JPH08201968A - Photographic base and silver halide photographic material formed by using the same - Google Patents

Abstract

PURPOSE: To obtain a styrene based photographic base of a structure to lessen the occurrence of pinhole trouble when this base is used for silver halide photographic sensitive materials by forming the base of a syndiotactic structure specified in breaking elongation. CONSTITUTION: This styrene based photographic base (SPS base) has the syndiotactic structure having the breaking elongation of >=30 to >=120%. Further, a vinylidene chloride polymer which is a hardly elongatable blank is applied on at least one side of the SPS base in order to suppress the growth of the generated pinholes. The SPS base having such breaking elongation is attained by executing an elongating and film forming method consisting of (1) the compsn. of the base polymer, (2) a heat treatment of the base before longitudinal and transverse stretching, (3) summation during heat fixing. Namely, the easily elongatable molecular structure curved by the polymer compsn. of (1) is adopted. Further, the breaking elongation is increased by adequately suppressing the molecular orientation by the film forming methods of (2) and (3).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a styrene-based photographic support having a syndiotactic structure which causes less pinhole failure when used in a silver halide photographic material, and adhesion to an emulsion layer using the same. A silver halide photographic material having good properties.

[0002]

2. Description of the Related Art Generally, a silver halide photographic light-sensitive material (hereinafter abbreviated as a light-sensitive material or a light-sensitive material) has a drawback that its dimensions are likely to change when temperature and humidity, especially humidity changes. This dimensional change becomes a very serious problem especially in a halftone image for multicolor printing and a printing photosensitive material which requires reproduction of a precise line drawing. That is, when the original film is overprinted for multicolor printing, color misregistration occurs. Polyethylene terephthalate (hereinafter abbreviated as PET) that has been generally used in the past has been used as a method for improving such drawbacks.
JP-A-3-131843 discloses a method of changing to a support made of a styrene-based polymer having a syndiotactic structure which is more excellent in moisture absorption dimension stability. However, a photosensitive material using this support is mechanically peeled off from the photosensitive layer due to pinhole failure, that is, minute irregularities on the surface of a roller or the like during development, as compared with the PET photosensitive material used conventionally. There was a problem in that the unexposed portion (black portion) had fine holes and a failure was likely to occur. Such a failure is a serious problem in the photosensitive material for printing, which has a problem of delicate image reproducibility, and improvement has been desired.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a styrene-based photographic support having a syndiotactic structure which causes less pinhole failure when used in a silver halide photographic material, and the use thereof. Another object of the present invention is to provide a silver halide photographic material having good adhesion to the emulsion layer.

[0004]

These objects have been achieved by a styrene type photographic support having a syndiotactic structure having a breaking elongation of 30% or more and 120% or less. The method of achieving this will be described in detail below.
As a result of intensive studies on the cause of pinhole failure in a styrene-based photographic support having a syndiotactic structure (hereinafter abbreviated as SPS support),
It was found that the cause was as follows. Although the photosensitive material rubs against the minute protrusions of the roller in the developing machine to generate pinholes, the generated pinholes are larger than those of PET even if they are rubbed with the same size protrusions on the SPS support. Prone. This is because the SPS support is fragile against breakage, and the breakage easily spreads to the periphery just like when ice is crushed. This is because SPS has a small elongation at break and is easily broken even by a slight deformation.
Furthermore, the generated pinholes on the SPS support are large and easily grow. This is because the Young's modulus of SPS is smaller than that of PET that has been used conventionally, and the surface of the support on the outer side of the roll is easily stretched when the photosensitive material is bent, and the pinhole is likely to grow accordingly. . Therefore, in the present invention, in order not to generate a large pinhole, the breaking elongation is 30% or more and 120% or less, more preferably 35% or more and 100% or less, and further preferably 40% or more and 80%.
The feature is that it is less than or equal to%. Further, in order to suppress the growth of the generated pinhole, it is characterized in that a vinylidene chloride polymer, which is a hard and less stretchable material, is applied to at least one side of the SPS support.

The SPS support having such elongation at break is characterized by (1) composition of the support polymer, (2) heat treatment of the support before longitudinal and transverse stretching, and (3) relaxation during heat setting. It is achieved by carrying out the stretching film forming method of the present invention. That is, the polymer composition of (1) has a bent and easily stretchable molecular structure. Further, by the film forming methods (2) and (3), the molecular orientation is appropriately suppressed and the breaking elongation is increased. However, with such film formation, it is easy to cause a decrease in transparency due to spherulites during heat setting, but (1)
The polymer composition also has the effect of improving this. The details of these methods are described below. The composition of the support having the syndiotactic structure, which is the first feature of the present invention, will be described. The styrene-based polymer having a syndiotactic structure used in the present invention is a steric structure in which a phenyl group and its derivative which are side chains with respect to the main chain formed from carbon-carbon bonds are alternately located in opposite directions. The stereoregularity (tacticity) thereof is generally quantified by a nuclear magnetic resonance method ( ¹³ C-NMR method) using isotope carbon and is excellent in accuracy. This ¹³ C-NMR
The stereoregularity measured by the method is the existence ratio of a plurality of continuous constitutional units, for example, in the case of two diads, 3
The case of three can be indicated by a triad, and the case of five can be indicated by a pendad. The styrene-based polymer having a syndiotactic structure referred to in the present invention is usually a racemic dyad of 75% or more and 100% or less, preferably 85%.
% Or more and 100% or less, or 30% or more and 100% or less, preferably 50% or more with a racemic penta head,
It has a stereoregularity of 100% or less. Polystyrene having such a syndiotactic structure has extremely high stereoregularity, and tends to have a structure in which the main chain extends straight. As a result, the elongation after stretch film formation is small and the elongation at break tends to be small. Therefore, by adding a component other than styrene and disturbing the stereoregularity, the polymer molecule is easily bent, and as a result, a film having a large elongation after stretching, that is, a large breaking elongation is easily achieved. The content of styrene monomer is 50% by weight or more and 99.5% by weight or less, more preferably 80% by weight or more and 99% by weight or less, and further preferably
It is preferably 90% by weight or more and 98% by weight or less.
When the content of the styrene monomer is 99.5% by weight or more, the elongation at break becomes small, which is not preferable. On the other hand, if the content of components other than styrene is less than 50% by weight, the tensile elastic modulus becomes too low, which is not preferable in handling. The preferred tensile elastic modulus is 300 kg / mm ² or more and 600 kg / mm ² or less, more preferably 330 kg / mm ² or more and 550 k.
g / mm ² or less, more preferably 350 kg / mm ² or more and 500 kg / mm ² or less. Further, the above polymer composition also has an effect of preventing spherulites during film formation and suppressing a decrease in transparency. Since the SPS support has an extremely high crystallization rate, when an attempt is made to form a film having a small elongation at break as in the present invention, that is, a film having a loose molecular orientation, spherulites are likely to occur during the film forming process. On the other hand, the above polymer composition disturbs the regularity of the molecular arrangement and slows the crystallization rate, so that the generation of spherulites is suppressed and a highly transparent film is realized. Such an effect is particularly effective for a thick (90 μm or more) support such as a photographic support. This is because the thicker support is more likely to shrink after heat setting than the thin (less than 90 μm) support, and spherulites are likely to occur during this period.

The components other than styrene may be added to these styrene polymers having a syndiotactic structure in the form of copolymerization, or a polymer containing a component other than styrene may be mixed (polymer). Blending) may be performed, and these two methods may be used in combination. In the case of a copolymer, the comonomer components include poly (alkylstyrene), poly (halogenated styrene),
In addition to styrene-based monomers such as poly (halogenated alkyl styrene), poly (alkoxy styrene) and poly (vinyl benzoate), olefin monomers such as ethylene, propylene, butene, hexene and octene, and diene monomers such as butadiene and isoprene. , Cyclic olefin monomers, cyclic diene monomers, polar vinyl monomers such as methyl methacrylate, maleic anhydride, and acrylonitrile. Here, as poly (alkylstyrene), poly (methylstyrene), poly (ethylstyrene), poly (propylstyrene), poly (butylstyrene), poly (phenylstyrene), poly (vinylnaphthalene), poly (vinylstyrene) ), Poly (acenaphthine) and so on. Examples of poly (halogenated styrene) include poly (chlorostyrene), poly (bromostyrene), and poly (fluorostyrene). Examples of poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene). Of these, alkyl styrene is particularly preferable, and p-methyl styrene, m-methyl styrene,
P-tert-butylstyrene and the like are preferable, and among these, p-methylstyrene is particularly preferable.

When the polymers are blended, the styrene-based polymer having the syndiotactic structure and the styrene-based polymer having the atactic structure are preferable as the preferable polymer blending component from the viewpoint of compatibility. . Of these, particularly preferred is polystyrene having a syndiotactic structure as a main component, and p-methylstyrene, m-methylstyrene,
A homopolymer of p-tertiary-butylstyrene, p-chlorostyrene, m-chlorostyrene, p-fluorostyrene, hydrogenated polystyrene having a syndiotactic structure or atactic structure, and / or at least one of these monomers. It is preferable to blend a copolymer having a syndiotactic structure or an atactic structure consisting of one kind and styrene. Particularly preferred is a blend of p-methylstyrene having a syndiotactic structure or a copolymer of p-methylstyrene having a syndiotactic structure and styrene with polystyrene having a syndiotactic structure.

Among these, preferable polymer compositions are shown below. (Where syn is syndiotactic, atc
Indicates atactic. (1) Copolymer (copolymer) wt% P-1: syn-poly (styrene / p-methylstyrene) (95/5) P-2: 〃-poly (styrene / p-methylstyrene) (85 / 15) P-3: 〃-poly (styrene / p-chlorostyrene) (95/5) P-4: 〃-poly (styrene / p-chlorostyrene) (85/15) P-5: 〃-poly ( Styrene / hydrogenated styrene) (95/5) P-6: 〃-poly (styrene / hydrogenated styrene) (85/15) P-7: 〃-poly (styrene / hydrogenated styrene / p-methylstyrene) ( 95/5/5) (2) Polymer blend wt% P-8: snd-poly (styrene) + syn-poly (p-methylstyrene) (95/5) P-9: 〃-poly (styrene) + (85 / 15) P-10: 〃-poly (styrene) + syn-poly (p-chlorostyrene) (95/5) P-11: -Poly (styrene) + 〃 (85/15) P-12: 〃-Poly (styrene) + syn-Poly (hydrogenated styrene) (95/5) P-13: 〃 -Poly (styrene) + 〃 (85 / 15) P-14: 〃-poly (styrene) + atc-poly (styrene) (95/5) P-15: 〃-poly (styrene) + 〃 (85/15) P-16: 〃-poly (styrene) + Atc-poly (p-methylstyrene) (95/5) P-17: 〃-poly (styrene) + 〃 (85/15) P-18: 〃-poly (styrene) + atc-poly (hydrogenated styrene) ( 95/5) P-19: 〃-poly (styrene) + 〃 (85/15) P-20: 〃-poly (styrene) + atc-poly (styrene) + syn-poly (p-methylstyrene) (95 / 5/5) P-21: snd-poly (styrene) + syn-poly (p-methylstyrene + styrene copolymer (molar ratio = 10: 90)) (70/30) P-22: sn -Poly (styrene) + syn-poly (p-methylstyrene + styrene copolymer (molar ratio = 10: 90)) (50/50) P-23: snd-poly (styrene) + syn-poly (p-methyl) Styrene + styrene copolymer (molar ratio = 5: 95)) (70/30) P-24: snd-poly (styrene) + syn-poly (p-methylstyrene + styrene copolymer (molar ratio = 30) : 70)) (90/10)

The weight average molecular weight of these styrene-based polymers is preferably 100,000 or more and 800,000 or less, and particularly preferably 200,000 or more and 600,000 or less. Further, the molecular weight distribution is such that the weight average molecular weight (Mw) / number average molecular weight (Mn) is 1.5 or more and 5 or less, more preferably 2 or more and 4 or less. The styrene-based polymer having such a syndiotactic structure is obtained, for example, in an inert hydrocarbon solvent or in the absence of a solvent, using a titanium compound and a condensation product of water and a trialkylaluminum as a catalyst. It can be produced by polymerizing a monomer (a monomer corresponding to the styrene polymer). (JP-A-62-187708). Alternatively,
It can be produced by polymerizing with a compound comprising a titanium compound and a cation and an anion in which a plurality of groups are bound to an element as a catalyst. (JP-A-4-24950
4). Further, within a range not hindering the object of the present invention, silica, talc, titania, alumina, calcium carbonate, calcium oxide, inorganic fine particles such as calcium chloride and mixtures thereof, crosslinked polystyrene, organic fine particles such as crosslinked polymethylmethacrylate, And an antioxidant, an antistatic agent, a dye and the like can be added. Further, in the present invention, in order to prevent monomer precipitation during film formation, the residual styrene monomer content in the styrene polymer or its composition is preferably 7,000 ppm or less.

After drying and crystallizing these styrenic polymers, they are melted by heating, extruded, cooled and solidified to form an unstretched film. The extrusion molding machine used here may be either a uniaxial extrusion molding machine or a biaxial extrusion molding machine, and may have a vent or a vent. In addition, it is preferable to use a mesh filter in the extruder for pulverizing and removing secondary agglomerated particles or removing dust and foreign matters. The extrusion temperature is preferably selected within a temperature range of not lower than the melting point of the polymer to be used and not higher than the decomposition temperature + 50 ° C., and it is preferable to use a T-die or the like. After the extrusion molding, the obtained unstretched (raw sheet) is cooled and solidified. At this time, various refrigerants such as gas, liquid and metal roll can be used. When using a metal roll or the like, a method such as an air knife, an air chamber, a touch roll, or electrostatic application may be used. Of these, the electrostatic application method is preferably used from the viewpoint of flatness. The temperature for cooling and solidification is the glass transition temperature (Tg) -7 of the original sheet.
It is in the range of 0 ° C or higher and Tg or lower, and more preferably Tg-50 ° C or higher and Tg-20 ° C or lower.

Next, the cooled and solidified raw sheet is stretched. The second feature for realizing the support having the elongation at break of the present invention is the heat treatment of the support performed before stretching. In a photographic support that requires vertical and horizontal homogeneity, stretching is carried out by vertical and horizontal biaxial stretching, but it is possible to increase the breaking elongation by heat-treating the support before stretching. it can. That is, since the molecular mobility is sufficiently enhanced by this heat treatment and then the film is stretched, a film having a large entropy in which the orientation of the molecules is appropriately disturbed can be formed. This has a margin for the molecules to expand when subjected to tension, and the breaking elongation tends to increase. On the other hand, if the film is stretched without such heat treatment, the film is stretched from a state of low mobility, so that the film tends to be tense and have a small elongation at break. The heat treatment temperature is preferably Tg-20 ° C. or higher and Tg + 70 ° C. or lower, more preferably Tg-10 ° C. or higher and Tg + 50 ° C. or lower, further preferably Tg or higher and Tg + 30 ° C. or lower. It is preferable in order to obtain a support of a certain degree. Further, the heat treatment time is preferably 0.2 minutes or more and 5 minutes or less, more preferably 0.3 minutes or more and 4 minutes or less, and 0.
It is more preferably 5 minutes or longer and 3 minutes or shorter. If the temperature and the time are exceeded, the elongation at break exceeds the range of the present invention, and the elastic modulus is reduced accordingly, which is not preferable. On the other hand, below this temperature and time range, the elongation at break is below the range of the present invention, and pinhole failure is likely to occur.

After such heat treatment, longitudinal and transverse stretching are carried out. In order to obtain the support of the present invention, sequential biaxial stretching in which longitudinal and transverse stretching is carried out is most preferable. As a stretching method,
There are a tenter method, a method of stretching between rolls, a method of rolling, and the like, and these may be applied in combination, but the method using a tenter and the method of stretching between rolls are preferable. More specifically, it is more preferable to perform longitudinal stretching by roll-to-roll stretching and then transverse stretching with a tenter. On the other hand, if the stretching is performed three times or more, the breaking elongation tends to be remarkably small, and the range of the present invention is likely to fall. In particular, after stretching the longitudinal and transverse area stretching ratio to 8 times or more,
When it is re-stretched, the elongation at break tends to be as small as 20% or less, which is not preferable. The stretching speed is 3000 to 100 in both length and width.
50000% / min, preferably 4000-40000%
/ Min, more preferably 5000-30000% / min. Generally, in order to increase the breaking elongation, it is necessary to reduce the stretching speed, but this lowers the productivity.
However, in the present invention, by performing the support composition as described above and the heat treatment before stretching, a large breaking elongation is achieved even when stretching is performed at a relatively high speed, and there is also a feature that high productivity can be maintained. are doing. Stretching temperature is Tg or higher, Tg +
60 ° C or lower, more preferably Tg + 10 ° C or higher, Tg +
50 ° C. or lower, more preferably Tg + 20 ° C. or higher, Tg
+ 40 ° C. or less is preferable, and the draw ratio is 2.5 in both length and width.
2 times or more and 4 times or less, more preferably 2.8 times or more and 3.8
It is less than or equal to double, and more preferably, more than or equal to 3 and less than or equal to 3.6.

The stretched film thus obtained is heat-set. The third feature of the present invention is to perform heat fixation while relaxing under a specific condition, that is, a specific range. The heat setting temperature is melting temperature (Tm) -50 ° C or higher, Tm + 20
℃ or less, more preferably Tm-40 ℃ or more, Tm + 10
C. or lower, more preferably Tm−30 ° C. or higher and Tm or lower. At this time, it is characterized by heat-fixing while relaxing. The preferred amount of relaxation is 0.1% or more, 15
% Or less, more preferably 1% or more and 13% or less, still more preferably 2% or more and 10% or less. Relaxation in this range can relax the molecular orientation and achieve the breaking elongation of the present invention. At this time, the polymer having the above composition is further added.
Is more effective. If the relaxation amount is increased in order to increase the breaking elongation, spherulites are generated during heat setting, and the transparency is likely to decrease. However, the above-mentioned polymer having the composition of the present invention has an effect of suppressing the generation of spherulites and has a characteristic that transparency is not easily impaired even if the relaxation amount is increased. As described above, the present invention is characterized by having a large elongation at break without impairing transparency. The heat setting time is preferably 10 seconds or more and 100 seconds or less, more preferably 15 seconds or more and 80 seconds or less, and further preferably 20.
It is at least 60 seconds but not more than 2 seconds If it is less than this range, the elongation at break is insufficient, and if it exceeds this range, coloring of the film occurs, which is not preferable. The thickness of the support of the present invention thus obtained is preferably 90 μm or more and 300 μm or less, more preferably 95 μm or more and 250 μm or less, and further preferably 100 μm or more and 200 μm or less. Below this range, the mechanical strength is insufficient and handling problems tend to occur. On the other hand, there is no need to increase the mechanical strength by making it thicker than this.

Further, in the present invention, the surface hardness is increased by undercoating the SPS support with a vinylidene chloride resin.
It is characterized by suppressing the growth of minute scratches during bending. When the film is bent, tensile stress acts on the outer surface, but since the SPS support has a smaller Young's modulus than PET, it is more easily stretched. Therefore, pinholes generated during development tend to grow large. On the other hand, it is effective to coat a material having a high Young's modulus on the surface, and the remarkable one is a vinylidene chloride polymer. The vinylidene chloride polymer (PVd used in the present invention
C) means vinylidene chloride monomer (Vd
The content of C) is 20 wt% or more and 100% wt or less, more preferably 25 wt% or 100 wt% or less, and further preferably 3
It means 0 wt% or less than 100 wt%. If the content is less than this range, the hardness of the coating film is lowered and the generation of pinholes cannot be suppressed. Vinylidene chloride and a preferable copolymerization monomer include vinyl chloride (VC), acrylonitrile (AN),
Acrylic acid (Aa) and its ester (for example, methyl ester (MA), ethyl ester (EA), isopropyl ester (iPA)), methacrylic acid (Ma) and its ester (for example, methyl ester (MMA), ethyl ester (EMA)) , Isopropyl ester (iPM
A)), styrene (ST), maleic acid diester, itaconic acid diester, acrylamide, methacrylamide, and the like. These polymers have a weight average molecular weight of 3,000 or more and 300,000 or less, more preferably 5,000 or more and 200,000 or less, and still more preferably 6,000 or more and 100,000 or less.

Specific examples of the compound include the following copolymers, but the invention is not limited thereto. (Figures copolymer composition exhibits a molar ratio) PVdC-1 - (VdC) 90 - (MMA) 8 - (AN) 1 - (Ma) 1 - PVdC-2 - (VdC) 50 - (MMA) 30 - _{(AN) 10 - (Ma)} 10 - PVdC-3 - (VdC) 30 - (MMA) 50 - (AN) 10 - (Ma) 10 - PVdC-4 - (VdC) 90 - (MMA) 8 - (AN _{) 1 - (Aa) 1 -} PVdC-5 - (VdC) 50 - (MMA) 30 - (AN) 10 - (Aa) 10 - PVdC-6 - (VdC) 30 - (MMA) 50 - (AN) 10 _{- (Aa) 10 - PVdC-} 7 - (VdC) 90 - (MA) 8 - (AN) 1 - (Ma) 1 - PVdC-8 - (VdC) 50 - (MA) 30 - (AN) 10 - ( _{Ma) 10 - PVdC-9 -} (VdC) 30 - (MA) 50 - (AN) 10 - (Ma) 10 - PVdC-10 - (VdC) 90 - (MMA) 9 - (AN) 1 - PVdC-11 _{- (VdC) 50 - (MMA} ) 40 - _{AN) 10 - PVdC-12 -} (VdC) 30 - (MMA) 60 - (AN) 10 - PVdC-13 - (VdC) 90 - (MMA) 1 - (Ma) 9 - PVdC-14 - (VdC) 50 _{- (MMA) 10 - (Ma} ) 40 - PVdC-15 - (VdC) 30 - (MMA) 20 - (Ma) 50 - PVdC-16 - (VdC) 90 - (MMA) 10 - PVdC-17 - (VdC _{) 50 - (MMA) 50 -} PVdC-18 - (VdC) 30 - (MMA) 70 - PVdC-19 - (VdC) 90 - (VC) 5 - (MMA) 5 - PVdC-20 - (VdC) 50 - _{(VC) 25 - (MMA)} 25 - PVdC-21 - (VdC) 30 - (VC) 35 - (MMA) 35 - these vinylidene chloride-based copolymer can be synthesized by the method of emulsion polymerization, specifically JP-A-61-1086
50, 62-256871, JP-A-3-1413.
46, U.S. Pat. Nos. 4,350,622 and 4,40
It can be synthesized according to the method described in 1,788, 4,446,273 and the like.

The coating of these vinylidene chloride polymers can be carried out by a generally well known method.
For example, dip coat method, air knife coat method, car
A ten coat method, a roller coat method, a wire bar coat method, a gravure coat method and the like can be used. The coating of such vinylidene chloride polymer is (a) SPS
It may be carried out after stretching and heat-setting the support, or (b) it may be carried out on an unstretched or uniaxially stretched film during the film-forming process, and then further uniaxially stretched and heat-set or heat-set. Fixation may be performed. Such coating may be carried out with a vinylidene chloride-based polymer alone, and a hydrophilic colloid typified by gelatin, a cross-linking agent, a cationic / anionic / nonionic surfactant, an antistatic agent, organic / inorganic fine particles may be applied. It is also preferable to add the like. These coatings may be performed on one side or both sides of the SPS support, but when coating on one side, it is necessary to coat at least on the photosensitive layer side. The preferred coating thickness of the vinylidene chloride layer after drying is 0.01 μm or more and 10 μm or less,
The thickness is more preferably 0.05 μm or more and 5 μm or less, still more preferably 0.1 μm or more and 3 μm or less. If it is less than this range, the effect of suppressing the generation of pinholes is small, and if it exceeds this range, cracks are likely to occur in the coating layer when bent, which is not preferable.

When coating these vinylidene chlorides,
There is a problem that it is difficult to obtain close contact between the vinylidene chloride layer and the SPS support. This problem occurs in any of the above methods (a) and (b), but is particularly remarkable in the method (a). This is because the SPS support has high crystallinity and strong chemical resistance, so that the surface thereof is difficult to mix with the undercoating liquid, and as a result, it is difficult to obtain adhesion. For this reason, it is preferable to perform surface treatment before coating. Preferred surface treatments include glow discharge treatment, corona discharge treatment, ultraviolet treatment, flame treatment and the like. This will be described below.

The glow treatment is a conventionally known method, for example, Japanese Patent Publication Nos. 35-7578 and 36-10336.
45-22004, 45-22005, 45
-24040, 46-43480, JP-A-53-
129262, U.S. Pat. Nos. 3,057,792, 3,057,795, 3,179,482, 3,288,638, 3,309,299, 3,424,735. Nos. 3,462,335, 3,475,307, 3,761,299, 4,072,769, British Patents 891,469, 997,093, etc. are used. be able to. With such a glow treatment, the most excellent adhesion effect can be obtained especially when water vapor is introduced into the atmosphere. Further, this method is also very effective for suppressing yellowing of the support and preventing blocking. The steam partial pressure when performing the glow treatment in the presence of steam is preferably 10% or more and 100% or less, and more preferably 40% or more and 90% or less. If it is less than 10%, it becomes difficult to obtain sufficient adhesiveness. The gas other than water vapor is air composed of oxygen, nitrogen and the like.

Further, it is effective to perform vacuum glow treatment in a state where the support to be surface-treated is heated, since the adhesive property is improved in a shorter time than the treatment at room temperature. The preheating temperature is preferably 50 ° C or higher and Tg or lower, more preferably 60 ° C or higher and T
g or less is more preferable, and 70 ° C. or more and Tg or less is further preferable. Preheating at a temperature of Tg or higher deteriorates adhesion. Vacuum degree during glow processing is 0.005 to 20 Torr
Is preferred. More preferably 0.02 to 2To
rr. Further, the voltage is preferably between 500 and 5000V. More preferably, it is 500-3000V.
The discharge frequency used is, as seen in the prior art, from direct current to several 1000 MHz, preferably 50 Hz to 20 MH.
z, and more preferably 1 KHz to 1 MHz. Discharge intensity is 0.01 KV · A · min / m ^{2 to 5} KV · A ·
Min / m ² is preferable, more preferably 0.15 KV · A ·
The desired adhesive performance can be obtained at min / m ^{2 to 1} KV · A · min / m ² . In this way, the support subjected to the glow treatment is
It is preferable to immediately use a cooling roll to lower the temperature.

Corona treatment is the most well-known method, and any of the conventionally known methods, for example, Japanese Patent Publication No. 48-
5043, 47-51905, and JP-A-47-28.
067, 49-83767, 51-41770.
No. 51-131576 and the like. Discharge frequency is 50Hz-500
0 kHz, preferably 5 kHz to several 100 kHz is suitable. The processing strength of the object is 0.001K
V · A · min / m ^{2 to 5} KV · A · min / m ² , preferably 0.
01 KV · A · min / m ^{2 to 1} KV · A · min / m ² is suitable. The gap clearance between the electrode and the dielectric roll is 0.
5 to 2.5 mm, preferably 1.0 to 2.0 mm is suitable.

The ultraviolet treatment is carried out according to JP-B-43-2603,
It is preferable that the treatment is performed according to the processing methods described in JP-B-43-2604 and JP-B-45-3828. The mercury lamp is a high-pressure mercury lamp or a low-pressure mercury lamp composed of a quartz tube, and it is preferable that the wavelength of ultraviolet rays is 180 to 380 nm. Regarding the method of ultraviolet irradiation, the irradiation light amount is 20 to 10000 (m in the case of a high-pressure mercury lamp having a main wavelength of 365 nm.
J / cm ² ) is preferable, and more preferably 50 to 2000 (m
J / cm ² ). In the case of a low-pressure mercury lamp having a main wavelength of 254 nm, the irradiation light amount is 100 to 10,000 (mJ
/ Cm ² ) is good, and more preferably 200-1500 (m
J / cm ² ).

The flame treatment method may be either natural gas or liquefied propane gas, but the mixing ratio with air is important. In the case of propane gas, a preferable mixing ratio of propane gas / air is 1/14 or more and 1/22 or less in volume ratio,
It is preferably 1/16 or more and 1/19 or less. Also,
In the case of natural gas, it is 1/6 or more and 1/10 or less, preferably 1/7 or more and 1/9 or less. Flame treatment is 1Kc
Al / m ² or more and 50 Kcal / m ² or less, more preferably 3 Kcal / m ² or less and 30 Kcal / m ² or less. It is more effective if the distance between the tip of the internal flame of the burner and the support is less than 4 cm. A frame processing device manufactured by Kasuga Electric Co., Ltd. can be used as the processing device. Further, the backup roll that supports the support during the flame treatment is a hollow roll, and it is preferable that the backup roll is water-cooled by cooling water and always treated at a constant temperature.

Further, in the case of the above-mentioned coating method (b) of vinylidene chloride, that is, a method of stretching after coating, heat-setting or heat-setting, local poor adhesion tends to occur. Against this, it is effective to perform relaxation during heat setting. Heat shrinkage stress is generated in the support during heat setting, but the SPS support has a large shrinkage amount, and this stress tends to be large. For this reason, if heat fixing is performed without relaxation, a large residual stress is likely to be generated locally, which is also accumulated between the support and the vinylidene chloride layer and causes a decrease in adhesion. On the other hand, if relaxation is performed during heat setting, the heat shrinkage stress becomes weak and is dispersed at the same time, and local concentration of residual stress can be suppressed. As a result, local reduction in adhesion can be suppressed. The preferred amount of relaxation is 0.1% or more and 15% or less, more preferably 1% or more and 13% or less, and further preferably 2% or more and 10% or less. Further, the temperature for heat setting is a melting temperature (Tm) of -50 ° C or higher and Tm + 20 ° C or lower, more preferably Tm-40 ° C or higher and Tm + 10 ° C or lower, and still more preferably Tm-30 ° C or higher and Tm or lower.

An undercoat layer may be provided on the support coated with such a vinylidene chloride layer before coating the photosensitive layer and / or the back layer. The preferred undercoat layer is mainly composed of gelatin, and any of those commonly used in the art such as so-called lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin, gelatin derivatives and modified gelatin can be used. . Coating of such a gelatin layer can be carried out by a generally well known method in which a gelatin layer is dissolved in water, a polar organic solvent (for example, methanol, ethanol, etc.) or a mixture thereof. For example, a dip coat method, an air-knife coat method, a carten coat method, a roller coat method, a wire bar coat method, a gravure coat method and the like can be used. The undercoat layer may be applied by the method (a) described above, that is, when a vinylidene chloride layer is applied after biaxial stretching and heat setting, a gelatin layer may be applied subsequently after applying this layer, After once coating and drying, a gelatin layer may be coated again. Also, in the case of the above-mentioned method (b), that is, when stretching and heat setting or heat setting after applying the vinylidene chloride polymer, the gelatin layer is continuously applied after applying the vinylidene chloride polymer. Two layers may be stretched and heat set together,
The same effect can be obtained by coating a vinylidene chloride-based polymer, stretching, heat-setting and then coating a gelatin layer.

Further, a back layer may be provided for the purpose of imparting scratch resistance, slipping property, curl compensation and antistatic ability to the back surface. The back layer may use a hydrophilic colloid as a binder and a hydrophobic polymer as a binder. The most preferable hydrophilic colloid is gelatin. As gelatin, so-called lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin, gelatin derivatives, modified gelatin, and the like commonly used in the art can be used. Among these gelatins, lime-processed gelatin and acid-processed gelatin are most preferably used. As hydrophilic colloids other than gelatin, colloidal albumin, proteins such as casein, agar, sodium alginate, sugar derivatives such as starch derivatives, cellulose compounds such as carboxymethyl cellulose and hydroxymethyl cellulose, polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylamide. Examples thereof include synthetic hydrophilic compounds and the like. In the case of a synthetic hydrophilic compound, other components may be copolymerized. These hydrophilic colloids may be used alone or in combination of two or more. When these hydrophilic polymers are used, it is also preferable to apply the same undercoat as the photosensitive layer and then apply the back layer in order to impart stronger adhesion.

As the binder for the hydrophobic polymer layer, a (meth) acrylic acid ester polymer such as polymethyl methacrylate or ethyl acrylate, an olefin polymer such as polyethylene, a styrene polymer, vinylidene chloride, a urethane polymer or a rubber system such as butadiene is used. A polymer or the like is used. This layer may be one layer or two or more layers. If necessary, a matting agent, a slip agent, a charge control agent, a surfactant, a cross-linking agent, or a conductive substance for reducing the surface resistivity described below may be added to these layers.
Such a back layer may be a single layer or multiple layers, and the thickness of each layer is preferably 0.02 μm or more and 10 μm or less, more preferably 0.1 μm or more and 7 μm or less, and the total thickness of these layers is 0. The thickness is preferably 1 μm or more and 10 μm or less, more preferably 0.5 μm or more and 5 μm or less.

A polymer latex may be further added to the back layer. The polymer latex used in the present invention is an aqueous dispersion of a water-insoluble polymer having an average particle size of 20 mμ or more and 200 mμ or less. Particularly preferably, it is 0.1 or more and 0.8 or less. Preferable examples of the polymer latex used in the present invention have acrylic acid alkyl ester, hydroxyalkyl ester or glycidyl ester, or methacrylic acid alkyl ester, hydroxyalkyl ester or glycidyl ester as a monomer unit and have an average molecular weight of 10 It is a polymer of 10,000 or more, particularly preferably 300,000 or more and 500,000 or less, and a specific example is represented by the following formula.

[0028]

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On the thus prepared undercoat layer, a silver halide photosensitive layer and a protective layer are applied. The silver halide emulsion of the silver halide photographic light-sensitive material used in the present invention is usually a water-soluble silver salt (eg silver nitrate) solution and a water-soluble halogen salt (eg potassium bromide) solution and a water-soluble polymer solution such as gelatin. Made by mixing in the presence of. As the silver halide, any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used, and the grain form and size distribution are not particularly limited. The silver halide emulsion layer comprises a film physical property improver such as a photosensitive silver halide, a chemical sensitizer, a spectral sensitizer, an antifoggant, a hydrophilic colloid (especially gelatin), a gelatin hardener, and a surfactant. It may contain a thickener and the like. About these, Research Disclosure, Vol. 176, Item 17643 (19
Dec. 1978), and JP-A-52-108130.
No. 52-114328, No. 52-121321
Nos. 53-3217 and 53-44025 can be referred to. These silver halides are preferably dispersed in the hydrophilic colloid layer. The same hydrophilic colloid as that used as the binder of the back layer can be used.

Since the photosensitive layer composed of such a hydrophilic colloid layer is dissolved in the developing solution as it is, it is generally performed by adding a crosslinking agent to prevent elution. When a support made of a syndiotactic polymer is used as in the present invention, it is difficult to secure close contact between the support and the photosensitive layer due to its high chemical resistance as described above. In particular, it becomes difficult to obtain a wet state, that is, a close contact in the developing solution. Such poor adhesion when wet is particularly noticeable with a vinylidene chloride undercoat. This is because vinylidene chloride is hard and has a small elongation when wet, whereas a hydrophilic colloid typified by gelatin easily swells when wet, resulting in a large dimensional change between the two. As a result, the adhesion tends to deteriorate when wet. In the present invention, in order to prevent this, the swelling rate of the entire film on the photosensitive layer side is preferably 150% or more and 400% or less.
% Or less, more preferably 180% or more and 350% or less,
More preferably, it is characterized by being 200% or more and 300% or less. The swelling ratio here means the total thickness on the photosensitive layer side after being immersed in pure water at 40 ° C. for 3 minutes at 25 ° C., 6
Divide by the total thickness of the photosensitive layer when the humidity is controlled under 0% RH, and divide by 1
It is a value multiplied by 00. When the swelling rate is less than this range, the developer is not sufficiently taken into the photosensitive layer and the developing density tends to be lowered. On the other hand, if it exceeds this range, the amount of swelling becomes too large, and poor adhesion tends to occur. Achieving such a swelling ratio is achieved by controlling the addition amount of the crosslinking agent. In the case of a bifunctional crosslinking agent, the preferable addition amount of the crosslinking agent is preferably 3 m with respect to 100 g of the hydrophilic colloid.
mol or more and 40 mmol or less, more preferably 5 mm
ol or more and 30 mmol or less, more preferably 8 mm
It is ol or more and 25 mmol or less. When using a trifunctional or higher functional cross-linking agent, the addition amount of these (functional group / 2)
Add only the value divided by. Examples of preferable crosslinking agents include 1,1′-bis (vinylsulfonyl) methane, 2,
4-dichloro-6-hydroxy-1,3,5 triazine sodium salt, 1,3-divinylsulfonyl-2-propanol, 1,2-bis (vinylsulfonylacetamide) ethane, glutaraldehyde, 1,2-bis −
Examples thereof include (2 ′, 3′-epoxy-propoxy) ethane and the following compounds, but are not limited thereto.

[0031]

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Such a hydrophilic colloid layer may be a single layer or multiple layers, and the thickness of each layer is preferably 0.02 to 10 μm, more preferably 0.1 to 7 μm, and the total thickness of these layers is 1. 0.5-10 micrometers is preferable. If necessary, an antistatic agent may be added to the back layer and / or the photosensitive layer to reduce the surface resistivity to 10 ¹² or less. There is no particular limitation on the means for lowering the surface resistivity. For example, JP-A-58-62648 and 58-626.
No. 49, No. 51-115291, etc., a method of adding fine powder of oxides of Sn, Zn, Ti, In, V, etc., JP-A Nos. 57-204540 and 54-54.
A method of adding a polymer disclosed in JP-A-133324, JP-A-64-26849 and JP-A-61-24.
There is a method of adding a surfactant disclosed in Japanese Patent No. 907, etc. Preferred of these methods is S
This is a method of adding a metal oxide such as nO ₂ .

Conductive crystals as fine powder of metal oxide
Oxides or complex oxides thereof are preferred. Conductive crystal
Volume resistance as fine particles of water-soluble oxide or its composite oxide
Rate is 10 ⁷Ωcm or less, more preferably 10^FiveΩ cm or less
Things are desirable. The particle size is 0.01 to 0.
7 μm, especially 0.02 to 0.5 μm is desirable.
Yes. Is a conductive crystalline metal oxide used in the present invention.
For a method for producing fine particles of a composite oxide, see Japanese Patent Laid-Open No.
It is described in detail in the official gazette of 6-143430. First
1 is made of metal oxide fine particles by oxidization to improve conductivity.
The method of heat treatment in the presence of the heteroatom to be added, secondly baking
To improve conductivity when producing metal oxide fine particles
Third method for coexistence of heteroatoms to achieve the above
When producing fine metal particles, lower the oxygen concentration in the atmosphere.
In addition, a method of introducing oxygen defects is easy. Raw metal
As an example including a child, Al, In, etc. for Ti, Zn, Ti
O₂For Nb, Ta, etc., SnO₂For S
Examples thereof include b, Nb and halogen elements. Heteroatom addition
The addition amount is preferably in the range of 0.01 to 30 mol%, but is preferably 0.
It is particularly preferably 1 to 10 mol%. Out of these
SnO with Sb added₂Fine particles are most preferred.

A dyed non-photosensitive hydrophilic colloid layer (hereinafter referred to as a dyed layer) may be provided for the purpose of preventing halation, improving safety of safelight, improving front / back discrimination. These are described in detail in the following patents, US Pat. Nos. 3,455,693 and 2,548,564.
No. 4,124,386, 3,625,694
JP-A-47-13935 and JP-A-55-33172.
No. 56, No. 56-64414, No. 57-161853,
52-29727, 61-198148, 6
1-177447, 61-217039, 61
No. 219,039, etc., a method of adsorbing a dye to a mordant, JP-A-61-213839, 63-2088.
46, 63-296039, Japanese Patent Laid-Open No. 1-1584.
No. 39, etc., a method using a diffusion resistant dye, JP-A-3-
A method of emulsifying and dispersing a dye dissolved in oil as described in No. 109535 in the form of oil droplets, US Pat. Nos. 2,719,088, 2,498,841, 2,496,843, and JP-A-60-45237. And a method of adsorbing a dye described in JP-A-3-5748 on the surface of an inorganic material, JP-A-2-29
A method of adsorbing a dye described in No. 8939 on a polymer,
JP-A-56-12639, JP-A-55-155350,
55-155351, 63-27838, 6
3-197943, European Patent No. 15,601, 2
74,723, 276,566, 299,43
5, World Patent (WO) 88/04794, JP-A-2
There is a method using a water-insoluble dye solid described in -264936 and the like. Among these methods, the method in which the dye is dispersed as a solid is preferable from the viewpoint of fixing the dye in the specific layer and reducing the residual color after the development processing.

Finally, the measuring method used in the present invention will be described. (1) Breaking elongation The sample was cut into a width of 10 mm, and the chuck distance was 100 mm.
Set the tensile tester in mm. This is 25 ℃, 6
Tensile at 10 mm / min under 0% RH, and the elongation at break is determined. The measurement was performed 5 times in each of the vertical direction and the horizontal direction, and the average value thereof was used. (2) Swelling rate The humidity of the photosensitive material is adjusted at 25 ° C. and 60% RH, and the total thickness of the photosensitive layer side is measured from the cross section using an optical microscope. (This is designated as L1) Further, this photosensitive material was immersed in pure water at 40 ° C. for 3 minutes, and then the total thickness on the photosensitive layer side was measured in the same manner. The swelling rate (let this be L2) is given by the following equation. Swelling rate (%) = (L2 / L1) X100 (3) Glass transition temperature (Tg), crystallization temperature (Tc),
Melting temperature (Tm) The melting temperature (Tm) was obtained as follows using a scanning differential thermal analyzer (DSC). Set 5 mg of sample in DSC and in a nitrogen stream at 20 ° C.
The temperature is raised to 330 ° C./min and then rapidly cooled to room temperature. The temperature is raised again in a nitrogen stream at 20 ° C./min, and the midpoint between the temperature at which the baseline starts to shift and the temperature at which a new baseline is formed is Tg. The temperature at the maximum exothermic point of a large peak exceeding Tg and appearing on the exothermic side is Tc. Let Tm be the temperature at the maximum endothermic point of a large peak exceeding Tc and appearing on the endothermic side.

[0036]

The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. Example 1 (1) Polymerization of Polymer To a reaction vessel, 6 liters of toluene as a reaction solvent, 5 mmol of tetraethoxy titanium and 500 mmol of aluminum atom as methylaluminoxane were charged,
Styrene 48.94: p-methylstyrene 1.06 was added at a molar ratio of 50 ° C., and a polymerization reaction was performed for 2 hours. After completion of the reaction, the product was washed with a mixed solution of hydrochloric acid and methanol to decompose and remove the catalyst component. Then, it was dried to obtain 640 g of a copolymer. The weight average molecular weight (Mw) of this copolymer was 440,000, and the number average molecular weight (Mn) was 240,000. The content ratio of the p-methylstyrene unit in this copolymer was 5 wt%. Also,
This copolymer was analyzed by ¹³ C-NMR to give 145.
11 ppm, 145.22 ppm, 142.09 ppm
Was observed, and the syndiotacticity of the styrene unit in the racemic pentad calculated from the peak area was 72%. The copolymer thus obtained was used in levels 1, 6-24. Similarly, styrene and p-
Level 2 in Table 1 by changing the charging ratio of methylstyrene
Polymerization of the copolymers of ~ 5 was performed. Mw of levels 1 to 5 is 400,000, 420,000, 410,000, 400,000, 430,000, Mn, respectively.
Are 220,000, 230,000, 220,000, 220,000, 240,000,
Syndiotacticity is 74, 71 and 7 respectively.
It was 2, 73, 75. Further, a copolymer having a p-methylstyrene content of 10 wt% prepared by the above-mentioned method and a styrene homopolymer having a level of 5 were kneaded and extruded at a weight ratio of 1: 1 to obtain a level of 25
A polymer blend (mixture) of was obtained.

(2) Film formation of support and coating of vinylidene chloride layer These pelletized polymers were dried at 150 ° C. for 5 hours under reduced pressure. The content of monomers in the pellet was 1,100 to 900 ppm. After that, extrusion was performed using a vented single-screw extruder at a temperature 30 ° C. higher than the melting temperature (Tm). At this time, the residence time of the polymer in the extrusion screw was 15 minutes in each case. After passing these through a sintered metal filter, Tm + 3
Extruded from a T-die heated to 0 ° C. This molten sheet is extruded onto the cooling drum using the electrostatic application method,
An unstretched sheet was obtained. This thickness is 1 after biaxial stretching and heat setting
It was prepared to have a size of 00 μm. This was heat-treated for 40 seconds at the temperature shown in Table 1, and then longitudinally stretched 3.3 times at a temperature 15 ° C. higher than the glass transition temperature (Tg). This stretching was performed by changing the roll speed at the inlet and the outlet, and the stretching speed was 10,000% / min. Level 24
Then, this was once cooled to room temperature, then heat-treated at the temperature shown in Table 1 for 40 seconds, and then laterally stretched 3.5 times at a temperature higher by 15 ° C. than Tg. Horizontal stretching uses a tenter,
The stretching speed was 10,000% / min.

For Levels 1 to 23 and 25, a vinylidene chloride (PVdC) layer was applied after the longitudinal stretching was completed. The vinylidene chloride-based polymer used here is vinylidene chloride (V
dC), methyl methacrylate (MMA), methacrylic acid (Ma) and acrylonitrile (AN) were copolymerized and prepared in the form of a latex liquid. The composition of PVdC is shown in Table 1. If the composition of VdC is Xwt%, MM
The composition of A, Ma and AN is (100-X) wt% respectively.
Was adjusted to 0.8 (0.05%) by 0.15 (wt%). The preparation of these is described, for example, in JP-A-3-
It can be prepared with reference to Synthetic Example 1 of 141346. The solid content concentration of the obtained latex solution is 50%,
The average particle size was 0.16 μm. Furthermore, the following undercoat liquid I was prepared using this.・ Undercoat liquid I Vinylidene chloride latex solution 15 wt% 2,4-Dichloro-6-hydroxy-S-triazine sodium salt 0.15 wt% Silica fine particles (average particle size 0.1 μm) 0.2 wt% Gelatin 1.0 wt% Methylcellulose 0.05 wt% C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.05 wt% Distilled water was added to 100 wt% This undercoat liquid I was adjusted to pH = 6 with 10% KOH, and -Coating was performed on both sides of the support so that the film thickness after heat setting by coating was 0.1 μm. Then, after heat-treating for 40 seconds at the temperature shown in Table 1, transverse stretching was performed 3.5 times at a temperature higher by 15 ° C. than Tg. The transverse stretching was performed using a tenter at a stretching rate of 10,000% / min. The stretched film of levels 1 to 25, which had been longitudinally and transversely stretched in this manner, was heat-set at Tm-20 ° C. for 40 seconds while being relaxed by the amount shown in Table 1.

[0039]

[Table 1]

[0040]

[Table 2]

(3) Surface Treatment of Support The support of level 24, which had been heat-set, was subjected to glow discharge and undercoating. The glow discharge treatment was applied to both sides of the support under the following conditions. Cross section is 2 cm in diameter and 150 in length
A rod-shaped electrode with a hollow part that is a column of cm and serves as a coolant channel,
Four insulating plates were fixed at 10 cm intervals. This electrode plate was fixed in a vacuum tank, the biaxially stretched film was run 15 cm away from this electrode surface so as to face the electrode surface, and the speed was controlled so that surface treatment was performed for 2 seconds. Just before the film passes through the electrodes, the film diameter 5
The heating roll is arranged so that it makes 3/4 round contact with the heating roll with a temperature controller of 0 cm, and the film surface temperature is brought to 70 ° C by bringing a thermocouple thermometer into contact with the film surface between the heating roll and the electrode zone. Controlled. The pressure in the vacuum chamber was 0.2 Torr, and the partial pressure of H ₂ O in the atmospheric gas was 75%. Discharge frequency is 30KH
z, output 2500 W, processing intensity 0.5 KV · A · min /
went in m ² . The support after the discharge treatment was wound in contact with a cooling roll with a temperature controller of 50 cm in diameter so that the surface temperature was 30 ° C. before being wound up. Then, an undercoat liquid II having the following composition was prepared using the above-mentioned vinylidene chloride latex solution.・ Undercoat liquid II Vinylidene chloride latex solution 15 wt% 2,4-dichloro-6-hydroxy-S-triazine sodium salt 0.15 wt% Silica fine particles (average particle size 0.1 μm) 0.2 wt% Add distilled water 100 wt% This undercoat liquid II was adjusted to pH = 6 with 10% KOH, and then applied on both sides of the support by bar coating so that the film thickness after drying was 0.1 μm. It was dried for 2 minutes. Further, an undercoat liquid III having the following composition was applied onto the both surfaces of the support so that the film thickness after drying was 0.1 μm, and dried at 120 ° C. for 2 minutes.・ Undercoat liquid III Gelatin 1.0 wt% C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.05 wt% Methylcellulose 0.05 wt% Distilled water added 100 wt%

In this way, the level 1 finished up to the undercoat
The breaking elongation, the tensile elastic modulus, and the ultraviolet light transmittance of the supports of Nos. 25 to 25 were measured according to the following methods and shown in Table 1. (1) Elongation at Break, Tensile Elastic Modulus The support was cut into a width of 10 mm and a length of 200 mm, and this was measured using a tensile tester at 25 ° C. and 60% RH under a chuck distance of 100 mm and a pulling speed of 10 mm / min. ,
Elongation at break and tensile modulus are determined. Breaking elongation (%) is
It is determined by {(length at break (mm))-100}. This measurement was repeated 5 times in the longitudinal direction and the width direction of the support, and the average value was displayed. (2) Ultraviolet light transmissivity A support is set on the sample side, air is used as a reference, and the light transmittance at 360 nm is measured and displayed in%.

(4) Preparation of photographic light-sensitive material A conductive layer and a back layer having the following compositions were coated on the side opposite to the emulsion coating surface and dried at 40 ° C. for 5 minutes. <Conductive layer> SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μm) 200 mg / m ² gelatin (Ca ²⁺ content 3000 ppm) 77 〃 compound -11 7 〃 sodium dodecylbenzene sulfonate 10 〃 Dihexyl-α-sulfosuccinate sodium 40 〃 Sodium polystyrene sulfonate 9 〃 <Back layer> Gelatin (Ca ²⁺ content 30 ppm) 3.6 g / m ² compound-11 3 mg / m ² polymethylmethacrylate fine particles ( Average particle diameter 3.4 μm) 50 〃 compound-12 40 〃 compound -13 40 〃 compound -14 80 〃 sodium dodecylbenzenesulfonate 75 〃 dihexyl-α-sulfosuccinate sodium 20 〃 compound -15 5 〃 N-pa Fluorooctanesulfonyl-N-propyl 7 〃 Glycine Potassium Sodium 50 〃 sodium acetate 85 〃 1,2-bis (vinylsulfonyl acetamide) ethane 150 〃

[0044]

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[0045]

[Chemical 4]

Then, an emulsion layer having the following composition, a protective layer lower layer, and a protective layer upper layer were simultaneously coated on the surface opposite to the back layer. <Emulsion layer> Emulsion control Liquid I Water 1000 ml Gelatin 20 g Sodium chloride 20 g 1,3-Dimethylimidazolidine-2-thione 20 g Sodium benzenesulfonate 6 mg Liquid II 400 ml Silver nitrate 100 g Liquid III 400 ml Sodium chloride 30.5 g Bromide Potassium 14 g Potassium hexachloroiridium (III) ate (0.001% aqueous solution) 15 ml Ammonium hexabromodium (III) ate (0.001% aqueous solution) 1.5 ml In liquid I kept at 38 ° C., pH = 4.5 Add Solution II and Solution III simultaneously with stirring for 10 minutes to give 0.16
Fine particles of μm were formed. Then, the following IV liquid and V liquid 10
Added over minutes. Further potassium iodide 0.15
g was added to complete the grain formation. IV solution Water 400 ml Silver nitrate 100 g V solution Water 400 ml Sodium chloride 30.5 g Potassium bromide 14 g K ₄ Fe (CN) ₆ 1 × 10 ^-5 mol / mole Ag Then, it is washed with water by a flocculation method according to a conventional method, 40 g of gelatin was added. This emulsion is p
Adjusting to H = 5.3 and pAg = 7.5, 5.2 mg of sodium thiosulfate, 10.0 mg of chloroauric acid and 2.0 mg of N, N-dimethylselenourea were added, and 2.0 mg of sodium benzenesulfonate was added. In addition, it is chemically sensitized at 55 ° C. so as to have the optimum sensitivity, and finally contains 80 mol% of silver chloride.
A silver iodochlorobromide cubic grain emulsion having an average grain diameter of 0.20 μm was prepared. Then, a sensitizing dye was added at 5 × 10 ⁻⁴ mol / mol Ag for ortho-sensitization. Further, as antifoggants, hydroquinone and 1-phenyl-5-mercaptotetrazole were added in amounts of 2.5 g and 50, respectively, per mol of Ag.
30 mg of colloidal silica (Nissan Chemical's SNO-TEX C, average particle size 0.015 μm) to gelatin is 30
% By weight, and polyethyl acrylate latex (0.05 μm) as a plasticizer with respect to gelatin at 40% by weight, and 1,1′-bis (vinylsulfonyl) methane as a cross-linking agent so that the values shown in Table 1 are obtained. Added to. The coating solution Ag3.9g / m ^2, was coated so as to be gelatin 1.8 g / m ^2.

[0047]

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<Protective Layer Lower Layer Formulation> Gelatin per m ² 0.7 g Sodium benzenesulfonate 4 mg 1,5-Dihydroxy-2-benzaldoxime 25 mg Polyethyl acrylate latex 125 mg <Protective layer upper layer formulation> Gelatin per m ² 0.5 g Polymethyl methacrylate fine particles (average particle size 2.5 μm) 40 mg Compound-16 (gelatin dispersion of slipping agent) 60 mg Colloidal silica (Nissan Chemical's Sunotex C) 60 mg Compound-17 5 mg Dodecylbenzenesulfone Sodium acid salt 22mg The dynamic friction coefficient of this sample is 0.22 ± 0.03 (2
5 ° C 60% RH, sapphire needle φ = 1mm, load 100
g, speed 60 cm / min).

[0049]

[Chemical 6]

(5) Evaluation of photographic light-sensitive material The sample thus obtained was coated at 25 ° C. for 6 days for 10 days.
After storage under 0% RH, the following evaluation was carried out. (1) Swelling rate on photosensitive layer side The swelling rate on the photosensitive layer side was measured according to the method described above. (2) Adhesiveness to emulsion layer in wet state After immersing the photosensitive material in pure water at 40 ° C. for 3 minutes, the surface on the photosensitive layer side was strongly rubbed with a fingertip and visually evaluated. ○ It may not come off at all, slightly from the edge etc. (width or length is 1 mm
Hereinafter, the peeled ones are indicated by Δ, and the peeled ones having a width or length of 1 mm or more are indicated by x. Acceptable are ○ and △. (3) Defective development An undeveloped photosensitive material was used as a developing solution and a fixing solution by using SR-D1 and SR-F1 manufactured by Fuji Photo Film Co., Ltd.
G-660F (Fuji Photo Film Co., Ltd.) 38 ° C 2
Development processing was performed for 0 seconds. After that, the light transmittance was measured at 600 nm using a spectrophotometer with air as a reference. If the desilvering is not completed due to insufficient development processing, the transmittance will be low. Transmittance of 65% or more,
100% or less ○, 60% or more, less than 65% △, 60
Less than% was defined as x. Allowed are O and Δ. (4) Pinhole Using the same method as above, apply the exposed A-4 size photosensitive material to the entire surface.
Develop 00 sheets. This was placed on a light table installed in a dark room, and the number of pinholes generated was visually counted.

(6) Results The results are shown in Table 1. (1) Breaking elongation and pinhole (levels 1 to 14) Those which achieved the breaking strength of the present invention by heat treatment before stretching and relaxation during heat setting showed good results with less pinhole generation. . On the other hand, when the elongation at break exceeded this range, the tensile elasticity was less than 300 kg / mm ^2, and there were frequent knicks due to bending during handling. When the elongation at break is less than this range, the pinholes are rapidly generated, and spherulites are easily generated during heat setting, and the ultraviolet light transmittance is less than 75%, which is not preferable. (2) Vinylidene chloride layer and pinhole (level 15-16,
22-24) By applying a layer having a vinylidene chloride content within the range of the present invention, pinhole generation can be suppressed. Below this range, the occurrence of pinholes increases. The same effect can be obtained by applying such a vinylidene chloride layer after stretching and heat setting, or by performing it between stretching and heat setting. (3) Swelling rate of emulsion and poor adhesion (levels 18 to 21) The swelling rate of emulsion was changed by changing the addition amount of the crosslinking agent. When the swelling ratio is within the range of the present invention, good adhesion is obtained.

[0052]

The present invention provides a styrene-based photographic support having a syndiotactic structure which causes less pinhole failure when used in a silver halide photographic material.

[Procedure amendment]

[Submission date] June 21, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction content]

[0039]

[Table 1]

Claims (4)

[Claims] 1. A styrene-based photographic support having a syndiotactic structure having a breaking elongation of 30% or more and 120% or less. 2. The photographic support according to claim 1, wherein a vinylidene chloride polymer layer is coated on at least one surface of the styrene-based photographic support having the syndiotactic structure. 3. The photographic support according to claim 1, wherein the vinylidene chloride-based polymer layer has a vinylidene chloride content of 20% or more and 100% or less. 4. A photosensitive layer is provided on the photographic support according to claim 1, 2 or 3, and the swelling ratio of the entire film on the photosensitive layer side is 150% or more and 400% or less. Silver halide photographic material to be used.