JPH08239497A - Styrene polymer film having coating layer, production thereof, and silver halide photosensitive material - Google Patents

Abstract

PURPOSE: To prevent a silver halide photosensitive material from giving a print having dimensional distortion or image blurring through contact printing by using a styrene polymer film having a substratum and regulated so as to have a corrugation height not larger than a specific value. CONSTITUTION: A film consisting mainly of a syndiotactic styrene polymer is coated with a layer. The coating layer is dried at 50-200 deg.C while the coated film is kept being transferred with rolls apart from each other at a distance of 0.1-10m at the most. The length of the zone where the film is contacted with the rolls is 3-200cm at the most, and the tension imposed on the film during the drying is 2-40kg/m. A silver halide photosensitive material comprises a base consisting mainly of a syndiotactic styrene polymer, a substratum and/or a back layer, and a silver halide emulsion layer, and the base has a corrugation height of 18mm or smaller.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a styrene polymer film containing a styrene polymer having a syndiotactic structure as a main component and having a coating layer, a method for producing the styrene polymer film and a silver halide photograph using the same as a support. It relates to a photosensitive material.

[0002]

2. Description of the Related Art Generally, a silver halide photographic light-sensitive material (hereinafter sometimes abbreviated as a light-sensitive material or a light-sensitive material) has a drawback that its dimensions are easily changed when temperature and humidity are changed. This dimensional change poses a very serious problem especially in a halftone image for multicolor printing and a photosensitive material for printing which is required to reproduce a precise line drawing. Such a dimensional change is caused by a change in the hygroscopic dimension of a layer containing a protective colloid such as gelatin (including a silver halide emulsion layer) and a support. Therefore, improvement of dimensional stability includes both improvement of the protective colloid layer and improvement of the support. As a method for improving the dimensional stability of the support, polyethylene terephthalate (hereinafter referred to as PET), which has been generally used conventionally, is used.
Abbreviated), there is a method of changing to a support having more excellent moisture absorption dimension stability. For example, the film containing a styrene polymer having a syndiotactic structure as a main component described in JP-A-3-131843 has high dimensional stability. Specifically, this styrene polymer film exhibits high humidity dimensional stability of about 10 times (the dimensional change is 1/10) that of the PET film. However, this styrene polymer film was coated with a photosensitive layer and a back layer of a photosensitive material for printing which requires the most dimensional stability, and a pattern close to the actual usage pattern, that is, a test chart was exposed to carry out overprinting. However, contrary to the result of the model evaluation (length measurement by a pin gauge) of the support alone or the film provided with the photosensitive layer, there was a problem that the dimensional deviation was larger than that of the sensitive material of the PET support. In addition, there is a problem that image blurring occurs.

[0003]

The present inventor has further studied the above-mentioned problems, and as a result of providing a coating layer on a film containing a styrene polymer having a syndiotactic structure as a main component, the treatment step causes It was found that the flatness of the film was reduced. When the flatness of the film deteriorates, a dimensional deviation occurs in an image forming process such as overprinting. As a result, the styrene polymer film having a syndiotactic structure, which has better dimensional stability than the PET film, has a PE layer when the undercoat layer is provided.
The phenomenon that the dimensional stability was inferior to that of the T film had occurred. An object of the present invention is to provide a film containing a styrene polymer having a syndiotactic structure as a main component, which has good dimensional stability even when an undercoat layer is provided. It is also an object of the present invention to provide a method for producing a styrene polymer film having a syndiotactic structure which has good dimensional stability even if an undercoat layer is provided. A further object of the present invention is to provide a silver halide photographic light-sensitive material which is less likely to cause dimensional deviation and image blur when overprinted.

[0004]

The objects of the present invention have been achieved by the following styrene polymer films (1) to (10), a method for producing the same and a silver halide photographic light-sensitive material. (1) A styrene polymer film containing a styrene polymer having a syndiotactic structure as a main component and provided with a coating layer, the wavy height of the film being 18
A styrene polymer film having a coating layer having a thickness of not more than mm. (2) A styrene polymer film having a coating layer according to (1), which has a Young's modulus at 110 ° C. of 50 to 300 kg / mm ² in both the longitudinal direction and the width direction. (3) The styrene polymer film according to (1), wherein the dimensional change in the longitudinal direction and the width direction before and after the heat treatment at 110 ° C. for 10 minutes is 0.8% or less.

(4) A styrene polymer film having a coating layer according to (2), which has an in-plane Young's modulus deviation at 110 ° C. of 30% or less. (5) A styrene polymer film having a coating layer according to (3), wherein the in-plane range of dimensional change before and after heat treatment at 110 ° C. for 10 minutes is 0.6% or less. (6) Difference in heat flow rate between 90 ° C and 115 ° C is 0.02
A styrene polymer film having a coating layer according to claim 1, wherein the styrene polymer film has a coating layer of from 0.1 to 0.07 W / g.

(7) A method for producing a styrene polymer film having a coating layer as defined in (1), which comprises coating the layer mainly on a styrene polymer having a syndiotactic structure; and While using a plurality of rolls whose maximum length between rolls is set to 0.1 to 10 m,
A method for producing a styrene polymer film having a coating layer, which comprises a step of drying at 0 to 200. (8) The manufacturing method according to (7), wherein in the drying step, the maximum length of the region where the film and the roll contact each other is 3 to 200 cm. (9) The production method according to (7), wherein the tension applied to the film in the drying step is 2 to 40 kg / m. (10) A silver halide photographic light-sensitive material comprising a support containing a styrene polymer having a syndiotactic structure as a main component, an undercoat layer and / or a back layer, and at least one silver halide emulsion layer. A silver halide photographic light-sensitive material characterized in that the support has a waviness height of 18 mm or less.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In order to use a polymer film as a photographic support, an undercoat layer is coated between the support and the emulsion layer in order to secure the adhesion between the support and the emulsion layer. According to the research conducted by the present inventor, the planarity of a film containing a styrene polymer having a syndiotactic structure as a main component (hereinafter abbreviated as SPS film) is likely to deteriorate after the coating. Specifically, a corrugated sheet-like corrugation that occurs at a cycle of 1 to 5 cm in the longitudinal direction (referred to as “stretching failure”) and a corrugated deformation that occurs at a cycle of 10 to 50 cm in the width direction (referred to as “corrugation failure”). ), Or fine irregularities having a diameter of about 1 to 5 mm (referred to as "bugs failure") are generated on the entire surface of the film. When a film with reduced flatness is used as a support in this way, when it is overprinted for printing, it cannot be exactly overlaid, resulting in the deviation of the test pattern and image blurring as described above. It became clear. That is, in the case of the photosensitive material for printing, the exposure is often overlaid on the original film, but if there is such a planarity failure, it cannot be superposed on the original film neatly and a dimensional deviation occurs. Such trouble could not be predicted at all by the model dimension evaluation, that is, the measurement by the pin gauge. This is because in the pin gauge method, a constant tension is applied to the film to measure the length, so that such a decrease in flatness is corrected and apparently good dimensional stability is obtained.

The gap between the original film and the original film caused by the reduction of the flatness causes blurring of the image.
This too could not be predicted from the above model evaluation. As described above, the present inventors have found that the cause of the dimensional deviation and the exposure blur at the time of overlay exposure is due to the deterioration of the flatness. Among such failures, the waving failure has a large effect on the dimensional deviation and the image blur. According to the present invention, the height of the corrugation is set to 18 mm or less, preferably 12 mm or less, more preferably 6 mm or less, further preferably 5 mm or less, and most preferably 4 mm or less, whereby dimensional deviation and exposure blur can be prevented.

The method of measuring the height of the corrugation is shown in FIG.
Will be described with reference to. FIG. 1 is a schematic sectional view showing a method for measuring the corrugation height. The film (2) provided with the coating layer (3) is allowed to stand on a horizontal and flat table without applying tension. The average value of the height (h) of the gap between the reference line (1) corresponding to the surface of the table and the film (2) is defined as the corrugation height. Note that, as shown in FIG. 1, the waviness is a wavy deformation in the width direction (TD) that occurs at a period of 10 to 50 cm with respect to the longitudinal direction (MD). The measurement is performed by sampling the film for 1 m.

The waviness failure occurs when a coating layer is formed on the film. As a result of the research conducted by the present inventor, the SPS support is more likely to undergo dimensional change due to heat than PET, which may cause various reductions in flatness including a corrugation failure in a drying process after applying a layer. found. For example, the streak failure results from the elongation associated with a decrease in the Young's modulus in the longitudinal direction during the film drying process, and its non-uniformity. When the film is used as a photographic support, an undercoat layer is essential for ensuring the adhesion between the emulsion layer and the support. In many cases, the undercoat layer mainly contains gelatin. Water of good solvent is required to dissolve such gelatin, and its drying temperature is above the boiling point of water, ie, at least 110.
Requires a temperature above ℃. However, 110 ° C is SPS
Above the glass transition temperature (Tg = 100 ° C.) of the support.
Since the Young's modulus of the SPS support is significantly lower than that of the PET support at a temperature exceeding Tg, the SPS support is easily stretched by the tension during the drying process. Further, the SPS film is more likely to have uneven thickness and uneven film formation than the conventionally used PET film, and in the stretching process, it is easy to proceed (necking phenomenon) from a weak portion of the film. As a result, the width of the more stretched portion becomes narrow, and the width does not become so narrow in a portion where the stretching is small.

In order to match the widths of these portions, slack in the width direction occurs in the wide portion. If this continues in the longitudinal direction, a "stretch failure" occurs as if a streak had occurred. Therefore, a support having a small Young's modulus at a high temperature (110 ° C.) in which necking is likely to occur is likely to cause this failure. Furthermore, if there is Young's modulus unevenness in the longitudinal direction, it tends to be unevenly stretched and more likely to occur. Naturally, this failure is also involved in the heat shrinkability, and is likely to occur if the heat shrinkage is large and the local variations are large.

Next, the waviness failure often results from the non-uniformity of the shrinkage behavior of the SPS film in the width direction. In a polymer film, especially a biaxially stretched film, there is stretching unevenness in the width direction, and accordingly, the shrinkage amount becomes uneven in the width direction. As a result, a portion with a small amount of contraction becomes slack and wavy as compared with a large portion. In this way, a "waviness failure" occurs. As described above, tension is not applied in the width direction during the coating process, and heat shrinkage and its anisotropy are the main causes. (This is the difference from the above "stretching" failure)

Further, as for the fault of the spot, the SPS film is
It often occurs due to uneven heat shrinkage when coming into contact with a transport roll during the drying process. When the SPS film comes into contact with the roll, air is trapped in a part between the film and the roll. Therefore, the film has a part that is in direct contact with the roll (there is no air) and a part that is not (there is air). Since the heat capacity of the roll is large,
The part in contact with the roll rapidly receives heat and contracts. On the other hand, the part that is not in contact has less heat shrinkage due to the less heat supply, and it seems that the part that is not in contact is elongated. This part becomes foamy. Therefore, this failure is
This is caused by the heat shrinkage of the SPS support.

The following two improving means are conceivable as a method for preventing the deterioration of the flatness of the SPS film during drying. (A) Improvement of physical properties of film (Young's modulus at high temperature, heat shrinkability, and uniformity in these planes) (B) Improvement of drying step

First, the improvement of the physical properties of the SPS film will be described. The important point for the physical properties of the film is 11
High Young's modulus at 0 ° C, low heat shrinkability,
These three points are that the in-plane anisotropy (unevenness) is small. The Young's modulus at 110 ° C. is preferably 50 to 300 kg / mm ² in both the longitudinal and width directions, more preferably 70 to 250 kg / mm ² , and most preferably 90 to 220 kg / mm ^2. preferable. If it is less than this range, the film is stretched during the step of drying the coating layer, and streaks and waviness are likely to occur. On the other hand, in order to exceed this range, it is necessary to increase the crystallinity in the film. When the crystallinity increases,
Along with that, haze increases and transparency decreases, which is not preferable as a photographic support. Further, from the mechanism of occurrence of the above-mentioned "stretching" failure, it is desirable to increase this Young's modulus only in the longitudinal direction. However, such a support having too large anisotropy in the length / width direction is used as a photographic support. It is hard to use. Therefore, the Young's modulus at 110 ° C in the width direction is also equal to 30% in the longitudinal direction.
Weaker ones are suitable as photographic supports. Regarding the heat shrinkability, the dimensional change in the longitudinal direction and the width direction before and after the heat treatment at 110 ° C. for 10 minutes is preferably 0.8% or less, more preferably 0.6% or less, and most preferably 0.4% or less. . Beyond this range, streaking, waving,
It is not preferable because it easily causes a fault.

The physical properties of the above film are preferably uniform in the plane. The in-plane deviation of the Young's modulus at 110 ° C. is preferably 30% or less, more preferably 25% or less, most preferably 20% or less. The in-plane range before and after the heat treatment at 110 ° C. for 10 minutes is preferably 0.6% or less, more preferably 0.4% or less, most preferably 0.3% or less. These in-plane deviations and in-plane ranges were 5 points at every 30 cm in the longitudinal direction of the width of the film, and 5 points obtained by dividing the width direction of the film into 5 equal parts, for a total of 10 points. It is a value obtained by measuring Young's modulus and heat shrinkage. The value obtained by dividing the absolute value of the difference between the maximum value and the minimum value at these measurement points by the maximum value is the "in-plane deviation". The absolute value of the difference between the maximum value and the minimum value is referred to as "in-plane range".

Furthermore, 90 measured by using a differential thermal analyzer
The difference between the heat flow rate at 0 ° C and the heat flow rate at 115 ° C is 0.
It is preferably from 02 to 0.07 W / g, and 0.0
More preferably from 3 to 0.06 W / g,
Most preferably, it is 0.035 to 0.05 W / g. This characteristic value is a measure of Young's modulus at a temperature exceeding Tg. If this value exceeds this range, high temperature (110
The Young's modulus at (° C.) Is low, which is not preferable. On the other hand, if it is less than this range, the haze is increased, which is not preferable. The haze of the film is preferably 2% or less, 1.5%
It is more preferably at most, and most preferably at most 1%. This difference in heat flow rate indicates a difference in structure around the glass transition temperature (100 ° C.) of the SPS film. Crystal, amorphous and its intermediate phase coexist in the film. The amorphous part shows a structural change at the glass transition temperature, and the structural change of this component appears as a difference in heat flow rate around Tg. Therefore, if this amount is large, it means that the amorphous part is melted and becomes suddenly softer when Tg is exceeded.

In order to reduce the difference in heat flow rate, there are a method of increasing the number of crystals and a method of increasing the number of intermediate phases. When the number of crystals is large, transparency is likely to decrease and haze is likely to increase. The amount of crystals was measured by using a differential thermal analyzer (DSC).
It can be obtained by measuring the endothermic amount of ku. A preferable heat absorption amount is 10 to 30 J / g or less, and 15 to 28 J / g.
g is more preferable, and 18 to 26 J / g is most preferable. The endothermic amount is measured in a nitrogen stream while heating a sample of 5 to 10 mg at 20 ° C./min. The intermediate phase is a molecule that exists as a bridge between amorphous / amorphous or amorphous / crystalline structures in the film, and does not have the rigidity as high as that of the crystalline part, but it rapidly becomes soft even at a temperature of Tg or higher. It never happens. Further, the intermediate phase also has a function of suppressing the movement of the amorphous part.

The surface roughness (Ra) of the film is preferably 0.001 to 0.02 μm on at least one side, more preferably 0.002 to 0.015 μm, and 0.003 to 0.010 μm. Is most preferable. If it is less than this range, air is not easily released between the film and the roll which are in contact with each other during coating and drying, and the remaining air bubbles cause "bugs failure". On the other hand, a film exceeding this range tends to have a high haze, which is not preferable as a photographic support. The thickness of the SPS film is 9
The thickness is preferably 0 to 300 μm, more preferably 95 to 250 μm, most preferably 100 to 200 μm.
If it is less than this range, it is unfavorable because it is easily stretched by the tension during the drying step. Also, breakage and knicks are likely to occur during handling. If it exceeds this range, the stiffness (strength of the waist) becomes too strong, and jamming is likely to occur in an automatic transport mechanism such as an automatic processor.

The physical property values of the film as described above are the regulations required before forming the coating layer on the film.
However, even if the coating layer is applied to the film,
The above physical properties hardly change (10
Within%). Therefore, in the present invention, the same values as above are defined as the physical property values of the film having the coating layer (that is, after the coating layer is provided). The SPS film having the above physical property values can be obtained by the following film forming process. (1) Drying The pelletized raw material is heated and dried in vacuum or in air to remove adsorbed water. At this time, the efficiency is good if the drying temperature is higher than the glass transition temperature and lower than the melting point.

(2) Extrusion The dried raw material pellets are melted by heating, extruded, cooled,
A film is formed by solidifying. 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 in the range of 50 ° C. higher than the melting point of the polymer used to the decomposition temperature, and the extrusion is preferably performed using a T-die or the like.

(3) Preparation of unstretched sheet After the extrusion molding, the obtained preform (unstretched 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 of the cooling and solidification is the glass transition temperature (Tg) of the original sheet-70 ° C to Tg, more preferably Tg-50 ° C.
To Tg-20 ° C.

(4) Stretching Next, the cooled and solidified unstretched sheet is stretched. In the case of a photographic support that requires vertical and horizontal homogeneity, stretching is preferably longitudinal and lateral multiaxial stretching, and more preferably longitudinal and lateral stretching biaxial stretching. On the other hand, if re-stretching is performed after these stretching, longitudinal and lateral heat shrinkage, Young's modulus and other anisotropy are likely to increase, and haze is likely to increase, which is not preferred in the present invention. In the present invention, by improving this stretching method, the Young's modulus at 110 ° C. achieves the in-plane deviation of the present invention, and the heat shrinkability achieves the support of the in-plane range of the present invention. Especially the point is
It is longitudinal stretching. This is because the in-plane non-uniformity here is further amplified in the subsequent transverse stretching. This is because the SPS film is much more likely to cause necking as compared with PET which has been conventionally used for photography. That is, if there is a slight unevenness in the thickness of the film after longitudinal stretching,
It is selectively stretched from there, resulting in thinner layers, causing large in-plane non-uniformities. Further, this longitudinal stretching step is also important in order to control the production of the amorphous phase and form a film of the support having a difference in heat flow rate according to the present invention.

The point of the longitudinal stretching process is to control the distance between the heater and the stretching roll. In the normal longitudinal stretching, a support heated by a heater is stretched through two rolls having different peripheral speeds. The longitudinal stretching will be described with reference to FIG. FIG. 2 is a schematic sectional view showing a preferred longitudinal stretching step. The film (22) transported to the longitudinal stretching device by the transport roll (23) has a low peripheral speed (24).
And is stretched by passing through a roll (25) having a high peripheral speed. In this stretching, the film is heated by a heater (2
1a, 21b, 21c). The important point is the last heater (21c) and the last roll (25)
Is the distance (L) between the two. This distance is 10 to 50 cm
It is preferable that the distance is 15 cm, more preferably 15 to 40 cm, and most preferably 20 to 35 cm. The distance (L) is, as shown in FIG.
Measure the distance between the center of the heater (21c) and the center of the roll (25). If more than one heater is installed, measure the distance between the heater and the roll closest to the last roll. The film is stretched as shown in FIG. 2, but if the distance (L) in FIG. 2 is large, the film is stretched in a wider range. That is, selective stretching that reflects slight unevenness in thickness and the like existing in the unstretched film is likely to occur. On the other hand, if this distance is narrow, there is no choice and the whole is stretched at once, so uniform stretching is likely to proceed. Therefore, if this distance exceeds the above range, a film with large in-plane non-uniformity is likely to be formed. On the other hand, if it is less than this range, it becomes difficult to increase the draw ratio, and as a result, the Young's modulus cannot be increased. Further, when the distance (L) between the heater and the roll is large, the amorphous or crystalline phase is extended to the intermediate phase which is entangled. As a result, the intermediate phase is converted to an amorphous phase, and the film has many amorphous phases, which is not preferable.

The heater used for the longitudinal stretching may be a halogen lamp, an infrared lamp, a bicole heater, a ceramic heater or the like placed on or under a support for heating, or may be heated by a heating roll. Alternatively, a heating medium (air, a heating gas such as nitrogen, etc.) may be sprayed. As the roll, it is preferable to use a metal roll or a ceramic roll having heat resistance and high mechanical strength. The diameter of the roll is preferably 50 to 500 mm,
More preferably, it is 100 mm to 350 mm. The longitudinal stretching temperature is the glass transition temperature (Tg) to Tg of the unstretched film.
It is preferably + 50 ° C., and Tg + 5 ° C. to Tg + 3
More preferably 0 ° C., Tg + 10 ° C. to Tg
Most preferably + 25 ° C. Longitudinal stretching speed is 1
000 to 8000% / min, and preferably 200
More preferably 0 to 6000% / min, 25
Most preferably, it is from 00 to 4000% / min. The longitudinal stretching ratio is preferably 2.8 to 4.5 times, and 3 to 4.2.
Double is more preferable, and 3.2 to 4 is most preferable.

The longitudinally stretched sheet thus obtained is further laterally stretched. It is preferable to preheat the support before performing the transverse stretching in order to ensure the uniformity of the support. The preheating temperature is preferably a horizontal stretching temperature of −30 ° C. or higher and a horizontal stretching temperature of + 30 ° C. or lower, more preferably a horizontal stretching temperature of −20 ° C. or higher, a horizontal stretching temperature of + 20 ° C. or lower, a horizontal stretching temperature of −10 ° C. or higher, and a horizontal stretching temperature of +10.
C. or less is more preferable. The preheating time is preferably 1 second to 3 minutes, more preferably 5 seconds to 2 minutes, and 10 seconds to 1
Minutes are most preferred. The transverse stretching is preferably performed with a tenter, and the stretching ratio is preferably 2.8 times or more and 4.5 times or less, more preferably 3 times or more and 4.2 times or less, and 3.2.
It is more preferably double or more and four times or less. The transverse stretching temperature is the glass transition temperature (Tg) to Tg + 50 ° C. of the unstretched sheet,
It is more preferably set to Tg + 5 ° C. to Tg + 30 ° C., and further preferably set to Tg + 10 ° C. to Tg + 25 ° C.
The transverse stretching speed is 1000 to 8000% / min, preferably 2000 to 6000% / min, and more preferably 250.
0 to 4000% / min.

(5) Heat setting The biaxially stretched film thus obtained is heat set. The heat setting is preferably carried out at 180 ° C. to 250 ° C. for 1 to 180 seconds in a tensioned state, a relaxed state or a restricted contraction state, and at 190 ° C. to 240 ° C.
It is more preferable to carry out from 90 seconds to 90 seconds, from 200 ℃ to 23
More preferably, it is carried out at 0 ° C. for 10 to 60 seconds.
Above this temperature, haze tends to increase, which is not preferable. On the other hand, when the temperature is lower than this temperature, heat shrinkage tends to be large, which is not preferable. At this time, it is more preferable to perform heat setting while relaxing by 1% to 10% in order to reduce heat shrinkage and haze.

Next, the styrene polymer having a syndiotactic structure used in the present invention will be described.
The syndiotactic structure means a three-dimensional structure in which a phenyl group which is a side chain and its derivative are alternately located in opposite directions with respect to a main chain formed from carbon-carbon bonds. Its stereoregularity (tacticity) is generally quantified by a nuclear magnetic resonance method ( ¹³ C-NMR method) using isotope carbon and is excellent in accuracy. The stereoregularity measured by the ¹³ C-NMR method should be indicated by the existence ratio of a plurality of continuous constitutional units, for example, diad in the case of 2 units, triad in the case of 3 units, and pendad in the case of 5 units. You can The styrene polymer having a syndiotactic structure referred to in the present invention is usually 75% or more and 100% or less, preferably 85% or more, as a racemic diad.
00% or less, or 30% or more and 100% or less, preferably 50% or more and 100% or less stereoregularity with a racemic penta head. By styrene polymer is meant polystyrene and its derivatives, its copolymers and mixed polymers containing it. Derivatives of polystyrene include poly (alkylstyrene), poly (halogenated styrene), poly (halogenated alkylstyrene), poly (alkoxystyrene) and poly (vinyl benzoate). 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). Among these, poly (styrene) and poly (methylstyrene) are more preferable, and poly (styrene) is more preferable.

The styrene polymer having a syndiotactic structure may be a copolymer other than the above homopolymer. As the comonomer component of the copolymer, in addition to the monomers constituting the above-mentioned styrene polymer, olefin monomers (eg, ethylene, propylene,
Butene, hexene, octene), diene monomers (eg,
Butadiene, isoprene), cyclic olefin monomer,
Examples thereof include cyclic diene monomers and polar vinyl monomers (eg, methyl methacrylate, maleic anhydride, acrylonitrile). Of these, styrene as the main component, alkyl styrene, hydrogenated polystyrene,
A copolymer of halogenated polystyrene is preferred.
Among these, p-methylstyrene, m-methylstyrene, p-tert-butylstyrene, p-chlorostyrene, m-chlorostyrene, p-fluorostyrene and hydrogenated polystyrene are preferable, and p is particularly preferable. −
It is methylstyrene. The proportion of monomers other than styrene in the copolymer is preferably 30 wt% or less, more preferably 1 to 20 wt%, and 2
Most preferably, it is from 10 to 10 wt%.

A styrene polymer having a syndiotactic structure and another polymer may be mixed and used. As a preferable polymer blend component, a styrene polymer having a syndiotactic structure as described above and a styrene polymer having an atactic structure are preferable from the viewpoint of compatibility. Among these, particularly preferred is polystyrene having a syndiotactic structure as a main component, and p-methylstyrene, m-methylstyrene, p-tert-butylstyrene, p-chlorostyrene, m- A homopolymer of chlorostyrene, p-fluorostyrene, hydrogenated polystyrene having a syndiotactic structure or atactic structure, and / or a copolymer having a syndiotactic structure or atactic structure composed of styrene and at least one of these monomers. Is preferably blended. 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. The film to which such components are added is more preferable than the film made of the SPS homopolymer because it easily lowers the haze and heat shrinkability. The ratio of the components other than SPS in the polymer mixture is preferably 30 wt% or less, more preferably 1 to 20 wt%, and 2
Most preferably, it is from 10 to 10 wt%.

The preferred polymer composition is shown below. Here, syn- is syndiotactic and atc- is atactic. (1) Homopolymer P-1: syn-poly (styrene) P-2: syn-poly (p-methylstyrene) P-3: syn-poly (p-chlorostyrene) P-4: syn-poly (hydrogen) Styrene) (2) Copolymer composition ratio (% by weight) P-5: syn-poly (styrene / p-methylstyrene) (95/5) P-6: syn-poly (styrene / p-methylstyrene) (85 / 15) P-7: syn-poly (styrene / p-chlorostyrene) (95/5) P-8: syn-poly (styrene / p-chlorostyrene) (85/15) P-9: syn-poly (Styrene / hydrogenated styrene) (95/5) P-10: syn-poly (styrene / hydrogenated styrene) (85/15) P-11: syn-poly (styrene / hydrogenated styrene / p-methylstyrene) (95/5/5)

(3) Polymer Blend Mixing Ratio (wt%) P-12: syn-poly (styrene) + syn-poly (p-methylstyrene) (95 + 5) P-13: syn-poly (styrene) + syn- Poly (p-methylstyrene) (85 + 15) P-14: syn-poly (styrene) + syn-poly (p-chlorostyrene) (95 + 5) P-15: syn-poly (styrene) + syn-poly ( p-chlorostyrene) (85 + 15) P-16: syn-poly (styrene) + syn-poly (hydrogenated styrene) (95 + 5) P-17: syn-poly (styrene) + syn-poly (hydrogenated styrene) ) (85 + 15) P-18: syn-poly (styrene) + atc-poly (styrene) (95 + 5) P-19: syn-poly (styrene) + atc-poly (styrene) (85 + 15) P- 20: syn-poly (styrene) + atc-poly (p-methylstyrene) (95 + 5) P-21: syn-poly (styrene) + atc-poly (p-methylstyrene) (85 + 15) P-22: syn-poly Styrene) + atc-poly (hydrogenated styrene) (95 + 5) P-23: syn-poly (styrene) + atc-poly (hydrogenated styrene) (85 + 15) P-24: syn-poly (styrene) + atc- Poly (styrene) + syn-poly (p-methylstyrene) (95 + 5 + 5) P-25: syn-poly (styrene) + syn-poly (p-methylstyrene + styrene copolymer (molar ratio = 10:90 )) (70 + 30) P-26: syn-poly (styrene) + syn-poly (p-methylstyrene + styrene copolymer (molar ratio = 10: 90)) (50 + 50) P-27: syn- Poly (styrene) + syn-poly (p-methylstyrene + styrene copolymer (molar ratio = 5: 95)) (70 + 30) P-28: syn-poly (styrene) + syn-poly (p-methylstyrene +) Styrene copolymer (molar ratio = 30: 70)) (90 + 10)

The weight average molecular weight of these styrene polymers is preferably 100,000 to 800,000, particularly preferably 200,000 to 600,000. 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).

The key to achieving a film having the Ra value described above is to prepare fine particles to be added to the film. Examples of the fine particles to be added to the film include inorganic fine particles such as silica, talc, titania, alumina, calcium carbonate, calcium oxide, calcium chloride and mixtures thereof, and organic fine particles such as crosslinked polystyrene and crosslinked polymethylmethacrylate. The addition amount of fine particles is preferably 20 to 300 ppm, more preferably 30 to 200 ppm, and 40 to 100 ppm
The following is more preferable. The particle size of the fine particles is 0.0
The thickness is preferably 1 to 5 μm, more preferably 0.05 to 3 μm, still more preferably 0.1 to 1 μm. The shape of the fine particles is spherical, irregular (crushed), needle-like or plate-like. Spherical or amorphous (crushed) fine particles are particularly preferable. In addition to the fine particles, the film may contain an antioxidant, an antistatic agent, and a dye. In order to prevent monomer deposition during film formation, it is preferable to adjust the amount of residual styrene monomer in the styrene polymer to 7,000 ppm or less.

Next, the improvement of the drying process of the coating layer will be described. Regarding the flatness of the film, the length between the pass rolls and the drying temperature in the coating layer drying step are the most important. If the path roll interval is long, the support will not be held during that time,
Heat shrinks more easily in the width direction. On the other hand, in the longitudinal direction, if this distance is long, it is more susceptible to stretching due to tension. As a result, "stretch failure" is likely to occur. On the other hand, when the distance between the pass rolls is short, the contraction in the width direction is suppressed on the pass rolls, and the elongation due to the tension is also small, so that this failure is unlikely to occur. Furthermore, “waviness failure” caused by non-uniformity of heat shrinkage in the width direction is likely to occur because the amount of shrinkage tends to be large because it can freely shrink if the interval between the pass rolls is long. If the length is short, the undulations on the pass roll are corrected to be flattened more frequently and are less likely to occur. In this way, it is effective to shorten the interval between the pass rolls for "stretch failure" and "wavy failure". However, if the interval between the pass rolls is too short, the route becomes complicated, which is not preferable in terms of maintenance. The interval between the pass rolls is preferably 0.1 to 10 m or less, more preferably 0.5 to 5 m, still more preferably 1 to 3 m.

In addition to the pass roll length, the drying temperature is also a major factor in the failure of flatness. As previously mentioned,
The flatness failure is caused by thermal contraction and stretching during drying. Therefore, it is preferable to carry out the drying step at a temperature as low as possible. An analysis of the heat shrinkage behavior of the SPS support revealed that the heat shrinkage dramatically increased above 200 ° C, resulting in a sharp increase in the frequency of "waviness failure" and "stretch failure". . A preferred temperature range is 50 ° C or higher and 200 ° C or lower, more preferably 60 ° C or higher and 170 ° C or lower, and further preferably 70 ° C or higher and 140 ° C.
It is the following. Within this temperature range, the same effect can be obtained by drying at a constant temperature or by drying while changing the temperature (heating and / or cooling). However, below this temperature, the adhesion of the back layer and / or the undercoat layer deteriorates, which is not preferable. On the other hand, above this temperature, the flatness tends to decrease. Such control of the drying temperature can be carried out by a conventional method. For example, the output of a heater such as a nichrome heater, an infrared lamp, a halogen lamp, or a mercury lamp may be controlled and implemented. Alternatively, hot air may be blown into the drying zone to control the temperature or air volume.

Furthermore, the tension during drying is also an important factor. If this is too large, the support will stretch in the transport direction,
The difference in the amount of expansion / contraction with the longitudinal direction becomes large, and "stretch failure" is likely to occur. In addition, stretch unevenness in the width direction becomes large, and “waviness failure” is likely to occur. Preferred tension is 2
To 40 kg / m, more preferable tension is 3 to 30 kg
/ M, and a more preferable tension is 4 to 20 kg / m. Below this tension, it is difficult to stably convey the support.

In regard to the above-mentioned "bump failure", it is particularly effective to adjust the contact length between the pass roll and the support. The spot failure is caused by non-uniform contact of the hot roll surface with the air of the support. Therefore, it is preferable that the contact length with the pass roll is as short as possible in order to suppress the occurrence of failure. On the other hand, if it is too short, problems may occur during transportation. Preferred contact length is 3 to 20
It is 0 cm, more preferably 5 to 150 cm, further preferably 10 to 100 cm. Such a contact length is determined by the diameter of the pass roll and the wrap angle, but they have little effect on the “bugs failure”, and are mainly affected by the contact length. The pass roll used is preferably as smooth as possible for the reasons described above. As the material, a metal material such as stainless steel, iron, aluminum, or a thermosetting resin can be used, but stainless steel that can be stably used at high temperature is preferable. By improving the dry zone as described above, the planarity failure of the SPS support can be overcome.

As described above, the drying temperature of the coating layer is preferably as low as possible. However, if the drying temperature is lowered,
Poor adhesion between the coating layer and the film is likely to occur. For this reason, it is preferable to perform surface treatment and then apply these coatings. Preferred surface treatments include glow discharge treatment, corona treatment, ultraviolet irradiation treatment, and flame treatment. The most preferred of these is glow discharge treatment. The surface treatments will be described below. Regarding the glow discharge treatment, Japanese Patent Publication Nos. 35-7578 and 36-1033.
No. 6, No. 45-22004, No. 45-22005,
45-24040, 46-43480, JP-A-53-129262, U.S. Pat.
No. 2, No. 3057795, No. 3179482, No. 3
No. 288638, No. 3309299, No. 342473
No. 5, No. 3462335, No. 3475307, No. 3
7612299, 4072,769, British Patent 89
It is described in the respective specifications of 1469 and 997093. In the glow discharge treatment, the best adhesive effect can be obtained 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 partial pressure of water vapor when the glow discharge treatment is carried out in the presence of water vapor is preferably 10 to 100%, more preferably 40 to 90%. 1
If it is less than 0%, it becomes difficult to obtain sufficient adhesiveness. The gas other than water vapor is air composed of oxygen, nitrogen and the like.

Further, when the vacuum glow discharge treatment is carried out in a state where the support to be surface-treated is heated, the adhesion is improved in a shorter time than the treatment at room temperature, which is effective. The preheating temperature is preferably 50 ° C. or higher and Tg or lower, and 60 ° C. or higher 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 discharge treatment 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 0.01KV · A · min / m2-5KV · 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 .

The oxygen abundance (the peak area of the signal appearing at 525 to 545 eV of 1 s of oxygen, which is determined by photoelectron spectroscopy (XPS) on the surface of the support thus obtained, is defined as the ionization cross section = 2.85. Divided by) and the abundance of carbon (the peak area of the signal appearing at 300 to 270 eV for 1 s of carbon divided by the ionization cross section = 1), the ratio (oxygen abundance / carbon abundance) is 0. 0.05 or more and 0.30 or less are preferable, 0.08 or more and 0.25 or less are more preferable, 0.10 or more and 0.23 or less are still more preferable. Also, the amount of nitrogen present (the peak area of the signal appearing at 410 to 390 eV for 1 s of nitrogen divided by the ionization cross section = 1.77) and the amount of carbon present (300 to 270 for 1 s of carbon).
The peak area of the signal appearing in eV is the ionization cross section =
(Value divided by 1) (amount of nitrogen present / amount of carbon present) is 0.
005 or more and 0.06 or less are preferable, 0.008 or more and 0.04 or less are more preferable, 0.010 or more,
0.03 or less is more preferable. It is preferable that the temperature of the support thus subjected to the glow discharge treatment is immediately lowered by using a cooling roll.

For corona treatment, Japanese Patent Publication No. 48-50
43, 47-51905, and JP-A-47-2806.
No. 7, No. 49-83767, No. 51-41770,
No. 51-131576. Discharge frequency is 50Hz-5000kHz, preferably 5k
Hz to several hundreds of kHz is suitable. Regarding the processing strength of the object to be processed, 0.001 KV · 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.

The ultraviolet treatment is carried out according to Japanese Examined Patent Publication No. 43-2603,
It is described in JP-B-43-2604 and JP-B-45-3828. The mercury lamp serving as a light source of ultraviolet rays is a high-pressure mercury lamp or a low-pressure mercury lamp composed of a quartz tube. The wavelength of ultraviolet rays is preferably between 180 and 380 nm. Regarding the method of irradiating with ultraviolet rays, the irradiation light amount is 20 to 100 for a high-pressure mercury lamp having a main wavelength of 365 nm.
00 (mJ / cm ² ) is preferable, and more preferably 50-
It is 2000 (mJ / 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 preferable, and more preferably 20.
It is 0 to 1500 (mJ / cm ² ).

The flame treatment can be carried out using natural gas or liquefied propane gas. The mixing ratio of gas and air is important. In the case of propane gas, a preferable mixing ratio of propane gas / air is 1/14 to 1/22, preferably 1/16 to 1/19 in terms of volume ratio. In the case of natural gas, it is 1/6 to 1/10, preferably 1/7 to 1/9. Thermal energy flame treatment is preferably prepared in the range of ^{1~50Kcal / m 2, 3~30Kcal / m} 2
It is more preferable to set the range to. 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.

Next, the coating layer provided on the film will be described. In a silver halide photographic light-sensitive material, a surface-treated film is provided with an undercoat layer and / or a back layer.
As the undercoat layer, a layer that adheres well to the support as the first layer (hereinafter, abbreviated as the first undercoat layer) is provided, and the second layer is formed thereon.
A so-called multi-layer method in which a layer for well adhering the undercoat first layer and the photographic layer (hereinafter abbreviated as the undercoat second layer) is applied as a layer, and a single layer method in which only one layer for well adhering the support and the photographic layer is applied. There is. In the first undercoat layer in the multi-layer method,
For example, copolymerization using a monomer selected from vinyl chloride, vinylidene chloride, butadiene, vinyl acetate, styrene, acrylonitrile, methacrylic acid ester, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, etc. as a starting material Coalescent, epoxy resin, gelatin, nitrocellulose, polyvinyl acetate, etc. are used. If necessary, a crosslinking agent such as triazine-based, epoxy-based, melamine-based, blocked isocyanate-based isocyanate-based, aziridine-based, oxazaline-based, etc., inorganic particles such as colloidal silica, surfactants, thickeners, dyes, preservatives. Agents and the like may be added. For these, EHImmergut "Polym
er Handbook "VI187-231, Intersciense Pub.Ne
w York 1966 and JP-A-50-39528, 50
No. 47196, No. 50-63881, No. 51-13
No. 3526, No. 64-538, No. 63-174698
Japanese Patent Application No. 1-240965, Japanese Patent Application Laid-Open No. 1-24096.
5, JP-A-2-184844, JP-A-48-89870.
And No. 48-93672. Gelatin is mainly used in the second undercoat layer.

In the single layer method, a method in which a polymer film as a support is swollen and interfacially mixed with an undercoating polymer to obtain good adhesiveness is often used. As the undercoat polymer, gelatin, gelatin derivative, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer,
Water-soluble polymers such as maleic anhydride copolymers, cellulose esters such as carboxymethyl cellulose and hydroxyethyl cellulose, vinyl chloride-containing copolymers, vinylidene chloride-containing copolymers, acrylic acid ester-containing copolymers, vinyl acetate-containing copolymers , Latex polymers such as vinyl acetate-containing copolymers, and the like are used. Of these, gelatin is preferred. 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. The point of the drying temperature in the single layer method and the multi-layer method is 50 ° C. or more and 150 ° C. or less as described above.
The coating layer (undercoat layer, back layer) provided on the film preferably has a thickness of 0.001 to 5 μm, and a thickness of 0.
More preferably 005 to 1 μm, and 0.0
Most preferably, it is 1 to 0.5 μm.

A back layer is coated for the purpose of imparting scratch resistance, slipping property, curl compensation, antistatic ability and the like 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. Of these gelatins,
Most preferably, lime-processed gelatin and acid-processed gelatin are 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 using these hydrophilic polymers,
In order to impart stronger adhesion, it is also preferable to apply the backing layer after applying the same undercoat as the photosensitive layer.

As the binder of the hydrophobic polymer layer, a (meth) acrylic acid ester polymer such as polymethylmethacrylate or ethylacrylate, an olefin polymer such as polyethylene, a styrene polymer, vinylidene chloride, a urethane polymer, a rubber system such as butadiene. 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 0.02 to 10 μm, more preferably 0.1 to 7 μm.
The range of μm is preferable, and the total thickness of these layers is 0 to 5 μm.
m is preferred.

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 to 200 mμ, and the preferable amount is 0.01 to 1.0 in terms of dry weight ratio to 1.0 of the binder, and particularly preferable. Is 0.1 to 0.8. 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 Or more, particularly preferably 300 to 500,000 polymers,
A specific example is shown by the following equation.

[0047]

Embedded image

The point of drying after coating the back layer is to carry out at a temperature of 50 ° C. to 150 ° C. as described above. A silver halide emulsion layer is coated on the thus prepared undercoat layer. 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 photosensitive silver halide, a chemical sensitizer, a spectral sensitizer, an antifoggant, a hydrophilic colloid (especially gelatin), a gelatin hardener, a surfactant, and other physical properties of the film. Agents, thickeners, etc. can be contained. These are described in Research Disclosure, Vol. 176, Item 17643 (Dec. 1978), and in JP-A Nos. 52-108130 and 52-114.
No. 328, No. 52-121321, No. 53-3217.
No. 53-44025 specification, etc. 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. Such a hydrophilic colloid layer may be a single layer or multiple layers, and the thickness of each layer is 0.02 to
The range is preferably 10 μm, more preferably 0.1 to 7 μm, and the total thickness of these layers is preferably 1.5 to 10 μm.

If necessary, an antistatic agent is added to the back layer and / or the photosensitive layer so that the surface resistivity is 10%.
It may be lowered to 12 or less. There is no particular limitation on the means for lowering the surface resistivity. For example, JP-A-58-62648
No. 58-62649, No. 51-11
No. 5,291, Sn, Zn, Ti, I
Method of adding fine powder of oxides of n, V, etc., JP-A-57 / 57
-204540, 54-133324 and other methods for adding the polymer disclosed in JP-A-64-64
No. 26849, No. 61-24907, etc., there is a method of adding a surfactant. Among these methods, the preferred method is to add a metal oxide such as SnO2.

As the fine powder of the metal oxide, a conductive crystalline oxide or a composite oxide thereof is preferable. The fine particles of the electrically conductive crystalline oxide or the composite oxide thereof preferably have a volume resistivity of 10 7 Ωcm or less, more preferably 10 5 Ωcm or less. The particle size is 0.01 to 0.
It is desirable that the thickness is 7μ, particularly 0.02 to 0.5μ.
Regarding the method for producing fine particles of a conductive crystalline metal oxide or composite oxide used in the present invention, Japanese Patent Application No. 55-
It is described in detail in the specification of No. 47663. Firstly, a method of forming the metal oxide fine particles by calcination and performing heat treatment in the presence of different atoms for improving conductivity, and second, for improving conductivity when producing the metal oxide fine particles by firing. A method of making different atoms coexist, a third method of introducing oxygen defects by lowering the oxygen concentration in the atmosphere when producing metal fine particles by firing, and the like are easy. Examples of containing metal atoms include ZnO, Al, In, etc., TiO.
Nb for _2, Ta, etc., Sb for SnO _2,
Examples include Nb and halogen elements. The addition amount of the heteroatom is preferably in the range of 0.01 to 30 mol%, but 0.1 to 30 mol%
It is particularly preferable if it is 10 mol%. Of these, Sb
Most preferred is SnO ₂ fine particles added with.

Further, 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. For example, US Pat.
Nos. 8564, 4124386, and 3625694, JP-A-47-13935, and 55-33.
No. 172, No. 56-36414, No. 57-16185.
No. 3, No. 52-29727, No. 61-198148.
No. 61, No. 61-177447, No. 61-217039.
And the method of adsorbing the dye described in JP-A-61-219039 on a mordant, JP-A-61-213839.
No. 63-208846, No. 63-296039.
JP-A-1-158439, a method of using a diffusion-resistant dye, JP-A-1-142688, a method of emulsifying and dispersing a dye dissolved in an oil into oil droplets, US Patents 2719088 and 2498841
Nos. 2496843, JP-A-60-45
A method for adsorbing the dye described in Japanese Patent Application No. 237, Japanese Patent Application No. Hei 1-136991 to the surface of an inorganic material, Japanese Patent Application No. Hei 1-1
A method of adsorbing a dye described in the specification of 19851 to a polymer, JP-A-56-12639 and JP-A-55-155.
No. 350, No. 55-155351, No. 63-2783.
No. 8, 63-197943, European Patent 15
No. 601, No. 274723, No. 276566, No. 2
99435, International Patent (WO) 88/04794,
There is a method of using a water-insoluble dye solid described in each specification of Japanese Patent Application No. 1-87367. 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.

[0053]

【Example】

Example 1 (1) Polymerization of Polymer To a reaction vessel, 6 liters of toluene as a reaction solvent, 5 mmol of tetraethoxytitanium 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 12 C-NMR to find that 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 glass transition temperature (Tg) and melting point (Tm) of this polymer were 97 ° C. and 250 ° C., respectively. This polymer is called SPS-1. Similarly, polymerization was carried out with the charging ratio (molar ratio) of styrene and p-methylstyrene being 50/0 and 47.88 / 2.12. These were designated as SPS-2 and 3, respectively. These Mw are 400,000 and 420,000 respectively, and Mn is 22 respectively.
10,000, 230,000 and 7 each for Syndiotacticity
4, 71 and Tg were 100 ° C. and 95 ° C., respectively, and Tm was 257 and 248, respectively. Thus, the styrene polymer having a syndiotactic structure, SPS
-1, 2 and 3 (p-methylstyrene contents were 5, 0 and 10 wt% respectively) were obtained.

The above Tg and Tm were determined as follows. 10 mg of a sample is set in a differential thermal analyzer, heated to 330 ° C. at 20 ° C./min in a nitrogen stream, and then rapidly cooled to room temperature. The temperature is raised again in a nitrogen gas 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 of the maximum endothermic point of a large peak appearing on the endothermic side is defined as Tm.

(2) Film formation of support SPS-1, 2 and 3 were dried at 150 ° C. under reduced pressure and dried 1
Crystallization was performed while stirring in hot air at 30 ° C. The content of the monomer in the crystallized pellet was 1,10
It was 0 to 900 ppm. After this, SPS-1, SP
S-2 was kneaded and extruded at 300 ° C. using a vented single-screw extruder. Further, SPS-2 and SPS-3 were kneaded and extruded at 300 ° C. using a twin-screw extruder with a vent so that the mixing ratio of each was 2/1. These were extruded from a T-die heated at 320 ° C. after passing through a sintered metal filter. This molten sheet was cast by biaxial stretching using an electrostatic application method so as to have the thickness shown in Table 1. The crystallinity of the transparent sheet thus obtained was 9%. This was sequentially biaxially stretched 3.2 times at 120 ° C. in the longitudinal direction and then 3.3 times at 125 ° C. in the transverse direction. After that, heat setting was performed at 240 ° C. for 30 seconds under a restricted shrinkage of 5%. In this way SPS-1, S
A support comprising a homopolymer of PS-2 and a polymer of SPS-2 + SPS-3 (hereinafter referred to as "SPS-2 / 3") was obtained. For reference, PET was used to form a film according to a conventional method.

(3) Surface Treatment of Supports Both surfaces of these supports were subjected to glow discharge treatment under the following conditions. A cylindrical electrode with a cross section of 2 cm in diameter and 150 cm in length and having a hollow portion that serves as a coolant channel is provided at intervals of 10 cm.
It was fixed in the shape of an insulating plate. This electrode plate was fixed in a vacuum tank, a 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. Immediately before the film passes through the electrode, the heating roll is placed so that it makes 3/4 round contact with the heating roll with a temperature controller of 50 cm in diameter, and a thermocouple thermometer is placed on the film surface between the heating roll and the electrode zone. By bringing them into contact with each other, the film surface temperature was controlled at 70 ° C. The pressure in the vacuum chamber is 0.2 Torr, and the partial pressure of H2O in the atmospheric gas is 75.
It went in%. Discharge frequency is 30 KHz, output 2500
W, the treatment intensity was 0.5 KV · A · min / 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.

(4) Preparation of photographic light-sensitive material The following undercoat was applied on both sides of the support subjected to glow discharge treatment. ──────────────────────────────────── Undercoat layer ──────────── ──────────────────────── Gelatin 10.0 parts by weight Water 24.0 parts by weight Metanol 961.0 parts by weight Salicylic acid 3.0 parts by weight Polyamide- Epichlorohydrin resin (described in Synthesis Example 1 of JP-A-51-3619) 0.5 part by weight Nonionic surfactant (Compound I-13 described in JP-B-3-27099) 1.0 part by weight ── ───────────────────────────────────

10 ml of this coating solution using a wire bar
/ M ^{2 was} applied. Then, it was dried for 5 minutes under the conditions shown in Table 1 below. The tension at this time is 10 kg at any level.
/ M. Then, the surface condition of the support was evaluated by the following method. The results are shown in Table 1 below.

[0059]

[Table 1] Table 1 ──────────────────────────────────── Support conditions for coating the polymer layer Surface condition number after application (1) (2) (3) (4) (5) (6) (7) ──────────────────────── ───────────── 1-1 SPS-1 100 2.0 15 12 12 0 2 2 1-2 SPS-1 210 2.0 15 15 12 4 42 53 53 1-3 SPS-1 185 2.0 15 12 0 12 11 1-4 SPS-1 60 2.0 15 12 0 1 0 1-5 SPS-1 40 2.0 15 15 12 0 1 0 1-6 SPS-1 100 9.0 9.0 1212 0 15 5 1-7 SPS-1 100 11.0 15 12 1 21 6 1-8 SPS-1 100 2.0 2.0 210 12 0 5 39 1-9 SPS-1 00 2.0 190 12 0 4 22 1-10 SPS-1 100 2.0 15 15 38 0 11 9 1-11 SPS-1 100 2.0 15 40 40 0 17 12 12-12 SPS-2 + 3 100 2.0 15 1203 3 1-13 SPS-2 + 3 210 2.0 15 15 12 4 44 63 1-14 SPS-2 + 3 185 2.0 15 15 12 0 15 17 1-15 SPS-2 + 3 60 2.0 15 15 12 0 1 0 1 -16 SPS-2 + 3 40 2.0 15 12 12 0 1 0 1-17 SPS-2 + 3 100 9 0 15 15 12 0 17 6 1-18 SPS-2 + 3 100 11.0 15 12 12 1 23 7 1-19 SPS-2 + 3 100 2.0 210 12 0 6 40 1-20 SPS-2 + 3 100 2.0 190 190 0 5 5 24 1-21 SPS-2 + 3 100 2.0 15 38 38 12 12 9 1-22 SPS-2 + 3 100 2.0 2.0 15 42 0 18 14 1-2 3 SPS-2 100 2.0 15 12 12 0 2 2 1-24 PET 100 2.0 15 15 2 0 0 0 ───────────────────────── ──────────── Note: (1) Drying temperature (℃) (2) Maximum length between pass rolls (m) (3) Maximum contact length between pass roll and film (cm) (4) Transfer Tension applied to the film at times (5) Stretching failure (pieces) The center of the film is sampled for 10 meters with a width of 30 cm, and the number of occurrences is visually counted while unwinding in sequence on the table without applying tension. This value was divided by 10 to give the number of occurrences per unit length. (6) Waviness failure (mm) Sample the support for 1 m and place it on the table without tension. At this time, the height of the undulations generated at both ends is 100% measured using a ruler. Find this average height. (7) Spot failure (pieces) The support is sampled at 5 points and 5 cm square at equal intervals in the width direction. The seeds generated in this are visually counted and the average number of 5 points is obtained.

A conductive layer and a back layer having the following compositions were coated on the side opposite to the undercoat layer of this support 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 mg / m ² compound-11 7 mg / m ² sodium dodecylbenzene sulfonate 10 mg / m ² dihexyl-α-sulfosuccinate sodium 40 mg / m ² sodium polystyrene sulfonate 9 mg / m ² ──── ────────────────────────────────

──────────────────────────────────── Back layer ────────── ─────────────────────────── Gelatin (Ca ²⁺ content 30ppm) 3.6g / m ² Compound-11 3mg / m ² Poly Methyl methacrylate fine particles (average particle size 3.4 μm) 50 mg / m ² compound-12 40 mg / m ² compound-13 40 mg / m ² compound-14 80 mg / m ² sodium dodecylbenzenesulfonate 75 mg / m ² dihexyl- α- Suruhosakushina - DOO sodium 20 mg / m ² compound -15 5mg / m ² N- perfluorooctane sulfonyl -N- propyl glycine Potassium 7 mg / m ² sodium sulfate 50 mg / m ² sodium acetate 85 mg / m ² 1,2- Bis (bini Lusulfonylacetamide) ethane 150 mg / m ²

[0062]

Embedded image

[0063]

Embedded image

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 support. ──────────────────────────────────── Solution I ──────────── ──────────────────────── Water 1000 ml Gelatin 20 g Sodium chloride 20 g 1,3-Dimethylimidazolidine-2-thione 20 g Sodium benzenesulfonate 6 mg

──────────────────────────────────── II liquid ────────── ─────────────────────────── Water 400ml Silver nitrate 100g ─────────────────── ─────────────────

──────────────────────────────────── III liquid ───────── ─────────────────────────── Water 400 ml Sodium chloride 30.5 g Potassium bromide 14 g Potassium hexachloroiridium (III) (0.001% Aqueous solution) 15 ml Ammonium hexabromodium (III) (0.001% aqueous solution) 1.5 ml ────────────────────────────── ───────

II solution in solution I kept at 38 ° C. and pH = 4.5
The liquid and the liquid III were added simultaneously with stirring for 10 minutes to form fine particles of 0.16 μm. Then IV below
Solution and Solution V were added over 10 minutes. Further, 0.15 g of potassium iodide was added to complete grain formation.

──────────────────────────────────── IV liquid ───────── ─────────────────────────── Water 400ml Silver nitrate 100g ─────────────────── ─────────────────

──────────────────────────────────── V liquid ────────── ─────────────────────────── Water 400 ml Sodium chloride 30.5 g Potassium bromide 14 g K ₄ Fe (CN) ₆ 1 × 10 ^-5 Mol / mol Ag ─────────────────────────────────────

Thereafter, according to a conventional method, the product was washed with water by the flocculation method and 40 g of gelatin was added. This emulsion was adjusted to pH = 5.3 and pAg = 7.5, 5.2 mg of sodium thiosulfate, 10.0 mg of chloroauric acid and N,
2.0 mg of N-dimethylselenourea and 2.0 mg of sodium benzenesulfonate were added, and chemical sensitization was performed at 55 ° C. to obtain optimum sensitivity, and finally 80 mol% of silver chloride.
A cubic silver iodochlorobromide cubic grain emulsion having an average grain size of 0.20 μm was prepared. Then, a sensitizing dye was added at 5.times.10@-4 mol / mol Ag for ortho-sensitization. Further, as antifoggants, hydroquinone and 1-phenyl-5-mercaptotetrazole were added in amounts of 2.5 per 1 mol of Ag, respectively.
g, 50 mg, colloidal silica (Nissan Chemical's SNO-TEX C, average particle size 0.015 μm) was added to gelatin in an amount of 30% by weight, and polyethyl acrylate latex (0.05 μm) as a plasticizer was added to gelatin to 4%.
0% by weight, 100 mg / m ^{2 of} 1,1′-bis (vinylsulfonyl) methane was added as a hardening agent. The coating solution Ag3.9g / m ^2, was coated so as to be gelatin 1.8 g / m ^2.

[0071]

[Chemical 4]

───────────────────────────────────── Protective layer lower layer per m ² ───── ──────────────────────────────── Gelatin 0.7g Sodium benzenesulfonate 4mg 1,5-Dihydroxy-2-benzald Kisme 25 mg Polyethyl acrylate latex 125 mg ─────────────────────────────────────

──────────────────────────────────── Protection layer upper layer per m ² ───── ─────────────────────────────── Gelatin 0.5g Polymethylmethacrylate fine particles (average particle size 2.5 μm) 40 mg Compound-16 (gelatin dispersion of lubricant) 60 mg Colloidal silica (Nissan Chemical's Sunotex C) 60 mg Compound-17 5 mg Sodium dodecylbenzenesulfonate 22 mg ──────────────── ───────────────────── The coefficient of dynamic friction of this sample is 0.22 ± 0.03 (2
5 ° C 60% RH, sapphire needle φ = 1mm, load 100
g, speed 60 cm / min).

[0074]

Embedded image

(5) Evaluation of Photosensitive Material The sample thus obtained was coated at 25 ° C. for 6 days for 10 days.
After storing at 0% RH, cut at 25 ° C and 60% RH.
After processing, the following evaluation was carried out. (5-1) Humidity dimension shift Sensitive material (60% RH) placed in high humidity has low humidity (20% RH)
Then, the exposure time is changed while the exposure time is changed. The one exposed immediately does not shrink the photosensitive material, and the photosensitive material shrinks sufficiently after being left for a long time (1 hour). The humidity dimensional stability is evaluated by measuring the distance between the exposure points of these two sensitive materials. (Exposure of photosensitive material) A photosensitive material cut into a width of 25.5 cm is
After adjusting the humidity to 25 ° C. and 60% RH, the magazine was loaded. The first plate was exposed immediately after being set on a scanner-exposure machine (Magnaset 350: manufactured by Fuji Photo Film Co., Ltd.) installed in a constant environment of 25 ° C. and 20% RH. For the exposure, a square of 0.5 mm was exposed on the four corners of the film (width direction: 250 mm intervals, longitudinal direction interval: 600 mm). After 1 hour, the second plate was exposed in the same manner. (Development of photosensitive material) Fuji Photo Film SR-D1 and SR-F1 were used as a developing solution and a fixing solution, and the temperature was 38 ° C. 2 with an automatic processor FG-660F (Fuji Photo Film).
A 0 second development process was performed.

Dimensional evaluation of the photosensitive material The developed photosensitive material was subjected to the first test in a constant environment of 25 ° C. and 60% RH.
After the squares of the plate and the second plate (A: the first exposed point) were overlapped with each other as a reference point, the distance between the other three squares was measured as follows. (1) Point B (indicating deviation in width direction): Width direction 2 of square A
The square exposed at 50 mm is designated as point B. First Edition and Second Edition
The shift in the width direction of the square at point B on the plate is measured. (2) Point C (indicating a deviation in the length direction): The square exposed in the length A of the square A is defined as the point C. The shift in the longitudinal direction of the squares at point C of the first and second editions is measured. (3) Point D (indicating deviations in the width and length directions): Square A
The square exposed in the diagonal direction is defined as point D. The deviation in the longitudinal direction: Dl and the deviation in the width direction: Dw of the squares of the first and second plates are measured.

(5-2) Evaluation of Image Blur When the flatness of the photosensitive material is poor, a gap is formed between the original film and the original film superimposed on it. This gap causes image blur. When exposure is performed at a high density of halftone dots, the halftone dots stick to each other due to image blurring, which can be visually confirmed. (Exposure) An original film (35 cm x 40 cm) was used with a contact exposure printer using a halftone original film having a halftone dot image of 10%.
cm) and the sample film were combined and subjected to vacuum contact exposure. This was done for 10 films per level. (Development) The development was performed in the same manner as in the above-mentioned item of dimension evaluation. (Evaluation) 10 points where the dots in the halftone image are stuck
The film was visually measured for each film.

(5-3) Evaluation of Adhesiveness After making cuts in a grid pattern on the emulsion surface with a razor at 5 mm intervals, an adhesive tape was attached and quickly peeled in the direction of 180 ° to evaluate the adhesion level. The peeled area is 5
% Or less A, 5% to 10% or less B,
A value exceeding 10% was designated as C. A and B are allowed
Is. The above results are shown in Table 2 below.

[0079]

[Table 2] Table 2 ──────────────────────────────────── Supports When layers are layered Dimensional deviation number Adhesion Width direction B Width direction D Longitudinal method C Longitudinal direction D Image blur ────────────────────────────── ────── 1-1 A 20μm 25μm 42μm 49μm 0 1-2 A 150μm 185μm 300μm 350μm 36 1-3 A 45μm 50μm 82μm 91μm 0 1-4 B 16μm 20μm 30μm 35μm 0 1-5 C 15μm 21μm 32μm 34μm 0 1-6 A 40 μm 42 μm 82 μm 90 μm 0 1-7 A 85 μm 90 μm 175 μm 190 μm 8 1-8 A 45 μm 48 μm 90 μm 96 μm 0 1-9 A 32 μm 35 μm 62 μm 1 72 μm 1- 0 A 38 [mu] m 39 [mu] m 82 [mu] m 86 [mu] m 0 1-11 A 48 [mu] m 50 [mu] m 88 [mu] m 90 [mu] m 0 1-12 A 22 [mu] m 27 [mu] m 46 [mu] m [mu] m [mu] m [mu] m 85 [mu] m 90 [mu] m 90 [mu] m 48 [mu] m 15 [mu] m 48 [mu] m 48 [mu] m 45 [mu] m 42 [mu] m 42 [mu] m [] 38 μm 0 1-16 C 18 μm 22 μm 35 μm 36 μm 0 1-17 A 41 μm 44 μm 83 μm 92 μm 0 1-18 A 88 μm 92 μm 117 μm 195 μm 0 μm 21 μm 21 μm 1 μm 19 μm 20 μm 1 μm 19 μm 20 μm 0 A 39 μm 42 μm 85 μm 88 μm 0 1-22 A 47 μm 52 μm 89 μm 10 μm 0 1-23 A 20 μm 24 μm 44 μm 48 μm 0 1-24 A 65 μm 69 μm 125 μm 150 μm 0 ─ ──────────────────────────────────

(6) Results PET of the comparative example (Level 1-2) was used for carrying out the present invention.
Compared to 4), the deviation was extremely small and a good value was exhibited even after the superposition. Furthermore, even when overprinted, good results were obtained without the occurrence of halftone dot sticking accompanying image blurring. On the other hand, when dried at a temperature exceeding the range of the present invention and a length between pass rolls, dimensional deviation and image blur occurred.
Under the drying temperature of the present invention, poor adhesion of the emulsion occurred. Furthermore, by implementing the maximum value of the length in contact with the pass roll and the tension within the range of the present invention, it is possible to further improve the dimensional deviation during repeated baking.

Example 2 (1) Polymerization of Polymer Styrene-based polymers having the syndiotactic structure described in Example 1, SPS-1, 2 and 3 (p-methylstyrene content of 5, 0 respectively) And 10 wt%) were obtained. To this, the fine particles shown in Table 3 were added. (2) Film formation of support SPS-1, 2 and 3 were decompressed at 150 ° C. and dried to 130
Crystallization was carried out while stirring in hot air at ℃. The content of the monomer in the crystallized pellet is 1,100 to
It was 900 ppm. After this, SPS-1, SPS-
No. 2 was kneaded and extruded at 300 ° C. using a vented single-screw extruder. Further, SPS-2 and SPS-3 were kneaded and extruded at 300 ° C. using a twin-screw extruder with a vent so that the mixing ratio of each was 2/1. These were passed through a sintered metal filter and then extruded from a T-die heated to 320 ° C. This fused sheet is used to
Casting was performed so that the thickness after axial stretching and heat setting would be the values shown in Table 2. The crystallinity of the transparent sheet thus obtained was 9%. This was passed between two rolls having different peripheral speeds and stretched in the longitudinal direction. An infrared heater was used to heat the support, and the distance between this and the roll with the higher peripheral speed (B-roll) was set to the value shown in Table 2. The stretching temperature is 120 ° C. and the stretching ratio is shown in Table 3.
Preheat this at 125 ℃ for 30 seconds,
The transverse stretching was performed at the magnification shown in the table. However, only 2-14 was transversely stretched and then re-stretched 1.3 times in the longitudinal direction at 130 ° C.
After that, heat setting was carried out for 30 seconds at the temperature shown in Table 3 below. At this time, the width was relaxed by the amount shown in Table 3.

[0082]

[Table 3] Table 3 ──────────────────────────────────── Support Polymer Polymer Thickness- added fine particles Longitudinal stretching Horizontal stretching Heat set number (μm) Particle size Amount Distance Magnification Magnification Temperature relaxation rate ─────────────────────────────── ───── 2-1 SPS-1 175 0.2 60 28 3.7 4.0 8.0 230 8 2-2 SPS-1 175 0.2 60 28 4.3 4.3 4.4 230 8 2-3 SPS- 1 175 0.2 60 60 28 2.7 2.7 230 8 2-4 SPS-1 175 0.2 60 60 2.8 2.9 230 8 2-5 SPS-1 175 0.2 60 60 3.7 4.0 230 8 2-6 SPS-1 175 None-28 3.7 4.0 230 230 2-7 SPS-2 + 3 175 5.1 350 28 3.7 4.0 230 8 8 2-8 SPS- 2 175 0.2 60 28 3.7 4.0 4.0 230 8 2-9 SPS-1 175 0.2 60 28 3.7 4.0 230 230 8 2-10 SPS-1 175 0.2 60 28 2.7 3.7 4. 0 230 8 2-11 SPS-1 85 0.2 60 28 3.7 4.0 4.0 230 8 2-12 SPS-1 100 0.2 60 28 3.7 4.0 230 230 8 2-13 SPS-1 175 0.2 60 28 3.7 4.0 4.0 260 0-14 SPS-1 175 0.2 60 28 3.7 x 1.3 4.0 260 0 ────────────────── ─────────────────── (Note) Average particle size of added particles: μm Amount of added particles: ppm Distance between longitudinal stretching: cm Heat setting temperature: ° C Heat setting relaxation rate:%

With respect to the biaxially stretched SPS support thus obtained, the heat shrinkage at 110 ° C., Young's modulus, difference in heat flow rate, and haze were measured. Also, at 25 ° C of these supports,
The rate of dimensional change in humidity was determined from the dimensional change in humidity from 60% RH to 25 ° C. and 20% RH. In all of the supports of the present invention, a good value of 0.5 to 1.5 × 10 −6 /% RH was obtained. Showed the value. (2) Young's modulus at 110 ° C. Using a tensile tester having a constant temperature layer, at 110 ° C., pulling speed 500 mm / min, chuck distance 100 m
m, sample width 10 mm. 5 points at equal intervals in the width direction and 5 points every 30 cm in the longitudinal direction (measured at the width center)
Measure the values in the longitudinal and width directions at 0 points respectively. The average value of each 10 points was obtained. For the in-plane deviation, the maximum value and the minimum value of 10 points in the longitudinal direction, 10 points in the width direction, and 20 points in total are used, and the in-plane deviation (%) = 100 × {(maximum value) − (minimum value)} / It was calculated as (maximum value) (%).

(3) Thermal dimensional change: After sampling at 25 cm × 5 cm, holes are made at 20 cm intervals, and the length is measured at 25 ° C. using a pin gauge.
(This is designated as L1) After this, at 110 ° C, without tension, 1
Leave for 0 minutes. After leaving this at 25 ° C. for 3 hours or more, the length is measured again with a pin gauge. (This is L2). The absolute value of 100 x (L2-L1) / L1 (%) is defined as the thermal dimensional change rate. 5 points at equal intervals in the width direction, 30c in the longitudinal direction
The values in the longitudinal direction and the width direction are measured at 10 points of 5 points per m (measured at the center of the width). The average value of each 10 points was obtained. The in-plane deviation range is calculated as in-plane range (%) = {(maximum value)-(minimum value)} using the maximum and minimum values of 20 points in the longitudinal direction and 10 points in the width direction, totaling 20 points. It was (4) Difference in heat flow rate Measure with a differential thermal analyzer (DSC). A film sample of 5 mg to 10 mg was precisely weighed, put in a pan, and then measured under a nitrogen stream while raising the temperature at 20 ° C./min. The difference between the heat flow rate at 90 ° C. and the heat flow rate at 115 ° C. Ask. (5) Surface roughness (Ra) Using a surface roughness measuring instrument (SE-3FK) manufactured by Kosaka Laboratory,
The tip radius of the stylus is 2 μm, the load is 30 mg, the measurement length is 2.5 mm, the cutoff is 80 μm, and the measured value is expressed in μm. The above results are shown in Table 4.

[0085]

[Table 4] Table 4 ──────────────────────────────────── Support 110 ° C Young's modulus 110 ℃ Heat shrinkage heat flow rate Haze number LD TD deviation LD TD Range difference (%) ────────────────────────────────── ──── 2-1 190 160 18 0.3 0.4 0.4 0.1 0.049 0.4 2-2 330 310 7 0.9 1.4 0.5 0.018 5.9 2-3 41 45 12 0.2 0.3 0.3 0.2 0.059 2.2 2-4 52 54 11 0.3 0.4 0.4 0.2 0.072 2.1 2-5 180 130 130 32 0.2 0.7 0.9 0.055 0.7 2-6 200 170 16 0.2 0.3 0.2 0.045 0.1 2-7 240 190 17 0.3 0.2 0.2 0.2. 042 2.6 2-8 150 130 14 0.3 0.7 0.7 0.5 0.042 0.7 2-9 210 150 150 32 0.3 0.7 0.1 0.037 1.8 2-10 190 160 18 0.3 0.4 0.4 0.049 0.4 2-11 180 160 11 0.3 0.4 0.1 0.046 0.2 2-12 185 160 9 0.3 0.3 0.3 0.048 0.3 2-13 200 200 180 15 0.7 0.7 0.7 0.7 0.052 3.4 2-14 230 200 19 0.9 0.9 0.5 0.5 0.035 3. 4 ──────────────────────────────────── (Note) Young's modulus: kg / mm ² Young's modulus In-plane deviation:% Heat shrinkage and its in-plane range:% Heat flow rate difference: W / g Haze:%

(3) Surface Treatment of Supports These supports were subjected to the glow discharge treatment described in Example 1 on both sides. (4) Undercoat of support The undercoat described in Example 1 was applied on both sides of the support subjected to glow discharge treatment. This coating solution was applied at 10 ml / m 2 using a wire bar. After this, the drying temperature is 110 ° C,
The drying zone was dried for 5 minutes at a maximum length between path rolls of 2 m, a maximum support roller contact length of 15 cm, and a tension of 12 kg / m. After this, the waviness height was evaluated according to the method described above. Further, the flatness after undercoating (strength failure, spot failure) was evaluated in the same manner as in Example 1. The results are shown in Table 5.

(5) Preparation of photographic light-sensitive material The following two types of back layers and photosensitive layers were coated on the support after undercoating. (A) Back layer / photosensitive layer = a (symbol in Table 5) The following back layer and photosensitive layer were coated on all the samples except 2-10. (1) Coating of Back Layer A conductive layer having the following formulation and a back layer were simultaneously coated on one side of the support in the order of being closer to the support using a slide coater. ──────────────────────────────────── (1-1) Conductive layer ─────── ───────────────────────────── Gelatin (Ca ²⁺ content: 3000ppm) 100mg / m ² Compound-A 1mg / m ² Dihexyl-α-sulfosuccinate sodium 11 mg / m ² Sodium dodecylbenzenesulfonate 15 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μm) 200 mg / m ² ────────────────────────────────────

──────────────────────────────────── (1-2) Back layer ──── ──────────────────────────────── Gelatin (Ca ²⁺ content: 30ppm) 1.5g / m ² Polymethyl Methacrylate fine particles (average particle size 3.4 μm) 20 mg / m ² compound-A 4 mg / m ² dye-60 mg / m ² dye-40 mg / m ² dye-32 mg / m ² dihexyl-α-sulfosuccinate sodium 20 mg / m ² Sodium dodecylbenzene sulfonate 80 mg / m ² Acetic acid 7 mg / m ² Sodium sulfate 200 mg / m ² Compound-C 8 mg / m ² Compound-D 9 mg / m ² Sodium polystyrene sulfonate 16 mg / m ² 1,3-bis (vinyl Sulfonyl) -propanol-2 1.8 wt% of gelatin ───────────────── ───────────────────

[0089]

[Chemical 6]

(2) Coating of photosensitive layer Next, a non-photosensitive layer, an emulsion layer and a protective layer were simultaneously coated on the other surface in the order of being closer to the support using a slide coater and dried. ──────────────────────────────────── (2-1) Non-photosensitive layer ────── ────────────────────────────── Gelatin 1.0 g / m ² Compound-A 2 mg / m ² Sodium polystyrene sulfonate 15 mg / m ² 2,4-dichloro-6-hydroxy-s-triazine 7 mg / m ² 1,3-bis (vinylsulfonyl) -propanol-2 15 mg / m ² polyethyl acrylate latex (particle size 0.05 μm) 600 mg / m ² ────────────────────────────────────

(2-2) Emulsion Layer A silver halide emulsion containing 30 mol% of silver bromide and 70 mol% of silver chloride containing 3.5 × 10 −7 mol of rhodium per 1 mol of Ag is well known in the art. Prepared by the usual method, and after removing soluble salts, gelatin was added. Ag in this emulsion
Sodium thiosulfate 6 mg, chloroauric acid 8.5 mg per mole
In addition, chemical sensitization was performed at 60 ° C. for 50 minutes. The average grain size of the resulting emulsion was 0.25μ cubic grains and emulsion 1
The amount of Ag per kg was 125 g and the amount of gelatin was 53 g.
1- (2-hydroxyethoxyethyl) -3- (pyridin-2-yl) -5 was added to this emulsion as an ortho sensitizing dye.
-[(3-Sulfobutyl-5-chloro-2-benzoxazolinidene) ethylidene] -2-thiohydantoin potassium salt 11 mg / m ² was added, and α-riboic acid 7 mg /
m ² , hydroquinone 27 mg / m ² , compound-3 mg / m ² ,
1-phenyl-5-mercapto-tetrazole 1 mg /
m ² , compound-1 mg / m ² , compound-6 mg / m ² , compound-4 mg / m ² , compound- ² mg / m ² , 6-as stabilizer
Methyl-4-hydroxy-1,3,3a, 7-tetrazaindene 8 mg / m ² , and as a hardening agent 1,3-bis (vinylsulfonyl) -propanol-2 40 mg / m ² were added, and ethyl acrylate was further added. 900 mg / m ^{2 of} latex (average particle size 0.05 μm) and 40 mg / m ² of polystyrenesulfonic acid sodium salt as a thickener were added. This coating solution was applied so that the amount of silver was 3.5 g / m ² and the amount of gelatin was 1.6 g / m ² .

[0092]

[Chemical 7]

──────────────────────────────────── (2-3) Protective Layer Prescription ─── ───────────────────────────────── Gelatin 1.0 g / m ² Polymethylmethacrylate fine particles (average particle size 2 .5 μm) 40 mg / m ² compound-B 50 mg / m ² sodium dodecylbenzene sulfonate 40 mg / m ² sodium polystyrene sulfonate 8 mg / m ² 2,4-dichloro-6-hydroxy-s-triazine 18 mg / m ² ── ───────────────────────────────────

[0094]

Embedded image

(B) Back layer / photosensitive layer = b (symbol described in Table 5) Sample No. 2-10 was coated with the following back layer and photosensitive layer. (1) Coating of back layer A conductive layer having the following formulation and a back layer were simultaneously coated on one side of the support in the order of proximity from the support using a slide coater, and dried at 40 ° C for 5 minutes. ──────────────────────────────────── (1-1) 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 mg / m ² compound-11 7 mg / m ² sodium dodecylbenzenesulfonate 10 mg / m ² dihexyl-α-sulfosuccinate sodium 40 mg / m ² sodium polystyrenesulfonate 9 mg / m ² ────────────────────────────────────

──────────────────────────────────── (2) Back layer ────── ────────────────────────────── Gelatin (Ca ²⁺ content: 30 ppm) 3.6 g / m ² Compound-11 3 mg / M ² Polymethylmethacrylate fine particles (average particle size 3.4 μm) 50 mg / m ² compound-12 40 mg / m ² compound-13 40 mg / m ² compound-14 80 mg / m ² sodium dodecylbenzenesulfonate 75 mg / m ² Dihexyl-α-sulfosuccinate sodium 20 mg / m ² compound-15 5 mg / m ² N-para-fluorooctanesulfonyl-N-propylglycine potassium 7 mg / m ² sodium sulfate 50 mg / m ² sodium acetate 85 mg / m ² 1,2-bis Vinylsulfonyl acetamide) ethane 150mg / m ² ────────────────────────────────────

[0097]

[Chemical 9]

(2) Coating of photosensitive layer Next, an emulsion layer having the following composition, a protective layer lower layer and a protective layer upper layer were simultaneously coated on the opposite surface of the support. (2-1) Emulsion layer ──────────────────────────────────── Solution I ───── ──────────────────────────────── Water 1000ml Gelatin 20g Sodium chloride 20g 1,3-Dimethylimidazolidin-2-thione 20g Sodium benzenesulfonate 6mg ────────────────────────────────────

──────────────────────────────────── II liquid water 400 ml silver nitrate 100 g ───── ───────────────────────────────

──────────────────────────────────── III liquid ────────── ─────────────────────────── Water 400 ml Sodium chloride 30.5 g Potassium bromide 14 g Potassium hexachloroiridium (III) (0.001% Aqueous solution) 15 ml Ammonium hexabromodium (III) (0.001% aqueous solution) 1.5 ml ────────────────────────────── ───────

II solution in solution I kept at 38 ° C. and pH = 4.5
The liquid and the liquid III were added simultaneously with stirring for 10 minutes to form fine particles of 0.16 μm. Then IV below
Solution and Solution V were added over 10 minutes. Further, 0.15 g of potassium iodide was added to complete grain formation. ──────────────────────────────────── IV liquid ──────────── ──────────────────────── Water 400ml Silver nitrate 100g ────────────────────── ──────────────

──────────────────────────────────── V liquid ───────── ─────────────────────────── Water 400 ml Sodium chloride 30.5 g Potassium bromide 14 g K ₄ Fe (CN) ₆ 1 × 10 -5 Mol / mol Ag ────────────────────────────────────

Then, according to a conventional method, the product was washed with water by the flocculation method and 40 g of gelatin was added. This emulsion was adjusted to pH = 5.3 and pAg = 7.5, sodium thiosulfate 5.2 mg, chloroauric acid 10.0 mg and N,
2.0 mg of N-dimethylselenourea and 2.0 mg of sodium benzenesulfonate were added, and chemical sensitization was performed at 55 ° C. to obtain optimum sensitivity, and finally 80 mol% of silver chloride.
A cubic silver iodochlorobromide cubic grain emulsion having an average grain size 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 an amount of 2.5 per mol of Ag, respectively.
g, 50 mg, colloidal silica (Nissan Chemical's SNO-TEX C, average particle size 0.015 μm) was added to gelatin in an amount of 30% by weight, and polyethyl acrylate latex (0.05 μm) as a plasticizer was added to gelatin. Four
0% by weight, 100 mg / m ^{2 of} 1,1′-bis (vinylsulfonyl) methane was added as a hardening agent. The coating solution Ag3.9g / m ^2, was coated so as to be gelatin 1.8 g / m ^2.

[0104]

[Chemical 10]

──────────────────────────────────── (2-2) Protective layer Lower layer per m ² ──────────────────────────────────── Gelatin 0.7g Sodium benzenesulfonate 4mg 1,5-dihydroxy -2-Benzaldoxime 25 mg Polyethyl acrylate latex 125 mg ─────────────────────────────────────

──────────────────────────────────── (2-3) Upper layer of protective layer per m ² ──────────────────────────────────── Gelatin 0.5g Polymethylmethacrylate fine particles (average particle size) Diameter 2.5 μm) 40 mg Compound-16 (gelatin dispersion of lubricant) 60 mg Colloidal silica (SUN-TEX C manufactured by Nissan Kagaku Co., Ltd.) 60 mg Compound-17 5 mg Sodium dodecylbenzenesulfonate 22 mg ──────────── ────────────────────────── 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).

[0107]

[Chemical 11]

(6) Evaluation of photographic light-sensitive material The light-sensitive material sample thus obtained was applied for 25 days for 10 days.
After storing at 60 ° C RH of 60 ° C, cutting and processing at 60% RH of 25 ° C, evaluation was performed as follows. (5-1) Dimensional deviation (exposure of photosensitive material) 2
The humidity was controlled in a moisture-proof bag overnight at 5 ° C. and 60% RH. This was opened and immediately exposed to flood bed using a LPP-3680 type exposure device at 25 ° C. and 20% RH. At this time, marks of 5 mm square were baked at the four corners of 30 cm in the longitudinal direction and 30 cm in the width direction.

(Development processing of light-sensitive material) An automatic developing machine FG-660F (manufactured by Fuji Photo Film) using HS-5 and LF-5 manufactured by Fuji Photo Film as developer and fixer.
After development at 32 ° C. for 60 seconds, it was dried at 42 ° C. for 60 seconds. (Dimensional Evaluation of Photosensitive Material) The developed photosensitive material was measured under constant environment of 25 ° C. and 60% RH using Mitutoyo FJ805 to measure the distance between the four exposure points. The difference between this value and the distance at the time of exposure is shown in Table 2 after averaging the dimensional deviation. (5-2) Evaluation of Image Blur Evaluation was performed in the same manner as in Example 1. The above results are shown in Table 5.

[0110]

[Table 5] Table 5 ──────────────────────────────────── Surface condition after coating the support Sensitive material / Photosensitive material characteristic number (5) (6) (7) Back layer dimensional change Image blur ───────────────────────────── ──────── 2-1 0 0 0 a 15 μm 0 2-2 8 8 42 a 88 μm 25 2-3 10 9 90 a 96 μm 33 2-4 12 9 0 93 μm 38 2 5 1 2 4 a 65 μm 0 pcs 2-6 0 0 3 a 23 μm 0 pcs 2-7 0 0 0 a 18 μm 0 pcs 2-8 1 2 0 a 60 μm 0 pcs 2-9 1 2 0 a 51 μm 0 pcs 2- 10 0 0 0 15 μm 0 pieces 2-11 1 3 0 b 45 μm 0 pieces 2-12 0 0 0 b 20 μm 0 pieces 2-13 3 5 5 i 55 μm 0 pieces 2-14 10 8 25 B 85 μm 22 pieces ──────────────────────────────────── Note: (5) Strengthening failure (piece ) The measuring method is the same as that of the first embodiment. (6) Rippling failure (mm) The measuring method is the same as that of the first embodiment. (7) Butt failure (pieces) The measuring method is the same as that of the first embodiment.

(6) Results By using the support of the present invention having a difference in Young's modulus at 110 ° C., heat shrinkage characteristics, and heat flow rate, excellent flatness after undercoating, excellent dimensional characteristics and double baking characteristics can be obtained. An excellent sensitive material can be provided. Furthermore, the in-plane deviation of these characteristics,
By further reducing the in-plane range, using the support having the thickness of the present invention, and adding fine particles to the support, more excellent flatness, photosensitive material properties, and haze were achieved. All the samples that were heat-set at 250 ° C. or lower had a low haze and were good. The sample subjected to re-stretching has high heat shrinkage and haze, and as a result, the waviness height exceeds the range of the present invention. Further, a sample prepared in exactly the same manner as the sample of the present invention was evaluated except that the thickness of the support was set to 310 μm, but it was not allowed due to jamming generated by an automatic processor.

[0112]

According to the present invention, a silver halide photographic light-sensitive material is obtained in which dimensional deviation and image blurring hardly occur when overprinted. This is an effect obtained by improving a styrene polymer film having a styrene polymer having a syndiotactic structure as a main component and having an undercoat layer and a method for producing the same.

[Brief description of drawings]

FIG. 1 is a schematic sectional view illustrating a method for measuring a corrugation height.

FIG. 2 is a schematic sectional view of a longitudinal stretching step.

[Explanation of symbols]

 h Wavy height MD Longitudinal direction TD Width direction 1 Reference line 2 Styrene polymer film 3 Coating layers 21a, 21b, 21c Heater 22 Styrene polymer film 23 Conveying roll 24 Low peripheral speed stretching roll 25 High peripheral speed stretching roll L Between stretching distance

Claims (10)

[Claims] 1. A styrene polymer film comprising a styrene polymer having a syndiotactic structure as a main component and provided with a coating layer, wherein the undulation height of the film is 18 mm or less. A styrene polymer film having 2. A styrene polymer film having a coating layer according to claim 1, wherein the Young's modulus at 110 ° C. is 50 to 300 kg / mm ² in both the longitudinal direction and the width direction. 3. The styrene polymer film according to claim 1, wherein the dimensional change in the longitudinal direction and the width direction before and after the heat treatment at 110 ° C. for 10 minutes is 0.8% or less. 4. The styrene polymer film having a coating layer according to claim 2, wherein the in-plane Young's modulus deviation at 110 ° C. is 30% or less. 5. A styrene polymer film having a coating layer according to claim 3, wherein the in-plane range of dimensional change before and after heat treatment at 110 ° C. for 10 minutes is 0.6% or less. 6. The styrene polymer film having a coating layer according to claim 1, wherein the difference in heat flow rate between 90 ° C. and 115 ° C. is 0.02 to 0.07 W / g. 7. A method for producing a styrene polymer film having a coating layer as defined in claim 1, wherein the layer is applied to a film containing a styrene polymer having a syndiotactic structure as a main component; And having a coating layer characterized by including a step of drying the coating layer at 50 to 200 while transporting using a plurality of rolls whose maximum length between rolls is set to 0.1 to 10 m. Method for producing styrene polymer film. 8. The manufacturing method according to claim 7, wherein the maximum length of the region where the film and the roll contact each other in the drying step is 3 to 200 cm. 9. The manufacturing method according to claim 7, wherein the tension applied to the film in the drying step is 2 to 40 kg / m. 10. A support containing a styrene polymer having a syndiotactic structure as a main component, an undercoat layer, and / or
Alternatively, a silver halide photographic light-sensitive material provided with a back layer and at least one silver halide emulsion layer, wherein the undulation height of the support is 18 mm or less. material.