JPH0990559A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material excellent in dimensional stability by using a syndiotactic polystyrene based supporting body for photography moreover low in humidity expansion coefficient and thermal expansion coefficient. SOLUTION: The syndiotactic polystyrene-based supporting body for photography having <=50×10<-6> / deg.C thermal expansion coefficient and 1.0×10<-6> /(%RH) humidity expansion coefficient is used. And, the syndiotactic polystyrene-based supporting body for photography having <=50×10<-6> / deg.C thermal expansion coefficient, 1.0×10<-6> /(%RH) humidity expansion coefficient and a facial direction refractive index of <=1.585 is used.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material having a biaxially stretched syndiotactic polystyrene photographic support. More particularly, it relates to a silver halide photographic light-sensitive material having excellent dimensional stability, which comprises a biaxially stretched syndiotactic polystyrene photographic support having a small coefficient of temperature expansion and coefficient of humidity expansion.

[0002]

2. Description of the Related Art A polyethylene terephthalate (hereinafter abbreviated as PET) film is used as a photographic support of a silver halide printing photographic light-sensitive material (hereinafter sometimes abbreviated as printing light-sensitive material). Previously, a cellulose triacetate photographic support was used, but PET that has high hygroscopicity and water absorption and a low elastic modulus has poor dimensional stability required for a photosensitive material for printing and is superior in properties.
Photographic supports have come into use.

Dimensional stability of a photosensitive material for printing is one of the most important properties for the photosensitive material in order to obtain a printed matter free from color shift when printing with the four photosensitive materials of different colors. is there. Dimensional stability refers to photographic support, photosensitive layer, etc. (collective term for emulsion layer, intermediate layer, protective layer, back layer, etc.)
It largely depends on the thickness, elastic modulus, coefficient of humidity expansion (hereinafter abbreviated as (α _h )) and temperature expansion coefficient (hereinafter abbreviated as (α _t )) of all layers. In addition, this is
As a relational expression relating to the dimensional stability of a silver halide photographic light-sensitive material, J. Q. Umberger: Photo. Sc
i. Eng. Volume 11, page 385 (1967). Four plates are processed at the same temperature and the same humidity to make a plate film, but if one of them has to be remade, the temperature or humidity may be different from the previous one, and the plate film baked afterwards There is some dimensional deviation from the previous ones. In such cases, 4
The sheets have to be reprinted, which is a waste of money and labor. Therefore, there has been a demand for a silver halide photographic light-sensitive material that is stable even under such slight changes in conditions. At present, a PET film is used as an inexpensive photographic support having a small water absorption, a relatively small (α _h ), and an inexpensive photographic support. With respect to the photosensitive layer and the like, it has been attempted to reduce the elastic modulus of the photosensitive layer by thinning the layer or mixing a polymer latex into the layer.

However, the thickness of the photosensitive layer, which has had a great influence on the dimensional stability of the photosensitive material for printing until now, can be made thinner and thinner, and the contribution of the photosensitive layer, etc. to the dimensional stability. Has become extremely small,
The contribution of the PET photographic support itself to the dimensional change of the photosensitive material for printing has become a problem.

In order to reduce the water absorbency of the PET photographic support, an attempt has been made to reduce the (α _h ) of the photosensitive material for printing by coating a vinylidene chloride resin having a small water permeability on the surface thereof. Made However, when incinerating used films for disposal, chlorine gas is generated, which damages the furnace and pollutes the environment. Therefore, a photographic support having a smaller (α _h ) than PET has been required.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material excellent in dimensional stability. In particular, it is an object of the present invention to provide a silver halide photographic light-sensitive material excellent in dimensional stability using a biaxially stretched syndiotactic polystyrene photographic support having a small coefficient of thermal expansion and a coefficient of humidity expansion.

[0007]

[Means for Solving the Problems] As a result of searching for a photographic support instead of PET, syndiotactic polystyrene (hereinafter sometimes abbreviated as SPS) -based film has a small (α _h ), and therefore as a substitute film for PET. I found it suitable. Recently, various proposals regarding SPS have been made. For example, SPS is disclosed in JP-A-3-131843 for photography, and for other applications, JP-A-11-110122 and JP-A-1-1687.
09, 1-182346, 2-279731.
No. 3, No. 3-74437, No. 3-131644, No. 6
-207636, 6-322149, 7-01
No. 3024, No. 7-001643, No. 7-00164
No. 4 and No. 7-24911 are proposed. As described above, the SPS-based film is excellent in transparency, has a small (α _h ), has a high mechanical strength, and is lightweight, and thus has been developed for various applications.

The present invention provides a biaxially stretched syndiotactic polystyrene photographic support having an (α _t ) of 50 × 10 ⁻⁶ / ° C. or less and an (α _h ) of 1 × 10 ⁻⁶ / (% RH) or less. Achieved by a silver halide photographic light-sensitive material having a body.

The materials (α _h ) and (α _t ) are generally determined by the material. The (α _h ) of the SPS-based photographic support is on the order of 1 × 10 ^-6 / (% RH), and that of PET is on the order of 2 × 10 ^-5 (% RH). The body is 1 more than that of PET
/ 20 to 1/50 small. (Α _h ) of a layer mainly composed of gelatin such as a photosensitive layer varies depending on the composition, but is generally 10 to 3
It is about 0 × 10 ^-5 / (% RH), and the effect of thickness is taken into consideration (the ratio of the thickness of the photosensitive layer / the thickness of the photographic support is 1/1).
Even if it is 0), it is considered that the (α _h ) of the SPS photographic support is so small that it no longer affects the (α _h ) of the entire silver halide photographic light-sensitive material. In other words, even if the thickness of all layers such as the photosensitive layer becomes considerably thin, SP
S based photographic support is that the would not be such as to affect the entire (alpha _h) of the silver halide photographic material, which can further reduce the SPS based photographic support the (alpha _h) It seems that the effect can be further reduced.

On the other hand, the (α _t ) of the SPS type film is 20 × 10 ^-6 / ° C., which is almost the same order as that of PET,
If this (α _t ) can be reduced to a small fraction, then the dimensional change with temperature of the silver halide photographic light-sensitive material can be reduced. Then, (α _t ) is 10 times or more larger than (α _h ), and reducing (α _t ) greatly contributes to dimensional stability.

As a result of diligent studies, the present inventor has made a diligent study as to whether (α _h ) and (α _t ) of the SPS-based photographic support can be further reduced under the film forming conditions. It was found that (α _h ) and (α _t ) changed depending on the conditions.

The present inventor has found that the value of the refractive index and both expansion coefficients have a substantially linear relationship. It is not clear why these expansion coefficients have such a relationship, but I think that there is some correlation between the orientation structure of syndiotactic polystyrene molecules and the expansion coefficient.

Hereinafter, the present invention will be described in detail.

The SPS of the present invention will be described. The SPS of the present invention, that is, a polystyrene-based polymer having a syndiotactic structure means that the stereoregular structure (tacticity) has a syndiotactic structure, that is, a main chain formed from carbon-carbon bonds. On the other hand, it has a steric structure in which phenyl groups and substituted phenyl groups, which are side chains, are alternately located in opposite directions. In SPS, not all styrene units of the main chain have a syndiotactic structure, but a part where several styrene units of syndiotactic structure are connected, and they are overlapped to form a crystal part. It has a structure. This chain is called racemo chain, and SPS is a composition having many polystyrene racemo chains in the main chain. When a plurality of continuous styrene constitutional units is 2, it is called diad, when it is 3 it is called triad, and when it is 5 it is called pentad. What is meant by the styrene polymer mainly having a syndiotactic structure in the present invention is Usually, the racemic diad content is preferably 75% or more, preferably 85% or more, or the racemic triad is 60% or more, preferably 75% or more, or the racemic pentad is 30% or more, 50% or more. This tacticity can be quantified by a nuclear magnetic resonance method ( ¹³ C-NMR method) using isotope carbon.

The SPS polymer of the present invention may be a styrene homopolymer, a composition containing a styrene derivative or another monomer, and is a styrene homopolymer. Polymerization by the method described in JP-A No. 62-117708, and regarding other polymers, JP-A Nos. 1-46912 and 1-178505.
It can be obtained by polymerization according to the method described in No.

Specific examples of the polymer constituting the SPS composition include styrene, alkylstyrene such as methylstyrene, halogenated (alkyl) styrene such as chloromethylstyrene and chlorostyrene, and alkoxy. Examples thereof include styrene and vinyl benzoate.

When the SPS photographic support of the present invention contains a monomer as a styrene derivative other than styrene, it may be contained in an amount of 15 mol% or less, preferably 10 mol% or less. Particularly, 5 to 10 mol% is preferable. In this case, 4-methylstyrene is preferable as the styrene derivative.

The polystyrene-based resin having a syndiotactic structure of the present invention uses the above-mentioned raw material monomers as a polymerization catalyst and is disclosed in JP-A-5-320448, pages 4 to 1.
(A) (a) a transition metal compound and (b) aluminoxane as a main component described on page 0, or (b) an ionic complex that reacts with (a) a transition metal compound and (c) a transition metal compound It can be produced by polymerization using a compound containing a compound capable of forming

In order to produce the styrenic polymer used for the SPS photographic support of the present invention, first, the styrenic monomer is sufficiently purified and then polymerized in the presence of any of the above catalysts. Let At this time, the polymerization method, polymerization conditions (polymerization temperature, polymerization time), solvent, etc. may be appropriately selected. Usually, the polymerization is carried out at a temperature of −50 to 200 ° C., preferably 30 to 100 ° C. for 1 second to 10 hours, preferably 1 minute to 6 hours. As the polymerization method, a slurry polymerization method, a solution polymerization method, a bulk polymerization method, a gas phase polymerization method, etc.
Any of them can be used, and either continuous polymerization or discontinuous polymerization may be used. Here, in the 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 may be used alone or in combination. 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. After completion of the polymerization, it is preferably pelletized by a conventional method before use.

SPS used in the photographic support of the present invention
The molecular weight of the polymer is not limited as long as it is formed into a film, but the weight average molecular weight is 10,000 to 300,000.
0 is preferable, and particularly 30,000 to 1500
000 is preferable. 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.

From the viewpoint of stereoregularity, the SPS photographic support of the present invention is preferably an SPS homopolymer, but in addition to the syndiotactic structure, an isotactic main chain is a mesochain. A styrene-based polymer (IPS) having a structure may be mixed, and this can control the crystallization rate and can form a stronger film. When SPS and IPS are mixed, the SPS: IPS ratio is preferably 30:70 to 99: 1, and particularly preferably 50:50 to 98: 2, although it depends on the stereoregularity of each other. .

In the photographic support of the present invention, inorganic fine particles, antioxidants, UV absorbers, antistatic agents, dyes, pigments and dyes are added for the purpose of imparting functionality to the extent that the objects of the present invention are not impaired. Etc. can be contained in the SPS resin pellets.

Before film formation, the SPS resin pellets of the present invention are preferably dried at 120 to 180 ° C. for 1 to 24 hours under vacuum or under atmospheric pressure in an inert gas atmosphere such as carbon dioxide or nitrogen.

Film formation of the SPS type photographic support of the present invention will be described. First, a known method can be applied as a method of extruding at the time of film formation, but for example, it is preferable to extrude with a T die. The vacuum-dried SPS pellets are put into an extruder, melted and extruded at 280 to 350 ° C., cooled and solidified while electrostatically loaded on a casting drum to produce an unstretched film.

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.・ Longitudinal stretching method, longitudinal / longitudinal / horizontal stretching method, or simultaneous 2
An axial stretching method or the like can be adopted. In the present invention, a sequential biaxial stretching method of first stretching in the machine direction (longitudinal direction or machine direction) and then in the transverse direction (width direction), or a method of further stretching in the machine direction is preferable.

Both (α _h ) and (α _t ) of the present invention can be brought within the scope of the present invention by the stretching conditions as described above. To satisfy both (α _h ) and (α _t ) of the present invention, SPS
Glass transition temperature (Tg = 100 ° C) of + 10 ° C to +5
In the range of 0 ° C, that is, 110 to 150 ° C, 3.0 to 6.
The film is longitudinally stretched 0 times, preferably 3.5 to 5.0 times, and then transversely stretched 3.0 to 6.0 times, preferably 3.2 to 5.0 times in the range of 115 to 160 ° C. Obtained by

Next, this stretched film is heat set. In order to achieve the object of the present invention, although it depends on various film forming conditions, heat setting treatment is also one of the important conditions. As the heat setting temperature suitable for the present invention, a temperature range of 220 to 270 ° C. is preferable, and a temperature range of 230 to 260 ° C. is preferable. The heat setting time is not particularly limited, but is usually about 3 to 100 seconds. At this time, if necessary, heat relaxation treatment may be performed in the vertical or horizontal direction.

Within the above range, as the draw ratio is increased, the refractive index becomes smaller, and when heat setting is carried out at 220 ° C. or higher, preferably in the range of 230 to 255 ° C., the refractive index changes to a smaller direction. Between the refractive index and (alpha _h) and (α _t), the refractive index becomes smaller (alpha _h) and (alpha _t) both nearly linear relationship such that small. The refractive index useful in the present invention is 1.585 or less, and the lower limit thereof is not limited, but 1.540 is preferable. It was also found that at the same stretch ratio, the refractive index was large and therefore (α _t ) was large at a temperature not heat-set or at a lower temperature.

As a result, (α _h ) is 1.0 × 10 ^-6 /
The following (% RH) was obtained. The (α _h ) of the SPS-based photographic support of the present invention is 1.0 × 10 ⁻⁶ / (% RH) or less, and the lower limit is about 0.1 × 10 ⁻⁶ / (% RH),
It is preferably up to 0.2 × 10 ⁻⁶ / (% RH).

Further, (α _t ) is 50 × 10 ^-5 / ° C. or less, and the lower limit is not limited, but it is preferably up to 20 × 10 ^-5 / ° C.

Refractive index, (α _h ) and (α _t ) in the present invention
The value of is the value of the surface of the photographic support, and is preferably substantially the same in all directions of the surface, and it is preferable to control the method of film formation as such. The fact that these numerical values differ greatly in all directions, such as the vertical direction, the horizontal direction, or the diagonal direction, makes registration difficult.

In any case, the object of the present invention can be achieved as long as both (α _h ) and (α _t ) in the claims of the present invention are satisfied without being limited to the above-mentioned film forming method. I can.

The thickness of the SPS-based photographic support thus obtained varies depending on the application of the silver halide photographic light-sensitive material, but is 50 to 130 μm for the color film, 70 to 200 μm for the printing light-sensitive material film, and X. Line film 1
The film-forming conditions mentioned above range from 50 to 80 μm.
It is effective for a thickness of 250 μm.

Next, the undercoating treatment of the SPS type photographic support will be described. Before 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,
Surface treatment such as laser treatment, mixed acid treatment and ozone oxidation treatment is preferred. By these treatments, the contact angle of water on the surface of the SPS type photographic support can be set to 65 ° or less, preferably 55 ° or less, and if the wettability and adhesiveness at the time of coating the undercoat layer are good. It is effective for tightening.

When the above corona treatment is performed, the discharge condition is set to a discharge frequency of 50 Hz to 5000 KHz.
In addition, it is preferable to set it to 5 KHz to several hundred KHz. 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, and the cost of the device becomes high, which is not preferable. The processing strength of the object to be treated is 5 to 20 W · min / m ² , and preferably 6 to 15 W · min / m ² for the SPS photographic support. The treatment strength may vary depending on the type of device (gap clearance between electrode and dielectric roll, discharge shape, discharge frequency, waveform, etc.), and the contact angle between the treated surface of the photographic support and water is in the above range, Adjust the device so that

The ultraviolet treatment is preferably performed by 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 ray treatment is preferably performed in the 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 ultraviolet irradiation method is preferably a high-pressure mercury lamp (generating a spectrum having a main wavelength of 365 nm), and the irradiation light amount is 100 to 1500 (mJ / m ² ).
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 also preferably 400 to 1300 (mJ
/ M ² ) is preferable. Since the processing strength cannot be strictly defined depending on the type of lamp, the type of device, etc., the contact angle between the treated surface of the photographic support and water may be adjusted so as to satisfy the above range.

As the undercoat layer, any of those used in the art can be used.

The undercoating of the SPS-based photographic support of the present invention may be carried out before stretching during film formation, after uniaxial stretching, after biaxial stretching before heat setting, or after biaxial stretching heat setting, as in the PET film. Can be done in that process. The SPS-based photographic support also has sufficient hindrance to the adhesion of the emulsion layer and the like even after the biaxially stretched and heat-fixed, but the subbing before the completion of oriented crystals is preferred. The drying temperature of the undercoat layer is 80 to 250 ° C.
It is better to carry out in the temperature range. The above-mentioned treatments such as UV irradiation and corona discharge before and after the undercoating are effective means for improving the adhesiveness to the SPS-based photographic support.

As the undercoat material for the SPS type photographic support of the present invention, methacrylic acid, acrylic acid, itaconic acid,
Unsaturated carboxylic acid or ester such as maleic anhydride (as the ester group, a C ₁ -C ₈ alkyl group, hydroxyethyl group, phenyl group, benzyl group, phenethyl group,
N, N-dimethylaminoethyl group, glycidyl group, etc.),
Acrylamide, N-substituted acrylamide (as a substituent, a C _{1 to} C ₄ alkyl group, phenyl group, sulfopropyl group, benzyl group, N-methylol group, etc.) Styrene, styrenesulfonic acid, vinylidene chloride, vinyl chloride, Examples thereof include polymers or copolymers obtained from monomers such as butadiene. Further, water-dispersed polyester, polyurethane, polyethyleneimine, epoxy resin and the like are also included. Of these, a styrene-butadiene copolymer is preferably used. Specifically, the styrene / butadiene molar ratio is 9/1 to 1 /
The copolymer of 9 is preferred. In addition, the comonomer having a hydrophilic group such as acrylic acid as the third comonomer is 2 to 10% by weight with respect to the styrene / butadiene copolymer.
Copolymerization and inclusion can provide the effect of further improving the adhesiveness between the SPS-based photographic support and the photographic emulsion layer. Another preferred specific example is a copolymer having a water-dispersible polyester and a styrene polymer as constituent elements.

The water-dispersible polyester 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,
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. 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. As the dicarboxylic acid having a sulfonate and / or an ester-forming derivative thereof, those having an alkali metal sulfonate group are particularly preferable,
For example, alkali metal salts such as 4-sulfoisophthalic acid, 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and 5- (4-sulfophenoxy) isophthalic acid,
Alternatively, an ester-forming derivative thereof is used, but 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.

The water-dispersible polyester and the copolymer having a styrenic (vinyl-based) polymer as a constituent are a method of chain transfer copolymerization with the water-dispersible polyester, and addition polymerization at the terminal of the water-dispersible polyester. Method of grafting by introducing a possible group and copolymerizing with a monomer of styrene (vinyl) copolymer, styrene (vinyl)
There is a method of introducing a reactive group at the time of condensation polymerization of a water-dispersible polyester such as a carboxylic acid, a glycidyl group or a substituted amino group as a monomer by polymerizing a copolymer. This styrene may be changed to another vinyl-based monomer and reacted.

When the vinyl monomer is copolymerized in the presence of the water-dispersible polyester, it is polymerized in the form of a latex. In this case, however, a surfactant is not particularly required and the polymerization reaction is possible. is there. However, in order to improve the polymerization stability, a surfactant may be used as an emulsifier in the system, and a general nonionic and anionic surfactant can be used.

The ratio of the water-dispersible polyester to the styrene copolymer is 99/1 to 5/95, preferably 9
7/3 to 50/50, more preferably 95/5 to 80 /
Twenty.

A polymerization initiator is used for these polymerizations.
As the polymerization initiator, persulfates such as ammonium persulfate, potassium persulfate and sodium persulfate, peroxides such as hydrogen peroxide, 4,4′-azobis-4-cyanovaleric acid or a salt thereof, 2,2- Azobis compounds such as azobis (2-aminopropane) hydrochloride can be used. Further, peroxides and persulfates can also be used as a redox initiator in combination with a reducing agent such as ferrous chloride, ferrous sulfate, and sodium ammonium ammonthiosulfate.

The SPS-based photographic support of the present invention may be subbed in an aqueous system, an organic solvent-containing aqueous system, or an organic solvent system. Among the organic solvents, as solvents for SPS, there are benzene, xylene, toluene, ethylbenzene, cyclopentane, hexane, heptane, octane, methyl ethyl ketone, and soclohexanone. If it is too much, the support will be damaged and the flatness will be impaired, so it is preferable to mix in a small amount in a poor solvent such as methanol, ethanol, propanol, cyclohexanol, or acetone. The amount is preferably 15% or less with respect to the poor solvent.

Further, a polymer latex is often used as an undercoat for the SPS type photographic support of the present invention. Water is used as the undercoat liquid for this purpose, but an organic solvent such as methanol, ethanol or acetone may be mixed therein.

The coating property of the undercoat liquid on the SPS type photographic support can be improved by containing the following water-soluble polymer. Useful water-soluble polymers include hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), methyl cellulose (MC), hydroxypropyl methyl cellulose (H
PMC), ethyl hydroxyethyl cellulose (EHE
C), modified hydroxyethyl cellulose (HMHE
C), polyvinylpyrrolidone (PVP), polyethylene oxide (PEO), xanthan, cationic hydroxyethyl cellulose (CATHEC), hydroxypropyl guar (HP guar), guar, polyvinyl alcohol (PVA), polyacrylamide, sodium alginate, and carbopol. (Carbopol; registered trademark) acrylamide thickening composition and the like, and particularly useful water-soluble polymers include CMC and MC.
Is preferred. For example, CMC-7LX (Aquaron,
Substitution degree = 0.65 to 0.80, viscosity at a concentration of 5% by weight in water is 200 to 1000 mPa.s. Although s) is suitable for the undercoat liquid of the SPS type photographic support, other types, those having various viscosities and those having various degrees of carboxymethyl substitution can be used. MC and H
EC (manufactured by Aqualon), EHEC (manufactured by Bellol and Nobelol, and HPMC (manufactured by Aqualon and Dow Chemical) are also useful as an undercoat liquid for the SPS photographic support.

The coating concentration of the undercoating polymer in the undercoating liquid for the SPS type photographic support of the present invention is preferably 20% by weight or less, and a concentration of 5 to 15% by weight is particularly preferable in view of uniform coating property. .

The coating amount of the undercoat liquid on the SPS photographic support is preferably 1 to 20 g / m ² after drying, and particularly preferably 5 to 15 g / m ² from the viewpoint of coating property and adhesiveness. . The coating amount of the subbing polymer may have a range of 10~3000mg / m ^2, more preferably in the range of 100-1000 mg / m ^2. By the way, the SPS-based photographic support has a smaller dielectric loss than that of the PET photographic support, and therefore has a property that it is difficult to remove the charge once it is charged. , The way the liquid adheres may change, and uneven coating may occur. In such a case, it is desirable to forcibly remove the charge before and after applying the subbing liquid. As the static elimination method, a method of grounding the roll in contact with the transport support, a method of spraying water atomized by ultrasonic waves, a method of ionizing the surrounding air with radiation to neutralize the electric charge, and a static elimination brush are used. The method used, the high-voltage application method, the method of producing ion wind and blowing it can be used.

The subbing layer may be a single layer, but it is desirable that it is a multi-layer in order to further enhance the functionality and enhance the adhesive strength. The subbing multilayer method will be described below. In the multilayer method, the undercoat layer is referred to as an undercoat layer, and the undercoat layer described below is referred to as an undercoat upper 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 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.

The subbing upper layer is preferably a hydrophilic binder layer for adhering the photographic emulsion layer well. As a binder constituting the hydrophilic binder layer, gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers, water-soluble polymers such as carboxymethyl cellulose and hydroxyethyl cellulose, sodium polystyrene sulfonate Examples include a combination of a copolymer and a hydrophobic latex, and of these gelatin is most preferable.

A hardener is preferably used for the binder layer in the undercoating upper layer to enhance the film strength. Examples of such hardener include aldehyde compounds such as formaldehyde and glutaraldehyde, US Pat. Second,
732, 303, 3,288,775, British Patents 974,723, 1,167,207 and the like, 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, US Pat.
763, 3,635,718, British Patent No. 99
Compounds having a reactive olefin described in U.S. Pat. No. 4,539,644, U.S. Pat. Nos. 3,539,644 and 3,642.
No. 486, Japanese Patent Publication No. 49-13568, No. 53-472.
71, 56-48860, and JP-A-53-5725.
No. 7, No. 61-128240, No. 62-4275,
Nos. 63-53541 and 63-264572, vinyl sulfone compounds, N-hydroxymethylphthalimide, U.S. Pat. Nos. 2,732,316 and 2,5.
N-methylol compounds described in US Pat. No. 86,168, isocyanate compounds described in US Pat. No. 3,103,437, US Pat. Nos. 2,983,611 and 3,10.
7,280, etc., aziridine compounds, US Pat. Nos. 2,725,294, 2,725,295, etc., acid derivatives, and US Pat. No. 3,100,704, etc., carbodiimides. Compounds, US Pat. No. 3,093
1,537, etc. epoxy compounds, US Pat. Nos. 3,321,313, 3,543,292 etc. isoxazole compounds, halogenocarboxaldehydes such as mucochloric acid, dihydroxydioxane. , Organic hardeners such as dioxane derivatives such as dichlorodioxane, and inorganic hardeners such as chrome alum, zirconium sulfate, and chromium trichloride. Further, as a hardener having a relatively fast hardening effect on gelatin, Japanese Patent Application Laid-Open No. 50-
Compounds having a dihydroquinoline skeleton described in JP-A-38540, JP-A-51-59625 and JP-A-62-26285.
No. 4, No. 62-264044, No. 63-184741.
N-carbamoylpyridinium salts described in JP-B No. 55-38655, acylimidazoles described in JP-B No. 55-238655, N-acyloxyimidazoles described in JP-B No. 53-22089, and N-acyloxy compounds described in JP-B No. 53-22089. A compound having two or more imino groups in the molecule,
Compounds having an N-sulfonyloxyimide group described in JP-A-52-93470, JP-A-58-113929
Compounds having a phosphorus-halogen bond described in JP-A-60-225148, JP-A-61-240236 and JP-A-6-240236.
A chloroformamidinium compound described in 3-41580 is known.

This undercoating upper layer preferably contains, as a matting agent, inorganic fine particles such as silicon dioxide and titanium oxide, and an organic matting agent (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.

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 / m ^{2 in} terms of coating liquid weight, and further 5 to ²
It is preferably 0 g / m ² .

As the method of applying the subbing liquid, various known methods can be applied. For example, roll coating method gravure roll coating method, spray coating method, air knife coating method, bar coating method, impregnation method and curtain coating method,
It can be applied alone or in combination.

The SPS-based photographic support thus obtained is not only used in silver halide photographic light-sensitive materials such as color films, printing light-sensitive material films and X-ray films, but also in materials other than silver halide photographic light-sensitive materials. , Printing film, OHP film, marking film, photochromic photosensitive film, photosensitive resin film, etc.

Next, the photosensitive layer of the silver halide photographic light-sensitive material will be described.

The silver halide emulsion layer may be black and white or color. Here, the silver halide photographic light-sensitive material for printing will be mainly described.

As the silver halide used in the silver halide photographic light-sensitive material of the present invention, silver bromide, silver chloride, silver iodobromide,
A normal silver halide emulsion of silver chlorobromide or silver chloroiodobromide can be used arbitrarily, and those obtained by any method such as an acid method, a neutral method, and an ammonia method can be used. Preferred silver halides for printing emulsions are silver chloride, silver chlorobromide containing 60 mol% or more of silver chloride, or silver chloroiodobromide containing 60 mol% or more of silver chloride.

The silver halide grains may be those having a uniform silver halide composition distribution within the grain or core / shell grains having different silver halide compositions inside the grain and on the surface layer. The particles may be formed mainly inside the particles.

As the silver halide grains, grains having a single shape may be used, or grains having various shapes may be mixed. Further, those having any particle size distribution may be used, and a polydisperse emulsion or a monodisperse emulsion may be mixed and used.

The emulsion grains of the silver halide photographic light-sensitive material for printing are preferably monodisperse. The emulsion of monodisperse grains is within a grain size range (variation coefficient) of ± 20% around the average grain size r. The silver halide contained in is 6 of all silver halides.
It is preferably at least 0%, particularly preferably 70%
Or more, and more preferably 80% or more. Here, the particle size in the case of spherical silver halide particles is the diameter thereof, or the diameter when a projected image of a particle having a shape other than a spherical shape is converted into a circular image of a peripheral area. A highly uniform monodispersion is preferred as a photographic image. Monodisperse emulsion is disclosed in JP-A-5
5-48521, 58-49938 and 60-
It can be obtained by referring to the method described in the specification such as 122935.

The shape of silver halide grains is not limited,
The shape may be flat, spherical, cubic, tetrahedral, octahedral, or any other shape. For example, JP-A-5-20407
Tabular grains can be obtained by the method described in No. 0 specification.

As the method of reacting the soluble silver salt and the soluble halogen salt in the present invention, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof can be used.

It is also possible to use a method of forming grains in the presence of excess silver ions (so-called reverse mixing method). As one type of the double jet method, a method of keeping pAg constant in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. Thus, a silver halide emulsion having a nearly uniform grain size can be obtained.

The silver halide grains used in the silver halide emulsion include cadmium salt, zinc salt, lead salt, thallium salt, iridium salt, rhodium salt, or a salt thereof in at least one of the grain forming process and the growing process. It is preferable to add a complex salt containing the above element.

For details of the silver halide emulsion and its preparation method, see Research Disclosure (Rese
arch Disclosure (hereinafter abbreviated as RD) No. 176, 17643, 22 to 23 (1978, 1
(February).

The light-sensitive silver halide emulsion can be used as it is as a so-called unripened (Primitive) emulsion without chemical sensitization, but it is usually preferable to carry out chemical sensitization.

In the silver halide emulsion of the silver halide photographic light-sensitive material used in the present invention, main photographic additives can be used in the steps before and after physical ripening or chemical ripening. Examples of the compound used in such a step include the following R
Each of the main compounds described in D can be used.

Among the silver halide photographic light-sensitive materials, in the light-sensitive material for printing, in order to improve the halftone quality, a silver halide emulsion layer or a non-light-sensitive layer may be added with a high-contrast agent, or a high-contrast treatment may be applied in the development process. Is done. Examples of excellent contrast agents include the following hydrazine compounds or tetrazonium compounds. Representative examples of these are given below, but the invention is not limited thereto.

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[Chemical 6]

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[Chemical 7]

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention can use various photographic additives in the steps before and after physical ripening or chemical ripening.
As the compound used in such a step, for example, R
DNo. 17643, RD No. 18716 and RDN
o. Various compounds described in 308119 (December 1989) can be used.

The types of compounds described in these three RDs and the locations where they are described are listed below.

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[Table 1]

The silver halide photographic light-sensitive material having a light-sensitive layer on one side includes a color film and a printing light-sensitive material, and there is also a material having a light-sensitive layer on both sides such as an X-ray film. In many cases, a film having a single-sided photosensitive layer has a back layer provided on the back side thereof and is in a roll-wrapped form. Generally, a silver halide photographic light-sensitive material for printing has at least one silver halide emulsion layer and at least one emulsion protection layer on the light-sensitive layer side on a photographic support, and on the other side, a layer having a certain function and There is a back layer in which at least one protective layer is provided. There is no particular limitation on the number of silver halide emulsion layers or back layers.

A function can be imparted to each layer of the back layer. For example, functionalized layers include an antistatic layer, an antihalation layer, an antiirradiation layer, and a magnetic recording layer. These layers may be adjacent to the subbing layer, may be on the surface, or may be present at any position depending on the purpose.

Gelatin is most preferably used as the binder used in the back layer. Examples of gelatin include lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin, gelatin derivatives and modified gelatin, and lime-processed gelatin and acid-processed gelatin are mainly preferably used. In addition, any of the other hydrophilic polymers commonly used in the art can be used.

It is important that the photosensitive material for printing has curl balance between the photosensitive layer side and the back layer side. for that reason,
Ratio of binder such as gelatin in the back layer and hydrophilic polymer such as gelatin in the photosensitive layer side (back layer / photosensitive layer side)
Is preferably 0.1 or more in terms of weight ratio, and practically designed to be 0.32 to 1.50. This ratio depends on the material and thickness of the photographic support of the silver halide photographic material, the total amount of hydrophilic polymers such as gelatin, the amount of silver or the amount of other additives (eg, polymer latex). It is determined by the design of the curl balance of the photosensitive material, the developing speed during the developing process, or the drying speed after the process.

The back layer has various functions as described above.

For example, for the image sharpness halation prevention and irradiation prevention functions of the silver halide photographic light-sensitive material, the corresponding antihalation dye and irradiation prevention dye described in the section of the dye of RD can be used. I can.

For the function of preventing sticking between the light-sensitive layer and the back layer of the silver halide photographic light-sensitive material, the matting agent and slipping agent of the RD can be appropriately used. Shape of matting agent,
The particle size is not limited, but the average particle size is 10 μm or more and 50 μm
The following spherical matting agents can also be used.

As the slip agent, in addition to the above RD, the following can be used as typical ones. For example, U.S. Pat. No. 3,042,522, British Patent No. 95
No. 5,061, U.S. Pat. Nos. 3,080,317, 4,004,927, 4,047,958, 3,489,576, and British Patent 1,143,118.
No. 2,454,043, US Pat.
32,305, 2,976,148, 3,20
No. 6,311, German Patent Nos. 1,284,295, 1,284,294, etc., higher fatty acid-based, alcohol-based, acid amide-based slip agents, and British Patent No. 1,263,7.
No. 22, metal soaps described in US Pat. No. 3,933,516, US Pat. Nos. 2,588,765 and 3,12.
1,060, Ester-based and ether-based lubricants described in British Patent 1,198,387, etc., and U.S. Pat. No. 3,5.
And taurine-based slip agents described in JP-A Nos. 02,437 and 3,042,222.

The antistatic function is achieved by providing at least one antistatic layer on the undercoat layer on the back layer surface side of the silver halide photographic light-sensitive material, but in the binder of the back layer or in the protective layer. It is also achieved by a layer mixed with an antistatic agent. As the antistatic agent, most of the antistatic agents conventionally used in the art can be used. For example, Japanese Patent Publication No. 47-28937 or 49-238.
No. 28 styrene-sodium maleate copolymer, JP-A No. 53-82876 sodium vinylbenzyl sulfonate copolymer and the like, JP-B-48-2345.
Anionic polymeric antistatic agents such as copolymers of sodium styrene sulfonate described in No. 1; JP-A-51-4253
No. 5, No. 54-159222, No. 55-7763, the ionene polymer (for example, polymer of triethylenediamine and xylidene dichloride), for example, polymethacroyl described in US Pat. No. 2,882,157. Ethyl diethyl methyl ammonium methyl sulfonate, JP-B-60-51693, JP-A-61-2237
No. 36 and No. 62-9346, cross-linked copolymer particles having a quaternary ammonium group in the side chain (for example, copolymer [N, N, N-trimethyl-N-vinylbenzylammonium chloride-co-divinylbenzene). ], Containing alumina sol as a main component described in JP-B-57-12979, Zn described in JP-A-57-104931
O, SnO ₂ , TiO ₂ , Al ₂ O ₃ , In ₂ O ₃ , Si
Fine particle metal oxides such as O ₂ , MgO, BaO, MoO ₃ and ZiO ₂ , metal oxide antistatic agents such as V ₂ O ₅ described in JP-B-55-5982, and higher fats described in JP-B-52-32572. Alcohol phosphate ester antistatic agent, JP-A-2-252726, JP-A-2-255770, 2-3
04-554, 2-308246, European Patent Application No. 0593111A1, edited by Naoya Ogata, “Conductive Polymer” (Kodansha, 1990), poly- (5-dodecylbenzothiophene), poly- (3,4). -Diethoxy-thiophene), poly (3,4-methoxypyrrole),
Examples include π-electron-type conductive polymers such as poly (paraphenylene vinylene) and methacryloylethyloxymethyl-3-polythiophene. As described above, the antistatic layer may contain a binder, and as the binder, gelatin, a gelatin derivative, cellulose diacetate, vinyl polymer latex, or the like can be used.

An antistatic layer is preferably provided on the back layer side of the printing light-sensitive material, and at least one layer is provided on any of the undercoat layer, the undercoat upper layer, the protective layer lower layer, or the protective layer upper layer. Good.

In the printing photosensitive material, the photosensitive layer has a low sensitivity in order to improve the shock of the worker due to static electricity, the difficulty of separating the film, the deterioration of the quality due to the adhesion of dust, etc. There is a demand for permanent antistatic properties that maintain antistatic performance. For that purpose, among the above, it is preferable to use an antistatic agent close to a semiconductor such as a fine particle metal oxide.

In addition, the back layer of the silver halide photographic light-sensitive material may contain a gelatin hardener as a binder, an ultraviolet absorber, a softener, a polymer latex and the like. As the hardener, those mentioned for the undercoat layer or those mentioned above can be used.

The method of applying the back layer of the silver halide photographic light-sensitive material of the present invention is not particularly limited, but it can be applied by the method described in the above-mentioned application of the undercoat liquid.

For development processing, refer to Journal of
The American Chemical Society (Journa
I of the American Chemica
l Society) 73, 3,100 (195
The known developer described in 1) can be used. The printing photosensitive material film is disclosed, for example, in JP-A-5-1.
Development can be carried out by the processing described in JP-A No. 23292 and JP-A No. 53-17719.

Here, a method for measuring the refractive index, (α _t ) and (α _h ) will be described.

<Refractive Index Measuring Method> Using an Abbe refractometer manufactured by Agota Co., Ltd., a polarizing plate was attached to an eyepiece lens, and the refractive index was measured by aligning the orientation of the polarizing plate and the orientation of the film with the measurement direction. . Α-Bromonaphthalene was used as an intermediate liquid. The refractive index of the photographic support in the longitudinal direction, the lateral direction, and the angle direction of 45 ° was measured at 5 points each, and the total average was taken to be the surface average refractive index.

Next, the (α _t ) and (α _h ) measuring methods will be described.

<Measurement Method of (α _t ) and (α _h )> (a) Humidity Expansion Coefficient (α _h ) A measurement sample is thermomechanical analyzer (TM).
A) It measured with ULVAC-TM7000 type (manufactured by Vacuum Riko Co., Ltd.). Cut the sample into 5 mm width x 25 mm length, hold 5 mm above and below the sample with a TMA clip, set the measured length to 15 mm, apply a load of 2 g, and change the humidity to 11 to 80% RH at 23 ° C. Changes were recorded continuously and (α _h ) was calculated from the slope.

(B) Temperature expansion coefficient (α _t ) Whether (α _t ) is measured by changing the temperature in the same manner as above, or
It was measured according to the description of ASTM D696-70. In the present invention, the latter is used.

Film-formed SPS-based photographic support and SPS-based photographic support obtained by finishing the silver halide photographic light-sensitive material and then removing the light-sensitive layer using a bleaching agent solution (Heater manufactured by Kao Corporation) And were measured for refractive index, (α _t ) and (α _h ), respectively, and it was confirmed whether or not there was a difference between the measured values. Since no difference was observed in the results, (α _t ) and (α _h ) were measured using the film-formed SPS-based photographic support.

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these.

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【Example】

[Preparation of SPS-based photographic support] <Preparation of SPS-based resin pellets> JP-A-3-13184
SPS resin pellets were produced according to No. 3. From the preparation of the catalyst to the polymerization reaction, all were carried out under a dry argon stream. Copper sulfate pentahydrate (CuSO ₄ .5H ₂ O) 17.8 g (71 mmol) purified benzene 200 ml and trimethylaluminum 24 in a glass container having an internal volume of 500 ml.
After adding ml, the mixture was stirred at 40 ° C. for 8 hours to adjust the catalyst. This was placed under an argon gas flow. After filtering through 3 glass filters, the filtrate was freeze-dried. Take this out, 2
It was put in a stainless steel container (1), 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. After that, the mixture was cooled to room temperature, 1 l of methylene chloride was added, and a methanol solution of sodium methylate was added with stirring to deactivate the catalyst. The contents were gradually dropped into 20 liters of methanol, and then No. It was filtered with a 3A glass filter, washed 3 times with 1 l of methanol, dried, and dried under reduced pressure at 150 ° C. for 12 hours to obtain an SPS resin. The weight average molecular weight of this polymer was 280, which was determined from the measurement results of GPC calibrated with standard polystyrene at 135 ° C. using 1,2,4-trichlorobenzene as a solvent.
It was 000. The melting point of this polymer was 245 ° C. It was confirmed by 13 C-NMR measurement that the obtained polymer had a syndiotactic structure. This SPS resin was introduced into an extruder at 300 ° C., extruded, and pelletized.

<Production of SPS-Based Photographic Support> The obtained SPS-based resin pellets were dried at 130 ° C. in a nitrogen atmosphere for 3 hours in a rotary vacuum dryer for crystallization. The crystallized SPS resin pellets are introduced into an extruder, melted at 330 ° C., melt-extruded from a T die at 40 ° C. into a sheet on a cooling drum, and the sheet is adhered onto the drum by an electrostatic loading method. It was rapidly cooled and solidified to prepare an unstretched sheet.
This unstretched sheet was uniaxially stretched at a ratio shown in Table 2 at 125 ° C. using a longitudinal stretching machine in which rolls were combined in the longitudinal direction, and subsequently, both ends of the uniaxially stretched film were held with clips at 128 ° C. in the transverse direction. Sequentially biaxially stretched at a stretch ratio shown in Table 2 below, further heat-set at a heat-setting temperature of 250 ° C. for 10 seconds, cooled, and then cooled to give 100 μm-thick SPS.
A system photographic support was obtained.

<Undercoating of SPS-based photographic support> Both surfaces of the obtained biaxially stretched SPS-based photographic support were continuously subjected to corona discharge under discharge condition 7 (W · min / m ² ). After the treatment, the ion blower (RH-20 type) is used to remove the charge on both surfaces with ionic wind, and the undercoating coating solutions a-1 and b-1 are dried on both sides with an air doctor type coating machine. To 1.0 μm and dried at 160 ° C. to obtain subbing layers A-1 and B-1.

Subsequently, the undercoating upper layer coating liquids a-2 and b-2 were similarly coated on the undercoating layer so that the dry film thickness was 0.2 μm, and dried at 140 ° C. to obtain the undercoating upper layer. A-2 and B-
And 2.

<< Undercoating Coating Solutions a-1 and b-1 >> Styrene-butadiene latex (Nippole LX432A, manufactured by Nippon Zeon Co., Ltd.) 25 parts by weight Methylcellulose (10%) 10.0 parts by weight Silica matting agent (average particle size 3. 0 μm) 0.5 parts by weight (C-1) 0.5 parts by weight Pure water 66 parts by weight << Undercoating upper layer coating liquids a-2 and b-2 >> Gelatin aqueous solution (10%) 80 parts by weight Methylcellulose (10%) 20 parts by weight C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ SO ₃ Na 4 parts by weight Proxel 0.3 parts by weight (C-1) 0.5 parts by weight Finish with pure water to 1 liter.

<Coating of Antistatic Layer> The undercoat layer surface (B-
2) was subjected to a corona discharge treatment of 8 W / m ² · min, and the following metal oxide complex antistatic coating liquid (b-3) was applied to the dried thickness of 0.1 μm, and at 160 ° C. It dried and formed the antistatic layer (B-3).

<< Preparation of Metal Oxide Complex Fine Particle Conductive Antistatic Agent >> 230 parts by weight of stannic chloride and 23 parts by weight of antimony trioxide were dissolved in 3000 parts by weight of ethanol to obtain a uniform solution. A 1N aqueous sodium hydroxide solution was added dropwise to this solution until the pH of the above solution reached 3, to obtain coprecipitation of colloidal stannic oxide and antimony oxide. The obtained coprecipitate was left at 50 ° C. for 24 hours to obtain a red-brown colloidal precipitate. The reddish brown colloidal precipitate was separated by centrifugation. Water was added to the precipitate to remove excess ions, and the precipitate was washed with water by centrifugation. This operation was repeated 3 times to remove excess ions. Colloidal precipitate 2 with excess ions removed
Disperse 00 parts by weight into 1500 parts by weight and spray into a baking furnace heated to 600 ° C. to obtain a bluish average particle size of 0.2 μm.
Fine powder of tin oxide-antimony oxide composite was obtained.
The specific resistance of this fine particle powder was 25 Ω · cm. PH of a mixed solution of 40 parts by weight of the fine particle powder and 60 parts by weight of water
After adjusting to 7.0 and roughly dispersing with a stirrer, a horizontal sand mill (trade name: Dynomill; WILLYA.BACHOFEN)
It was adjusted by dispersing with AG) until the residence time reached 30 minutes.

<< Antistatic Coating Liquid (b-3) >> The conductive fine particle dispersion liquid 10 parts by weight Gelatin 1 part by weight Water 10 parts by weight Methanol 62 parts by weight Polyoxyethylene nonylphenyl ether 0.01 parts by weight Hexamethylene-1 , 6-Bisethylene urea 0.6 part by weight <Preparation of comparative sample> Commercially available biaxially stretched and heat-set thickness 1
Both sides of a 00 μm PET film were subjected to a corona discharge treatment of 8 w / m ² · min.
1 is applied to a dry film thickness of 0.8 μm and dried to form an undercoat layer A-11, and the undercoating solution b-11 below is applied to the opposite surface to a dry film thickness of 0.8 μm. It was applied to and dried to obtain an undercoat layer B-11.

<< Undercoating Liquid a-11 >> Copolymer latex liquid of butyl acrylate (30% by weight) t-butyl acrylate (20% by weight) styrene (25% by weight) 2-hydroxyethyl acrylate (25% by weight) (Solid content 30%) 270 parts by weight (C-1) 0.6 parts by weight Hexamethylene-1,6-bis (ethyleneurea) 0.8 parts by weight Finish with water to 1 liter << Undercoating liquid b-11 >> Butyl acrylate (40% by weight) Styrene (20% by weight) Glycidyl acrylate (40% by weight) Copolymer latex liquid (solid content 30%) 270 parts by weight (C-1) 0.6 parts by weight Hexamethylene-1, 3,6-bis (ethyleneurea) subsequently finished into 1l 0.8 parts by weight water, on the surface of the undercoat layer a-11 and subbing layer ^{B-11, 8w / m 2} · min Corona discharge, subbing layer A-1
The undercoating upper layer coating solution a-21 below is used as the undercoating layer A-21 so that the dry film thickness is 0.1 μm, and the undercoating upper layer coating solution below is provided on the undercoating layer B-1. b-2 is an undercoat upper layer B having an antistatic function so that the dry film thickness becomes 0.8 μm.
It was applied as -21.

<< Undercoating Upper Layer Coating Liquid a-21 >> Gelatin 0.4 g / m ² Weight (C-1) 0.2 parts by weight (C-2) 0.2 parts by weight (C-3) 0. 1 part by weight Silica particles (average particle size 3 μm) 0.1 part by weight Finish with water to 1 liter <Undercoating upper layer coating liquid b-21> (C-4) 60 parts by weight Latex liquid containing (C-5) as a component (Solid content 20%) 80 parts by weight Ammonium sulfate 0.5 parts by weight (C-6) 12 parts by weight Polyethylene glycol (weight average molecular weight 600) 6 parts by weight Finish with water to 1 liter.

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8 W / m ² · on the undercoat layer surface (B-21)
Minute corona discharge treatment, and the thickness of the metal oxide complex antistatic coating liquid (b-3) after drying is 0.1 μm.
And was dried at 160 ° C. to form an antistatic layer (B-31).

[Preparation of silver halide photographic light-sensitive material having SPS-based photographic support and preparation of comparative sample] The following silver halide was prepared on A-2 and comparative sample A-21 of each SPS-based photographic support. A back layer coating solution and the like were coated on the emulsion coating solution and B-3 and B-31 to obtain a silver halide photographic light-sensitive material for printing.

<Preparation of Silver Halide Emulsion A> A silver chlorobromide core grain having an average thickness of 0.05 μm and an average diameter of 0.15 μm, which is composed of 70 mol% of silver chloride and the rest is silver bromide, is prepared by the simultaneous mixing method. did. K ₃ RhBr ₆ was added to silver 1 when core particles were mixed.
8 × 10 ⁻⁸ moles were added per mole and the core particles were shelled using the double-mix method. At that time, 3 × 10 ⁻⁷ mol of K ₂ IrCl ₆ was added per mol of silver. The obtained emulsion has a core of an average thickness of 0.10 μm and an average diameter of 0.29 μm /
The emulsion was a tabular grain emulsion of shell type monodisperse (variation coefficient of 10%) silver chloroiodobromide (90 mol% silver chloride, 0.2 mol% silver iodobromide, the rest being silver bromide). Then, JP-A-2-28
No. 0139, denatured gelatin (in which the amino group in gelatin is substituted with phenylcarbamyl, for example, Compound G-
Desalting was performed using 8). EAg after desalting is 190 at 50 ° C
It was mv.

4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the resulting emulsion in an amount of 1 × 10 ^-3 mol per mol of silver, and potassium bromide and citric acid were further added. PH of 5.6 and EAg of 123 mv, chloroauric acid was added in an amount of 2 × 10 ^-5 mol, and then inorganic sulfur was added in an amount of 3 × 10 ^-6 mol, and chemical aging was performed at a temperature of 60 ° C. until maximum sensitivity was obtained. . After aging, 4-hydroxy-6-
Methyl-1,3,3a, 7-tetrazaindene was added in an amount of 2 × 10 ^-3 mol per mol of silver, 1-phenyl-5-mercaptotetrazole in an amount of 3 × 10 ^-4 mol, and gelatin.

<Preparation of Silver Halide Emulsion B> 60 mol% of silver chloride, 2.5 mol% of silver iodide, the rest of which is silver bromide by the simultaneous mixing method. The average thickness is 0.05 μm and the average diameter is 0.1.
5 μm silver chlorobromide core particles were prepared. At the time of mixing the core particles, K ₃ RhBr ₆ was added in an amount of 2 × 10 ⁻⁸ mol per mol of silver, and the core particles were shelled by the simultaneous mixing method. At that time, 3 × 10 ⁻⁷ mol of K ₂ IrCl ₆ was added per mol of silver. The resulting emulsion had a core / shell type monodisperse (variation coefficient 1 with an average thickness of 0.10 μm and an average diameter of 0.42 μm).
0%) silver chloroiodobromide (90 mol% silver chloride, silver iodobromide 0.
The emulsion was tabular grains (5 mol%, balance silver bromide). Then, the modified gelatin described in JP-A-2-280139 (a gelatin in which an amino group is substituted with phenylcarbamyl, for example, JP-A-2-280139 28)
The salt was desalted using Exemplified Compound G-8) on page 7 (3). The EAg after desalting was 180 mv at 50 ° C.

4-Hydroxy-6-methyl-1,3,3a, 7-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. PH 5.6 and EAg123mv, and after adding 2 × 10 ⁻⁵ mol of chloroauric acid, N, N,
3'10 ^-5 mol of N'-trimethyl-N'-heptafluoroselenourea was added and chemical ripening was carried out at a temperature of 60 ° C until maximum sensitivity was obtained. After aging, 4-hydroxy-6-
Methyl-1,3,3a, 7-tetrazaindene was added in an amount of 2 × 10 ^-3 mol per mol of silver, 1-phenyl-5-mercaptotetrazole in an amount of 3 × 10 ^-4 mol, and gelatin.

<Preparation of silver halide photographic light-sensitive material for printing plate-making scanner for HeNe laser light source> On the undercoating upper layer A-2 of each SPS photographic support and Comparative Sample A-21, the following Formulation 1 was used. The gelatin layer was adjusted to 0.5 g / m ² , and the silver halide emulsion 1 of Formula ² was further added thereto so that the silver amount was 1.5 g / m ² and the gelatin amount was 0.5 g / m ^2. On top of that, a coating solution having the following formulation 3 was used as an intermediate protective layer so that the amount of gelatin would be 0.3 g / m ² , and a silver halide emulsion layer 2 having a formulation 4 was additionally provided thereon with a silver amount of 1.4 g / m ^2.
m ² and the amount of gelatin were 0.4 g / m ^2, and the coating of the following formulation 5 was simultaneously multilayered by an extruder type coating machine so that the amount of gelatin was 0.6 g / m ² . Further, a back layer having the following formulation 6 was formed on the opposite subbing upper layers B-3 and B-31 so that the amount of gelatin was 0.6 g / m ^2, and a polymer layer having the following formulation 7 was further added thereon. Further, a back layer protective layer having the following formulation 8 was prepared with a gelatin content of 0.
Simultaneous multi-layer coating of 4 g / m ² was carried out to obtain a silver halide photographic light-sensitive material sample for a HeNe laser light source and a plate-making scanner.

Formulation 1 (gelatin layer composition) Gelatin 0.5 g / m ² AD-1 solid dispersion fine particles (average particle size 0.1 μm) 25 g / m ² Sodium polystyrene sulfonate 10 mg / m ² Sodium-isoamyl-n- Decyl sulfosuccinate (S-1) 0.4 mg / m ² Formulation 2 (composition of silver halide emulsion layer 1) Silver halide emulsion A Solid dispersion of AD-8 so that the amount of silver is 1.5 / m ^2. Fine particles (average particle size 0.1 μm) 20 mg / m ² cyclodextrin 0.5 g / m ² sensitizing dye d-1 5 mg / m ² sensitizing dye d-2 5 mg / m ² H-7 20 mg / m ² RE- 1 20 mg / m ² compound e 100 mg / m ² latex polymer f 0.5 g / m ² hardener g 5 mg / m ² S-1 0.7 mg / m ² 2-mercapto-6-hydroxypurine 5 mg / m ² EDTA 30 mg / m ² colloidal silica (average particle size 0.05 μm) 10 mg / m ² formulation 3 (intermediate layer composition) gelatin 0.3 g / m ² S-1 2 mg / m ² formulation 4 (silver halide emulsion layer 2 composition) ) Silver halide emulsion B 1.4 g / m ² Sensitizing dye d-1 3 mg / m ² Sensitizing dye d-2 3 mg / m ² H-20 20 mg / m ² Na-3 40 mg / m ² RE-2 20 mg / m ² 2-mercapto-6-hydroxypurine 5 mg / m ² latex polymer f 0.5 g / m ² EDTA 20 mg / m ² S-1 0.5 mg / m ² Formulation 5 (emulsion protective layer composition) Gelatin 0.6 mg / m ² AD-5 solid dispersion fine particles (average particle size 0.1 μm) 40 mg / m ² S-1 12 mg / m ² monodispersed silica (average particle size 0.05 μm) 25 mg / m ² 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 K-1 30 mg / m ² Formulation 6 (back layer composition) Gelatin 0 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 formulation 7 (hydrophobic polymer layer composition) latex (methyl methacrylate: acrylic acid = 97: 3) 1.0 g / m ² hardener g 6 mg / m ² formulation 8 (back layer protective layer) gelatin 0.4 g / m ² single Dispersed polymethylmethacrylate (average particle size 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 K-1 20 mg / m ²

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[Chemical 12]

[Development Processing] <Development> << Developer formulation (g in 1 liter) >> Diethylenetriamine pentaacetic acid (40% aqueous solution) 3.63 g Sodium sulfite 16 g Potassium bromide 76 g Potassium carbonate 0.9 mol S-360 1g A-18 25g Dimezone S 1.5g 2-4 0.05 mol Benzotriazole 0.21g 1-Phenyl-5-mercaptotetrazole 0.025g pH 10.3 Add water and sodium hydroxide or sulfuric acid At the time of use, the pH was adjusted to a predetermined pH and the whole was adjusted to 500 ml. At the time of use, 500 ml of water was added to make a 1 l developer.

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<Fixing liquid composition> Ammonium thiosulfate (70% aqueous solution) 200 ml Sodium sulfite 22 g Boric acid 9.8 g Sodium acetate trihydrate 34 g Acetic acid (90% aqueous solution) 14.5 g Tartaric acid 3.0 g Aluminum sulfate (27% aqueous solution) ) 25 ml The pH of the working solution was 4.9.

Sulfuric acid was added to water to make 500 ml, and the pH was adjusted to 4.9 at the time of use. Incidentally, 500 ml of water was added at the time of use to prepare a fixing solution.

<< Composition of Rinse Solution >> EDTA.2Na 40 g Potassium hydroxide 23 g Potassium carbonate 12 g Potassium sulfite 110 g Sunbag-P (manufactured by San-ai Petroleum Co., Ltd.) 20 g << Processing conditions >> Development 35 ° C. 14 seconds Fixing 33 ° C. 9 seconds Rinse 33 ° C. 8 seconds Squeeze 2.5 seconds Drying 9.5 seconds Total 43 seconds [Evaluation method] <Evaluation of practical stability of dimensional stability of silver halide photographic light sensitive material> A sample is cut into a size of 30 cm × 61 cm, and 23 ° C.
Humidity was conditioned for 3 hours in a dark room where the atmosphere was set to 55% RH. Separately prepared negative and positive register marks (thin-line thin lines) are printed on two places at intervals of 60 cm, and the register original film is also conditioned under the same conditions as above, and then the glass surface of the printer of the halogen lamp light source. Place the manuscript film on the top with the emulsion side facing up, stack the sample with the emulsion side on top of it, spread it well with your palm, put another glass plate on it, and expose appropriately with a halogen lamp light source, The exposed sample was processed under the above-mentioned development conditions with a GX680 automatic developing machine manufactured by Konica Corporation. Humidify the developed sample under the same conditions as above, and after 2 hours, overlay the original film and the developed sample with each other on the emulsion side, and at the register mark, use a loupe with a scale to indicate how much the sample and the original are. Read Six kinds of samples were used for the measurement, and the average value was used as the measured value. Further, the same conditions as described above were applied even when the atmosphere conditions were 23 ° C. and 40% RH. In Table 2, any numerical value is displayed. If the deviation exceeds | 20 μm |
If it exceeds m, dimensional deviation will be noticed.

The above results are shown in Table 2.

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[Table 2]

[Results] As shown in Table 2, the SPS photographic support biaxially stretched at different magnifications has a smaller refractive index, a smaller humidity expansion coefficient and a smaller temperature expansion coefficient as the stretching magnification increases. Recognize. And the refractive index is 1.585
Below, both the coefficient of humidity expansion and the coefficient of temperature expansion,
1.0 × 10 ⁻⁶ / (% RH) or less, and 50, respectively
It can be seen that it becomes less than × 10 ^-6 / ° C and there is almost no deviation in the practical test of dimensional stability. Further, the coefficient of humidity expansion of the PET photographic support is about 20 to about that of the SPS photographic support.
It was as large as 40 times, and the deviation of the practical use of the silver halide photographic light-sensitive material using the PET photographic support was large, and the deviation was visually recognized.

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The silver halide photographic light-sensitive material having a syndiotactic polystyrene photographic support having a smaller coefficient of humidity and coefficient of thermal expansion obtained by improving film forming conditions such as stretching and heat setting. By using the material, a printed matter or the like having excellent dimensional stability can be obtained.

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Claims (2)

[Claims] 1. A biaxially stretched syndiotactic polystyrene photographic support having a temperature expansion coefficient of 50 × 10 ⁻⁶ / ° C. or less and a humidity expansion coefficient of 1.0 × 10 ⁻⁶ / (% RH) or less. A silver halide photographic light-sensitive material having a body. 2. A temperature expansion coefficient of 50 × 10 ⁻⁶ / ° C. or less and a humidity expansion coefficient of 1.0 × 10 ⁻⁶ / (% RH) or less,
A silver halide photographic light-sensitive material comprising a biaxially stretched syndiotactic polystyrene-based photographic support having a refractive index in the plane direction of 1.585 or less.