, a gravure roll coating method, a spray coating method, an air knife coating method, a bar coating method, an impregnation method, a curtain coating method, or the like can be applied alone or in combination. When the contact angle with water after the surface treatment described in the claims of the present invention is satisfied, the coating speed is 80 m / min or more, preferably 1
It can be applied without problems at a rate of 00 m / min or more. The upper limit is 145 m / min when the contact angle with water is 55 to 39 °.

The silver halide photographic light-sensitive material according to the present invention is preferably subjected to photographic processing after exposure by an automatic processor having at least four processes of development, fixing, washing (or stabilizing bath) and drying.

As the developing solution used in the present invention, known developing agents can be used. Specifically, dihydroxybenzenes (e.g., hydroquinone, hydroquinone monosulfonate, etc.), 3-pyrazolidones (e.g., 1-phenyl-3-pyrazolidone, 1-phenyl-4-)
Methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-
Pyrazolidone, etc.), aminophenols (eg, o-aminophenol, p-aminophenol, N-methyl-
o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.), ascorbic acids (ascorbic acid, sodium ascorbate, erythorbic acid, etc.) and metal complex salts (EDTA iron salt, DTPA)
(Iron salt, DTPA nickel salt, etc.) can be used alone or in combination. Among them, it is preferable to use a developer containing ascorbic acid and its derivative. Ascorbic acid and its derivatives are known as a developing agent, for example, US Pat. No. 2,688,548,
2688549, 3022168, 3512981
Nos. 4,975,354 and 5,326,816 can be used.

Further, a developing agent for ascorbic acid and its derivatives and 3-pyrazolidones (for example, 1-phenyl-
3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl- 3-pyrazolidone) and aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4)
-Diaminophenol, etc.) or dihydroxybenzenes substituted with a hydrophilic group (for example, hydroquinone monosulfonate, hydroquinone monosulfonic acid sodium salt,
It is preferable to use a developing agent such as 2,5-hydroquinone disulfonic acid potassium salt) in combination. When used in combination, the developing agent for 3-pyrazolidones, aminophenols and dihydroxybenzenes substituted with a hydrophilic group is usually 0.0
It is preferably used in an amount of 1 or more and less than 0.2 mol.
In particular, a combination of ascorbic acid and its derivative with 3-pyrazolidones, and a combination of ascorbic acid and its derivative with 3-pyrazolidones and dihydroxybenzenes substituted with a hydrophilic group are preferably used.

An alkaline agent (sodium hydroxide, potassium hydroxide, etc.) and a pH buffering agent (eg carbonate, phosphate, borate, boric acid, acetic acid, oxalic acid, alkanolamine, etc.) are added to the developer. Preferably. As the pH buffering agent, carbonate is preferable, and the addition amount thereof is preferably 0.5 mol or more and 2.5 mol or less, and more preferably 0.75 mol or more and 1.5 mol or less, per liter. If necessary, a solubilizing agent (for example, polyethylene glycols, their esters, alkanolamines, etc.), a sensitizer (for example, nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc.), surfactants, Antifoaming agents, antifoggants (for example, halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (for example ethylenediamine tetrachloride). Acetic acid or its alkali metal salts, nitrilotriacetic acid salts, polyphosphate salts, etc., development accelerators (eg US Pat. No. 2,304,025)
No. 1, No. 47-45541), a hardener (for example, glutaraldehyde or its bisulfite adduct), or a defoaming agent. The pH of the developer is preferably adjusted to 7.5 or more and less than 10.5. More preferably, the pH is 8.5 or more 1
It is 0.4 or less.

As the fixing liquid, those having a generally used composition can be used. The fixing solution generally has a pH of 3-8. As a fixing agent, sodium thiosulfate,
Potassium thiosulfate, thiosulfates such as ammonium thiosulfate, sodium thiocyanate, potassium thiocyanate,
In addition to thiocyanates such as ammonium thiocyanate, organic sulfur compounds capable of forming a soluble stable silver complex salt and known as a fixing agent can be used.

The fixer contains a water-soluble aluminum salt that acts as a hardening agent, such as aluminum chloride, aluminum sulfate, potassium alum, and aldehyde compounds (eg, glutaraldehyde and a sulfite adduct of glutaraldehyde).
Etc. can be added.

If desired, the fixer may include preservatives (eg, sulfite, bisulfite), pH buffers (eg, acetic acid, citric acid), pH adjusters (eg, sulfuric acid), and chelates having a water softening ability. Compounds such as agents may be included.

After fixing treatment, washing and / or stabilizing bath treatment is carried out. As a stabilizing bath, for the purpose of stabilizing an image, inorganic and organic acids and salts thereof, or alkali agents and salts thereof for adjusting the film pH (to adjust the film surface pH after treatment to 3 to 8) ( For example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid,
Used in combination with polycarboxylic acid, citric acid, oxalic acid, malic acid, acetic acid, etc.), aldehydes (eg formalin, glyoxal, glutaraldehyde etc.), chelating agents (eg ethylenediaminetetraacetic acid or its alkali metal salts, nitrilotriacetic acid salts) , Polyphosphate, etc., antifungal agent (eg phenol, 4-chlorophenol, cresol, O-phenylphenol, chlorophene, dichlorophene, formaldehyde, P-hydroxybenzoic acid ester, 2- (4-thiazoline) -benzo. Imidazole, benzisothiazolin-3-one, dodecyl-benzyl-methylammonium chloride, N- (fluorodichloromethylthio) phthalimide, 2,4,4'-
Trichloro-2'-hydroxydiphenyl ether, etc.), color tone adjuster and / or residual color improver (for example, a nitrogen-containing heterocyclic compound having a mercapto group as a substituent;
Specifically, sodium 2-mercapto-5-sulfonate-benzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole,
Mercapto-5-propyl-1,3,4-triazole, 2-mercaptohypoxanthine, etc.).
Among them, it is preferable that the stabilizing bath contains an anti-binder. These may be replenished in liquid or solid form.

The temperature of the developing, fixing, washing and / or stabilizing bath is preferably between 10 and 45 ° C., and the temperature of each may be adjusted separately.

Due to the demand for shortening the developing time, the total processing time (Dry) from when the leading edge of the film is inserted into the automatic developing machine to when it comes out of the drying zone when processing using the automatic developing machine
to Dry) is preferably 60 seconds or less and 10 seconds or more.

The halogen composition of silver halide in the silver halide emulsion is not particularly limited, but silver chloride, 60 mol% is used when processing is performed with a small replenishing amount or when rapid processing is performed.
It is preferable to use a silver halide emulsion having the above composition of silver chlorobromide containing silver chloride and silver chloroiodobromide containing 60 mol% or more of silver chloride.

The average grain size of silver halide is 1.2 μm.
m or less, and particularly 0.8 to 0.1 μm
Is preferred. The average particle size is a term that is commonly used by experts in the field of photographic science and is easily understood. The particle size means a particle diameter when the particles are spherical or spherical particles. If the particles are cubic, they are converted into spheres, and the diameter of the sphere is defined as the particle size. For details of the method for determining the average particle size, see Mies, James: The Theory of the Photographic Process (CE.
Mees & T. H. By James: The theor
y of the photographic pro
ccs), 3rd edition, pp. 36-43 (1966 (published by Macmillan "Mcmilllan")).

The shape of the silver halide grains is not limited,
The shape may be flat, spherical, cubic, tetrahedral, octahedral, or any other shape. Further, it is preferable that the particle size distribution is narrower, and in particular, a so-called monodisperse emulsion in which 90%, preferably 95% of the total number of particles falls within a particle size range of ± 40% of the average particle size is preferable.

For details of the silver halide emulsion and its preparation method, see Research Disclosure (Res).
(Earth Disclosure) 176 No. 1764
3, pages 22 to 23 (December 1978).

The silver halide emulsion may or may not be chemically sensitized. As chemical sensitization methods, sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and noble metal sensitization are known, and any of these may be used alone or in combination.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. That is, azoles, mercaptopyrimidines, mercaptotriazines, azaindenes, benzenethiosulfonic acid, benzenesulfinic acid,
Many compounds known as antifoggants or stabilizers, such as benzene sulfonic acid amide, can be added.

As the binder or protective colloid of the photographic emulsion, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

Examples of gelatin include lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Enzymatic degradation products of gelatin can also be used.

Inorganic or organic hardeners are added to the photographic emulsion and the non-photosensitive hydrophilic colloid layer as a crosslinking agent for hydrophilic colloids such as gelatin. These hardeners are available from Research Disclosure (Research Di
176) 17643 (July 1978)
Issued in February) P. 26, A to C.

Various other additives are used in the light-sensitive material. For example, a desensitizer, a plasticizer, a slipping agent, a development accelerator, an oil and the like can be mentioned.

For the above-mentioned additives and other known additives, see Research Disclosure N.
o. No. 17643 (December 1978); 187
16 (November 1979) and No. 16 308119
(December 1989).

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 such as color or black and white negative film, and direct viewing.

[0087]

Hereinafter, specific examples of the present invention will be described.
The embodiment of the present invention is not limited to this.

Example 1 << Preparation of Support >> (1) Polymerization of SPS SPS pellets were prepared according to JP-A-3-131843. That is, everything from the preparation of the catalyst to the polymerization reaction was carried out under a stream of dry argon. Glassy container copper sulfate having an inner volume of 500 ml 5-hydrate _{(CuSO 4 · 5H 2 O)} 17.8
g (71 mmol) of purified benzene (200 ml) and trimethylaluminum (24 ml) were added, and the mixture was stirred at 40 ° C. for 8 hours to adjust the catalyst. N under an argon stream
o. After filtering through 3 glass filters, the filtrate was freeze-dried. This was taken out, 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 in this, and the polymerization reaction was continued at this temperature for 8 hours. Thereafter, the mixture was cooled to room temperature, 1 l of methylene chloride was added, and a methanol solution of sodium methylate was added to the catalyst to deactivate the catalyst while further stirring. The contents were gradually dropped into 20 l of methanol, filtered through a glass filter, washed with methanol three times, and then dried. The weight average molecular weight of this polymer was 280,000, which was determined from the measurement results of GPC measured with standard polystyrene at 135 ° C. using 1,2,4-trichlorobenzene as a solvent. The melting point of this polymer was 245 ° C., and it was confirmed from the ¹³ C-NMR measurement that the polymer had a syndiotactic structure, which was then pelletized with an extruder.

(2) Preparation of SPS Film The obtained SPS polymer pellets were heated at 150 ° C. for 3 hours,
Dry in a nitrogen atmosphere, melt extrude into a film form from a T-die at 330 ° C., and make the sheet 4 by electrostatic loading.
An unstretched film was prepared by rapid cooling and solidification on a 0 ° C. cooling drum to obtain an unstretched film having a thickness of 1090 μm.
This unstretched film was stretched 3.3 times in the longitudinal direction at 130 ° C., then successively biaxially stretched 3.3 times in the transverse direction at 135 ° C., heat set at 245 ° C. for 30 seconds, wound, and spun.
An S roll film was obtained.

(1) Surface Treatment Both surfaces of the biaxially oriented SPS roll film (which was an SPS film having a contact angle of 90 °) obtained as described above were as shown in Table 1. And subjected to corona discharge treatment to obtain SPS films (supports) F-1 to F-7 having different contact angles.

(2) Undercoat of SPS film On the surface-treated SPS film of (1) above, an antistatic undercoat layer containing styrene-glycidyl acrylate and tin oxide fine particles was formed.

<< Preparation of Silver Halide Emulsion A >> Silver chlorobromide core particles having an average thickness of 0.05 μm and an average diameter of 0.15 μm, which are composed of 70 mol% of silver chloride and the balance is silver bromide, are prepared by the simultaneous mixing method. Prepared. At the time of mixing the core particles, 8 × 10 ⁻⁸ mol of K ₃ RuCl ₆ was added per mol of silver. The core particles were shelled using a double jet method. At that time, K ₂ I
3 × 10 ⁻⁷ mol of rCl ₆ was added per mol of silver. The obtained emulsion has an average thickness of 0.10 μm and an average diameter of 0.25.
μm core / shell monodisperse (variation coefficient 10%) (1
Chloroiodobromide (silver chloride 90
Mol%, silver iodobromide 0.2 mol% and the rest silver bromide). Then, JP-A-2-280
Modified gelatin described in JP-A-139 (a gelatin in which an amino group in gelatin is substituted with phenylcarbamyl, for example, Japanese Patent Laid-Open No. 2-53967).
-280139, Exemplified compound G-8 on page 287 (3))
It was desalted using. EAg after desalting is 190 mv at 50 ° C
Met.

To the obtained emulsion, 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene was added at 1 × 10 ^-3 mol per mol of silver, and potassium bromide and citric acid were further added to adjust the pH to 5. .6, adjust to EAg123mv,
After adding 2 × 10 ^-5 mol of chloroauric acid, add 3 × of inorganic sulfur
Chemical ripening was performed at a temperature of 60 ° C. until the maximum sensitivity was obtained by adding 10 ⁻⁶ mol. After completion of ripening, 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene was used in an amount of 2 × 10 ^-3 mol, 1-phenyl-5-mercaptotetrazole and 3 × 10 ^-4 mol per mol of silver and gelatin. Was added.

<< Preparation of Silver Halide Emulsion B >> Using the simultaneous mixing method, 60 mol% of silver chloride, 2.5 mol% of silver iodide and the rest of silver bromide having an average thickness of 0.05 μm and an average diameter of 0.
15 μm silver chloroiodobromide core grains were prepared. At the time of mixing the core particles, K ₃ Rh (H ₂ O) Br ₅ was added in an amount of 2 × 1 per mole of silver.
^0-8 moles were added. The core particles were shelled using a double jet method. At that time, K ₂ IrCl ₆ was added in an amount of 3 × 10 ⁻⁷ mol per mol of silver. The resulting emulsion was a core / shell type monodisperse (coefficient of variation: 10%) silver chloroiodobromide (90 mol% silver chloride, 0.5 mol silver iodobromide) having an average thickness of 0.10 μm and an average diameter of 0.42 μm. %, The rest consisting of silver bromide)
The emulsion was a tabular grain emulsion. Then, JP-A-2-28013
No. 9 described in Japanese Unexamined Patent Publication (Kokai) No. 2-2 (the modified gelatin wherein the amino group in the gelatin is substituted with phenylcarbamyl).
Desalting was carried out using the exemplified compound G-8) of No. 80139, page 287 (3). The EAg after desalting was 180 mv at 50 ° C.

4-Hydroxy-6-methyl-1,3,3a7-tetrazaindene was added to the resulting emulsion at 1 × 10 ^-3 mol per mol of silver, and potassium bromide and citric acid were further added to adjust the pH to 5. .6, adjust to EAg123mv,
After adding 2 × 10 ⁻⁵ mol of chloroauric acid, N, N, N′-
3 × 1 of trimethyl-N′-heptafluoroselenourea
0 ^-5 mol added to up sensitivity out at a temperature 60 ° C. chemically ripened. After completion of ripening, 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene was used in an amount of 2 × 10 ^-3 mol, 1-phenyl-5-mercaptotetrazole and 3 × 10 ^-4 mol per mol of silver and gelatin. Was added.

(3) Preparation of silver halide photographic light-sensitive material for printing plate making scanner for HeNe laser light source For each of the seven types of supports obtained in the above (2), one of the following prescription 1 was prepared on one undercoat layer. Formulate a gelatin subbing layer so that the amount of gelatin is 0.5 g / m ² and formula 2
The silver halide emulsion layer 1 was prepared so that the silver amount was 1.5 g / m ² and the gelatin amount was 0.5 g / m ^2. 0.3 g / m ² , and further the formulation 4
The silver halide emulsion layer 2 was prepared so that the silver amount was 1.4 g / m ² and the gelatin amount was 0.4 g / m ² , and the following formulation 5 was further added.
Was applied simultaneously so that the amount of gelatin became 0.6 g / m ² . On the other side of the undercoat layer, a backing layer of the following formulation 6 was formed so that the amount of gelatin was 0.6 g / m ^2, and a hydrophobic polymer layer of the following formulation 7 was formed on the backing layer, and the following formulation Seven kinds of light-sensitive materials are prepared by simultaneously coating the backing protective layer of No. 8 with the emulsion layer side so that the amount of gelatin is 0.4 g / m ² .

Formulation 1 (Composition of gelatin subbing layer) Gelatin 0.5 g / m ² Solid dispersion fine particles of dye AD-1 (average particle size 0.1 μm) 25 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² S-1 (Sodium-iso-amyl-n-decylsulfosuccinate) 0.4 mg / m ² Formulation 2 (composition of silver halide emulsion layer 1) Silver halide emulsion A Dye AD-8 so that the amount of silver is 1.5 g / m ^2. Solid dispersion fine particles (average particle diameter 0.1 μm) 20 mg / m ² cyclodextrin (hydrophilic polymer) 0.5 g / m ² sensitizing dye d-1 5 mg / m ² sensitizing dye d-2 5 mg / m ² hydrazine derivative H-7 20mg / m ² redox compound: RE-1 20mg / m ² compound e 100 mg / m ² latex polymer f 0.5 g / m ² hardener ^{g 5mg / m 2 S-1} 0. mg / m ² 2-mercapto-6-hydroxy purine ^{5mg / m 2 EDTA 30mg / m} 2 Colloidal silica (average particle size 0.05 .mu.m) 10 mg / m ² Formulation 3 (intermediate layer composition) Gelatin 0.3 g / m ² S -1 2 mg / m ² formulation 4 (composition of silver halide emulsion layer 2) silver halide emulsion B so that the amount of silver becomes 1.4 g / m ² sensitizing dye d-1 3 mg / m ² sensitizing dye d-2 3 mg / m ² hydrazine derivative H-20 20 mg / m ² Nucleation accelerator: Exemplified compound Nb-12 40 mg / m ² Redox compound: RE-2 20 mg / m ² 2-mercapto-6-hydroxypurine 5 mg / m ² EDTA 20 mg / m ² latex polymer ^{f 0.5g / m 2 S-1} 1.7mg / m 2 formulation 5 (emulsion protective layer composition) solid dispersion of gelatin 0.6 g / m ² dye AD-5 (average particle ^{0.1μm) 40mg / m 2 S-} 1 12mg / m 2 Matting agent: average particle size 3.5μm monodisperse silica 25 mg / m ² nucleation accelerator: Example Compound Na-3 40mg / m ² 1,3- Vinylsulfonyl-2-propanol 40 mg / m ² Surfactant h 1 mg / m ² Colloidal silica (average particle size 0.05 μm) 10 mg / m ² Hardener: K-1 30 mg / m ² Formulation 6 (backing layer composition) Gelatin 0.6 g / m ² S-1 5 mg / m ² Latex polymer f 0.3 g / m ² Colloidal silica (average particle size 0.05 μm) 70 mg / m ² Sodium polystyrene sulfonate 20 mg / m ² Compound i 100 mg / m ² prescription 7 (hydrophobic polymer layer composition) latex (methyl methacrylate: acrylic acid = 97: 3) 1.0 g / m ² hardening agent g 6 mg / m ² prescription 8 (backing) Protective layer) Gelatin 0.4 g / m ² Matting agent: Monodisperse polymethylmethacrylate having an average particle size of 5 μm 50 mg / m ² Sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ² Surfactant h 1 mg / M ² Dye k 20 mg / m ² H- (OCH ₂ CH ₂ ) ₆₈ -OH 50 mg / m ² Hardener: K-1 20 mg / m ²

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The surface resistivity of the backing side after coating and drying was 6 × 10 ¹¹ at 23 ° C. and 20% RH, and the film surface pH of the emulsion side surface was 5.5 and the swelling degree was 175.

<Evaluation> The wettability of the undercoat layer and the adhesiveness of the coating film were evaluated as follows.

<< Wettability of Undercoat Layer >> The wettability of the undercoat layer was evaluated on a scale of 5 according to the following criteria.

An undercoat layer was applied at a coating speed of 80 m / min by the wire bar coating method, and evaluated with the naked eye according to the following evaluation criteria.

(Evaluation Criteria) 1. The wettability is very poor, and the vertical and horizontal stripes of the undercoat layer coating are very noticeable and cannot be put to practical use. Even if the application speed was reduced, there was no prospect of streaking. The wettability is poor, and the vertical and horizontal stripes of the undercoat layer coating stand out,
Not practical. Lower the coating speed to 50m / min,
I finally got the aim of eliminating the streaks, but it markedly impairs productivity and is not practical. The wettability is slightly poor, and the vertical and horizontal stripes of the undercoat layer coating appear thin. Even if the emulsion layer is coated on the upper layer, the problem cannot be solved. By lowering the coating speed to 65 m / min, I got the aim of eliminating streaks,
3. It impairs productivity significantly and is not practical 4. It has good wettability and no vertical stripes or horizontal stripes of undercoat layer are visible. Continuous application for 30 days was possible. 4. The coating speed was increased to 100 m / min, and vertical stripes and horizontal stripes of the undercoat layer were not generated, and continuous coating for 30 days was possible. It has very good wettability and no vertical or horizontal streaks of the undercoat layer are visible. At 100 m / min, continuous application for 30 days was possible. Increase coating speed to 145m / min,
Similarly, continuous application for 30 days was possible.

<< Adhesiveness of Coating Film >> On the emulsion side of the silver halide photographic light-sensitive material obtained above, cuts are made in a lattice pattern with a razor, a cellophane tape is pressure-bonded, and rapidly peeled off to form an undercoat layer. The peeled area of the (primer layer) was evaluated on a 5-point scale.

(Adhesiveness Evaluation Criteria) 1. The adhesive strength is very weak, and 100% of the area is completely peeled off.

Areas of 2.50% or more and less than 100% are peeled off.

3. Areas of 10% or more and less than 50% are peeled off.

4. The adhesive strength is strong, and an area of 5% or more and less than 10% peels off.

5. Adhesive strength is very strong, peeling area is 5%
Almost no peeling occurs when less than.

(Adhesiveness) In addition, 1 to 3 are levels that cannot be practically used; x 4 is a level that can be sufficiently practically used; o 5 is a very excellent level;

The above results are shown in Table 1.

[0115]

[Table 1]

As is apparent from Table 1, the experiment No. 1 to
1 to 4 (invention) and Experiment No. 1 to 5 to 1 to 7
From comparison with (Comparison), it is understood that the contact angle with water satisfying the preferable ranges of wettability and adhesiveness is 65 ° or less and 39 ° or more, preferably 55 ° or less and 39 ° or more.

Example 2 Wettability and adhesiveness were evaluated in the same manner as in Example 1 except that the corona treatment was changed to the ultraviolet treatment of a low pressure mercury lamp as shown in Table 2.

Table 2 shows the results.

[0119]

[Table 2]

As is apparent from Table 2, the experiment No. Two
1 to 2 to 4 (invention) and Experiment No. 2-5-2-7
From the comparison with (Comparison), even when the surface treatment method is changed from corona treatment to low-pressure mercury lamp, the contact angle with water satisfying the preferable ranges of wettability and adhesiveness is 65 ° or less and 39 ° or more, preferably It is understood that is less than 55 ° and greater than 39 °.

From the above results, the wettability of the undercoat layer of the silver halide photographic light-sensitive material of the present invention and the adhesiveness of the silver halide photographic light-sensitive material are not related to the surface treatment method, If the contact angle satisfies a specific angle, namely 65 ° or less and 39 ° or more, preferably 55 ° or less and 39 ° or more,
Understand what can be achieved. The coating speed is
It can be understood that a combination of 80 m / min or more, preferably 100 m / min or more can be achieved.

[0122]

According to the present invention, it has excellent thermal, mechanical, physical, chemical, and optical properties, especially optical properties (light transmittance, haze, etc.), dimensional stability (hygroscopic expansion coefficient). It was possible to provide a silver halide photographic light-sensitive material excellent in productivity and excellent in film productivity.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display location G03C 1/81 G03C 1/81 1/91 1/91 // B29K 25:00

Claims (5)

[Claims] 1. A photographic light-sensitive material having at least one silver halide emulsion layer on a support, the support being a syndiotactic polystyrene support, and a surface applied before applying an undercoat layer. A silver halide photographic light-sensitive material having a contact angle with water after processing of 39 to 65 °. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the contact angle of the support with water after the surface treatment is 39 to 55 °. 3. The undercoat layer coating speed after the surface treatment of the support is 80 m / min or more.
Or the silver halide photographic light-sensitive material described in 2. 4. The silver halide photographic light-sensitive material according to claim 1, wherein the coating speed of the undercoat layer after the surface treatment of the support is 100 m / min or more. 5. A method for producing a silver halide photographic light-sensitive material according to claim 1.