KR960004313B1 - Photographic film - Google Patents

Abstract

A photographic film which comprises (A) a stretched film of a styrene polymer having a syndiotactic configuration or a composition containing it, wherein the thickness is 20 to 500 mu m, haze is not more than 3% and moisture expansion coefficient is not more than 1 x 10<-><6>/%RH, and (B) a photosensitive layer, which is light and excellent in mechanical properties, is disclosed.

Description

Photographic film

The present invention relates to a photographic film, and more particularly, to a photographic film made of a specific base film layer and a photosensitive layer, which is light in weight, has excellent mechanical properties, and also has good dimensional stability.

Conventionally, as a base film of a photographic film, a cellulose crab polymer film, a polyester film, the polystyrene film of the atactic structure, etc. are used. In particular, as a film base other than the winding film, a polyester film having excellent mechanical properties and other balance is used.

However, the cellulose-based polymer film is expensive because of producing the film by the wet method, and the mechanical strength is not sufficient. On the other hand, polyester film has the disadvantage of high specific gravity and weak humidity, and when it is dried at a high temperature in a state of containing moisture, there is a risk of deterioration due to hydrolysis. There is a desire for improvement in applications such as master films where changes occur and (humidity expansion coefficient 1-2 × 10 ^-5 /% RH) precision is required.

In addition, the polystyrene film of the atactic structure is excellent in transparency, humidity dimensional stability, water absorption, etc., but inferior in heat resistance and mechanical properties. Thus, the conventionally used base film has various problems, and the physical properties of the obtained photo film were not necessarily satisfied.

Thus, the present inventors made diligent research to develop a photo film having better physical properties. As a result, a styrene polymer having a syndiotactic structure or a composition thereof has a significantly lower humidity expansion coefficient than that of a conventional heat resistant resin, and is found to be suitable as an introduction of a photographic film, and has a specific thickness and haze value. It has been found that the photographic film using the film of the humidity expansion coefficient as the base film achieves the above-mentioned object. The present invention has been completed based on these findings.

That is, the present invention (A) made of a styrenic polymer having a syndiotactic structure or a composition containing the same, at the same time 20-500 ㎛ stretch haze 3% or less, humidity expansion coefficient of 1 × 10 ^-6 /% RH It is to provide a photo film composed of a film layer (hereinafter referred to as A layer) and (B) photosensitive layer (hereinafter referred to as B layer). The layer A in the present invention uses a styrenic polymer having a syndiotactic structure or a film containing a composition as one component as a so-called base film of a photographic film.

Here, the styrene-based polymer having a syndiotactic structure is one having a three-dimensional structure in which phenyl groups or derivatives thereof, which are side chains, are alternately located in opposite directions with respect to the main chain formed from a carbon-carbon bond. The surname (taxicity) is generally quantified by the nuclear magnetic resonance method ( ¹³ C-NMR method) by carbon isotope and is excellent in precision.

The stereoregularity quantified by the ¹³ C-NMR method can be expressed as a plurality of consecutive unit abundances, for example, two cases of diamonds, three cases of triads, and five cases of pentads.

Styrene-based polymers having a syndiotactic structure as used in the present invention are usually at least 75%, preferably at least 85%, or at least 30%, preferably at least 50%, of racemic dies. Having a last name.

Specifically, stereoregular polystyrene, poly (alkylstyrene), poly (halogenated styrene), poly (halogenated styrene), poly (alkoxy styrene), poly (vinylbenzoic acid ester), hydrogenated polymers thereof and mixtures thereof or these Refers to an interpolymer containing a structural unit of

In addition, as poly (alkyl styrene), poly (methyl styrene), poly (ethyl styrene), poly (propyl styrene), poly (butyl styrene), poly (phenyl styrene), poly (vinyl naphthalene), poly (vinyl styrene) And poly (acenaphthalene), and the like (poly (halogenated styrene)) include poly (chlorostyrene), poly (bromostyrene), poly (fluorostyrene) and the like.

Examples of poly (alkoxy styrene) include poly (methoxy styrene) and poly (ethoxy styrene).

In addition to the monomers of the above-described styrene-based polymers, as the hybrid monomer component of the interpolymer containing these structural units, olefin monomers such as ethylene, propylene, butene, hexene and octene, diene monomers such as butadiene and isoprene, And cyclic olefin monomers, cyclic diene monomers or polar vinyl monomers such as methyl methacrylate, maleic anhydride and acrylonitrile.

Among these, particularly preferred styrene polymers include polystyrene, poly (alkyl styrene), hydrogenated polystyrene, and interpolymers containing these structural units.

There is no particular limitation on the molecular weight of the styrene polymer, but the weight average molecular weight is preferably 10,000 or more and 3,000,000 or less, particularly preferably 50,000 or more and 1,500,000 or less.

Moreover, although various things can be covered, it is preferable that weight average molecular weight (Mw) / number average molecular weight (Mn) is 1.5 or more and 8 or less.

In addition, the styrene polymer having the syndiotactic structure is remarkably excellent in heat resistance as compared with the conventional styrene polymer of the atactic structure.

Styrene-based polymers having such syndiotactic structure include styrene-based monomers (the styrene-based polymers described above) using, for example, a condensation product of a titanium compound and water and trialkylaluminum in an inert hydrocarbon solvent or in the absence of a solvent. It can manufacture by superposing | polymerizing in the monomer). (Japanese Unexamined-Japanese-Patent No. 62-187708).

Moreover, about poly (halogenated alkyl styrene), Unexamined-Japanese-Patent No. 1-46912, these hydrogenated polymers can be obtained by the method of Unexamined-Japanese-Patent No. 1-l78505.

In the present invention, the layer A basically uses the above-described styrene-based polymer as the material of the film, but may further contain other resin components in consideration of forming properties, mechanical properties, surface properties, and the like.

For example, styrene polymers, polyphenylene ethers, and the like of atactic or isotactic structures tend to be compatible with the styrene polymers having the syndiotactic structure described above, and crystallization is controlled when preparing preforms for stretching. It is effective for the subsequent stretching property, and it is easy to control extending | stretching conditions, and the film excellent in mechanical properties can be obtained.

In the case of containing a styrenic polymer having a double atactic structure and / or isotactic structure, it is preferably made of a monomer such as a styrene polymer having a syndiotactic structure.

Moreover, the content rate of these compatible resin components is 70-1 weight%, Especially preferably, it is 50-2 weight%.

Here, when the content rate of compatible resin component exceeds 70 weight%, since the heat resistance etc. which are the advantage of the styrene polymer of a syndiotactic structure are damaged, it is unpreferable.

Moreover, as incompatible resin, For example, polyolefin, such as polyethylene, a polypropylene, a polybutene, a polypentene; Polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; Polyamides such as nylon-6 or nylon-6,6; Polythioethers such as polyphenylene sulfide; Polycarbonates; Polyarylates; Polysulfones; Polyether ether ketone; Polyether sulfone; Polyimide; Halogenated vinyl polymers such as teflon; Acrylic polymers such as polymethyl methacrylate; All other than the above-mentioned compatible resins such as polyvinyl alcohol, and the like, and cross-linked resins containing the above-mentioned compatible resins may be mentioned again.

Since these resins are incompatible with the styrenic polymer having the syndiotactic structure of the present invention, when contained in a small amount, it is possible to disperse like islands in the styrenic polymer of the syndiotactic structure, giving a considerably gloss after stretching. It is effective in improving the lubricity of the surface.

The content of these incompatible resin components is preferably 50-2% by weight for the purpose of gloss and 0.001-5% by weight for the purpose of controlling the surface properties.

In addition, when the temperature used for a product is high, it is preferable to use resin which is heat resistant.

In addition, an inorganic filler, an antioxidant, an antistatic agent, a dye, or the like can be blended within a range not impairing the object of the present invention.

Here, as inorganic fillers that can be used, oxides, hydroxides, sulfides, nitrides, halogens of Groups IA, IIA, IVA, VIA, VIIA, VIII, Ib, IIB, IIIB, IVB elements Cargoes, carbonates, acetates, phosphates, phosphites, organic carboxylates, silicates, titanates, borates and their hydrous compounds, composite compounds based on them, natural mineral particles and the like.

Specifically, Group IA element compounds, such as lithium fluoride and borax (sodium borate hydrochloride); Magnesium carbonate, magnesium phosphate, magnesium oxide (magnesia), magnesium chloride, magnesium acetate, magnesium fluoride, magnesium titanate, magnesium silicate, magnesium silicate function (talc), calcium carbonate, calcium phosphate, calcium phosphite, calcium sulfate (gypsum) Group IIA elements, such as calcium acetate, calcium terephthalate, calcium hydroxide, calcium silicate, calcium fluoride, calcium titanate, strontium titanate, barium carbonate, barium phosphate, barium sulfate, and barium phosphite; Group VIA elements such as elemental IVA compounds such as titanium dioxide (titania), titanium monoxide, titanium nitride, zirconium dioxide (zirconia) and zirconium oxide, molybdenum dioxide, molybdenum trioxide and molybdenum sulfide; Group VIII element compounds such as group VIIA element compounds such as manganese chloride and manganese acetate, cobalt chloride and cobalt acetate; IB group element compounds, such as cuprous bromide; Group IIB element compounds such as group IIB elements such as zinc oxide and zinc acetate, aluminum oxide (alumina), aluminum hydroxide, aluminum fluoride, and aluminosilicate (alumina silicate, kaolin, kaolinite); Group IVB elements such as silicon oxide (silica, silica gel), quartz, carbon, graphite, glass, etc .; Particles of natural minerals, such as kaanilite, kineite, mica (mica, gold mica) and lead manganese, are mentioned.

The film which comprises A-layer of this invention is a film which consists of a raw material as mentioned above, and is 20-500 micrometers in thickness, and a haze is 3% or less.

It is preferable that the crystallization rate is relatively slow in order to obtain a film having a thickness and haze in this range.

For example, (1) the above-mentioned styrene-based polymer polymerized with an aromatic hydrocarbon solvent having a solubility parameter δ of 8.5 (cal / cm 3) ^1/2 or more, and (2) the above-mentioned made of a compatible thermoplastic resin as described above. Styrene-based polymer and (3) Among the above-described styrene-based polymers, there are random interpolymers having a content of 30 mol% or less.

As a specific example of the solvent of (1), in addition to alkylbenzenes, such as benzene, toluene, ethylbenzene, xylene, and propylbenzene, the styrene monomer in bulk polymerization, for example, styrene, alkylstyrene, a halogenated styrene, etc. are contained.

In addition, there is no limitation on the method of containing the compatible thermoplastic resin of (2), but the method of adding or simultaneously producing | generating at the time of superposition | polymerization, or melt-mixing method is preferable. In addition, in the layer A of the present invention, in order to obtain the above-mentioned film, the styrene polymer or the residual styrene monomer in the composition is preferably 7000 ppm or less.

In order to obtain such a styrene polymer or composition, it may be based on the following method.

(1) A method of drying the styrenic polymer after polymerization or again after the treatment under reduced pressure, in which the drying temperature is a temperature higher than the glass transition temperature of the polymer, the efficiency is good.

(2) Again, it is degassed with an extruder and it is set as a molding material (pellet) at the same time.

In this case, the extruder is preferably attached with a vent, and a single screw or a twin screw extruder may be used.

Here, when the residual monomer volatile content exceeds 7000 ppm, foaming occurs during extrusion molding, the surface becomes rough during stretching, and the haze exceeds 3%, which is undesirable.

The film of A layer is manufactured using the styrene-type polymer of this invention as described above, or the composition containing this polymer as a raw material.

What is necessary is just to perform the manufacturing method of a film on the conditions which can achieve the objective mentioned above, and there is no restriction | limiting in particular.

Specifically, it is produced by hot melting, extruding, cooling and solidifying.

The extruder used herein may be either a single screw extrusion machine or a twin screw extrusion machine, or may be any one having no bends and no vents, but a uniaxial tandem type is preferable.

In the compressor, a suitable mesh may be used for pulverizing, removing secondary dust, or removing dust or foreign matter. In addition, the extrusion conditions are not particularly limited, and may be appropriately selected according to various situations. Preferably, the temperature is selected within a range of 50 ° C. higher than the melting point-decomposition temperature of the molding material.

Examples of the die to be used include a T-die and a round ring die.

The preform (original sheet) obtained after the above-mentioned extrusion molding is cooled and solidified.

Refrigerant at this time can use various things, such as a gas, a liquid, and a metal roller.

In the case of using a metal roller or the like, it is effective to prevent an unbalanced or surge of thickness by a method such as a knife, an exhaust chamber, a touch roll, and an electrostatic reduction.

The temperature of the cooling solidification is usually in the range of 30 ° C higher than the glass transition temperature of 0 ° C.-original sheet, and preferably in the range of the temperature-glass transition temperature 50 ° C lower than the glass transition temperature.

Moreover, a cooling rate is suitably selected in the range of 200-3 degreeC / sec.

The disc sheet thus obtained is in the range of 100-5,000 μm in thickness.

Subsequently, the original sheet which cooled and solidified is extended | stretched uniaxially or biaxially.

In the case of biaxial stretching, stretching may be performed simultaneously in the transverse direction (TD) and the longitudinal direction (machine direction (MD)), but may be performed in any order.

In addition, extending | stretching may be performed in one step, and you may carry out by multistage.

Here, as the method of yarn, there are various methods such as a tenter, a method of stretching between rolls, a method of bubbling using a gas pressure, a method of rolling, and the like, and these may be appropriately selected or combined and applied.

In general, the stretching temperature may be set between the glass transition temperature and the melting point of the original sheet.

However, in the case of sequential stretching or multi-stage stretching, it is preferable to perform the glass transition temperature and the cold crystallization temperature in the first step later, in the range of the glass transition temperature and the melting point.

Further, the drawing speed is usually 1 × 10 −1 × 10 ⁵ % / min, preferably 1 × 10 ³ -1 × 10 ⁵ % / min.

There is no restriction | limiting in particular about draw ratio, It is preferable to set it as 6 times or more.

Six times alone, a film having sufficient mechanical properties and humidity expansion coefficient cannot be obtained.

It is preferable to heat-set the stretched film obtained by extending | stretching on the conditions mentioned above again, in order to improve the dimensional stability at the time of high temperature, heat resistance, and the balance of strength in the film plane.

The heat setting can be carried out in the usual manner, but the stretched film is in the range of 0.5 to 180 degrees of glass transition temperature-melting point, preferably upper limit of use environment temperature-melting point of the film under tension, relaxation or limited shrinkage. It may be carried out for a second.

In addition, this heat setting can be performed twice or more by changing conditions within the above-mentioned range.

In addition, this heat setting may be performed under inert gas atmosphere such as argon gas and nitrogen gas.

If this heat setting is not performed, deformation is particularly likely near the glass transition temperature, and there are limitations in processing or use.

Moreover, it is preferable to set it as the film excellent in physical properties, such as transparency, by adjusting conditions of extending | stretching and heat setting so that the absolute value | (DELTA) n | of birefringence of a film may be 40x10 <^-3> or less.

The stretched film of the styrene polymer or the composition thus obtained has a thickness of 20-500 µm, in particular 50 µm or more, and has a haze of 3% or less and a humidity expansion coefficient of 1 × 10 ⁻⁶ /% RH or less. It can be used as A layer of.

The photo film of the present invention is obtained by further laminating the photosensitive layer of A layer on the film of this A layer as a support.

The surface of this A layer can be colonized for the purpose of improving the adhesive force with the layer adjacent to this A layer.

The photosensitive layer which is B layer in this invention is suitably selected by the purpose of use and the kind of photosensitive material, and what is necessary is just to laminate | stack by a normal method.

Specifically, as the photo film on which the photosensitive layer is formed, (1) silver dye photo film using silver salt photosensitive material, (2) diazo photosensitive film using diazo photosensitive material, (3) photochromic film using photochromic photosensitive material or (4) photoconductive material. And thermoplastic recording film using.

Hereinafter, each will be described.

In addition, the layer A mentioned above is used as a base film used here.

First, (1) A silver salt photographic film basically consists of a protective layer / silver dye photosensitive layer / undercoating layer / base film / back coating layer.

Here, various gelatin etc. are used for a protective layer.

In addition, the silver salt photosensitive layer is a gelatin emulsion layer consisting of a photosensitive resin such as silver bromide salt, chromium salt, Jay silver salt and a gelatin of a binder, and the lower coating layer is selected in consideration of the adhesion between the base film and the gelatin emulsion layer.

For example, natural polymers, such as gelatin and casein; Polyvinyl alcohol and its derivatives, interpolymers with maleic anhydride and methyl vinyl ether, vinyl acetate, methyl methacrylate, styrene and the like and interpolymers with methacrylic acid, acrylic acid, atacone and vinyl acetate, methyl methacrylate and styrene Single or a mixture thereof, and the like.

In the case of color photographs, a color developer is dispersed in the silver dye photosensitive layer, and the silver dye photosensitive layer is formed by sandwiching a plurality of layers, an intermediate gelatin layer or a filtration layer therebetween.

Moreover, as a silver salt photosensitive material, you may laminate | stack a halation prevention layer, an antistatic layer, etc. other than the above-mentioned lamination | stacking agent.

In addition, there is an X-ray photographic use as one of the uses of the silver salt photosensitive material. In this case, a gelatin emulsion layer serving as a photosensitive layer is provided on both sides of the base film (base material) of the present invention.

The lamination of each layer is usually carried out by application, and the thickness of each layer is 20-500 µm, preferably 25-300 µm, particularly preferably 75-250 µm, and the layer B is 1-50 µm. Preferably it is 3-30 micrometers, a protective layer is 0.01-10 micrometers, Preferably it is 0.1-5 micrometers, A rear coat layer is 0.01-20 micrometers, Preferably it is 0.1-10 micrometers, and a lower coat layer is 10 micrometers. Hereinafter, Preferably it is 5 micrometers or less.

Next, a diazo photosensitive film is demonstrated.

The diazo photosensitive material usually consists of a diazo photosensitive layer / base film / back coating layer.

The diazo photosensitive layer is composed of a composition and a binder composed of a common diazonium and a coupler, but examples of the binder used in the photosensitive layer include polyvinyl alcohol-based binders, cellulose-based binders such as cellulose butyrate, nitrocellulose, and cellulose acetate, and polyvinyl chloride. And vinyl chloride binders such as lidene and polyvinyl chloride, polymethacrylate ester binders such as polyacrylic acid esters, polystyrenes such as polystyrene and maleic acid, acrylic ester binders, and polyamide binders.

The diazo photosensitive layer made of such a binder is provided on one side of the base film with a thickness of 0.1-15 μm, preferably 2-8 μm.

In addition, when providing a rear part coating layer in the film, it is apply | coated to the thickness of 0.1-15 micrometers, Preferably it is 2-8 micrometers.

By providing such a rear coating layer, it is possible to improve the anti-curing and scratch defects of the film.

The thickness of the layer A (base film) in the diazo photosensitive material is 25-500 µm, preferably 38-300 µm.

If necessary, an appropriate adhesive layer and an anchor coating layer may be further provided on the A layer.

(3) The photochromic film is composed of a layer of photosensitive material coated with spiropyrane (a cyclic compound containing one carbon atom common to two rings) and a binder, the thickness of which is 0.1-15. [Mu] m.

In addition, (4) The thermoplastic video recording film is composed of a thermoplastic resin layer / transparent or reflective conductive layer / base film containing a transparent photoconductive material.

As the transparent conductive layer, deposited gold, copper, conductive tin oxide, and the like are used, and as the reflective conductive layer, a layer of evaporated aluminum is used.

These lamination methods are preferably a method of applying a thermoplastic resin layer containing a photoconductive material in a thickness of 0.5-5 μm after laminating 50-5000 mm 3 of a transparent conductive layer on a base film by vapor deposition.

Any of the photo films obtained as described above is excellent in various physical properties because the A film of the present invention is used as the base film.

The photo film of the present invention thus obtained is lighter than the conventional photo film because of its excellent physical properties as a base film, and has extremely good mechanical properties, dimensional stability and the like.

Therefore, the photographic film of the present invention is widely used as photographic films such as black and white photographs, color photographs, printing plates, X-ray photographs, and copies.

The present invention is described in more detail below as examples and comparative examples.

Preparation Example 1

(1) Preparation of contact product of trimethylaluminum and water

Copper sulfate pentahydrate (CuSO ₄ .5H ₂ O) 17.8 (71 mmol), 200 ml of toluene and 24 ml (250 mmol) of trimethylaluminum were added to a glassware container having an argon-substituted content of 500 ml, and reacted at 40 ° C for 8 hours.

Thereafter, toluene was further distilled off under reduced pressure from the solution obtained by removing the solid portion at room temperature to obtain 6.7 g of a contact product.

The molecular weight of this contact product was found to be 610 by the solidification point method.

(2) Preparation of styrene polymer

Inner capacity 2 In the reaction vessel of, purified styrene 1 The polymerization product was carried out at 90 DEG C for 5 hours using 5 mmol of aluminum as the aluminum atom, 5 mmol of triisobutyl aluminum and 0.025 mmol of pentamethylcyclopentadienyl titanium trimethoxide as the aluminum atom.

After the completion of the reaction, the product was decomposed into a methanol solution of sodium hydroxide, the catalyst component was repeatedly washed with methanol and dried to obtain 308 g of a polymer.

The weight average molecular weight of this polymer measured by kel permeation chromatography at 135 degreeC using 1,2,4-trichlorobenzene as the solvent was 389,000, and the weight average molecular weight / number average molecular weight was 2.64.

Furthermore, melting point and ¹³ C-NMR measurement confirmed that this polymer was polystyrene with syndiotactic structure.

Preparation Example 2

In Preparation Example 1 (2), a syndiotactic structure having a weight average molecular weight of 412,000 and a weight average molecular weight / number average molecular weight of 2.28 was prepared in the same manner as in Production Example 1 (2) except that 500 ml of heptane was added as a polymerization solvent in the polymerization. Polystyrene was obtained.

Preparation Example 3

In Production Example 2, the polymerization process was carried out as in Production Example 2, except that hybrid polymerization was carried out using 950 ml of styrene and 50 ml of p-methylsterene as raw material monomers.

It was confirmed by ¹³ C-NMR that all the obtained interpolymers contained 9.5 mol% of p-methylstyrene units in syndiotactic structure.

The weight average molecular weight was 438,000 and the weight average molecular weight / number average molecular weight was 2.51.

Example 1

The styrene polymer prepared in Production Example 1 was pressed at 150 ° C., dried, and pelletized by a vented single screw extruder, and the pellet was crystallized while stirring in hot air at 130 ° C.

The styrene monomer content in this crystallization pellet was 1,100 ppm.

This pellet was then extruded with an apparatus in which a T-die was attached to the tip of an extruder present in a 250 mesh filter.

Melting temperature at this time was 330 degreeC.

The molten sheet was molded into a sheet having a crystallinity of 12% and a thickness of 1 mm using a touch roll take-off machine having a roll surface adjusted to 55 ° C.

The obtained sheet was stretched three times in the longitudinal direction (MD), three times in the lateral direction, and 1.3 times in the longitudinal direction (MD) and at 120 ° C.

Subsequently, heat treatment was performed at 230 ° C. for 20 seconds under limited shrinkage.

The obtained film had a thickness of 85 μm, a haze of 1.8, and an absolute value | Δn | of birefringence of 10 × 10 ⁻³ .

Moreover, the density of this film was 1.06 g / cm <3>.

In addition, the coefficient of humidity expansion of the film was measured as an average of 20% RH to 80% RH at room temperature with a humidity variable device fitted to a thermal mechanical analysis, and was 5 × 10 ⁻⁷ /% RH.

Subsequently, as a representative example of the silver salt photographic film, the performance of the simulated X-ray photographic film was evaluated in the following order.

(1) gelatin

1 part of 4 weight% formalin was added with respect to 9 parts of 5 weight% gelatin aqueous solution, and it dried at 100 degreeC for 3 minutes, apply | coating to the above-mentioned laminated | multilayer film so that thickness might be 0.7 micrometer.

(2) emulsion for X-ray photographic film

Kojimi Miyamoto Book "Photosensitive Materials and Handling" Koritsu Co., Ltd. In 1955, the emulsion described on page 84 was used.

(3) Protective film and back coating gelatin layer

To 9 parts of 2% by weight gelatin aqueous solution, 1 part of 4% formalin was added to the emulsion layer surface so as to have a thickness of 0.3 µm and an emulsion layer 7 µm on the opposite side, and dried at room temperature.

The X-ray diffraction image of Al foil was imaged and developed using this photographic film.

At this time, the state of the image, the tensile test (JIS C 2318) and the density after 12 hours at 80 ° C. and 85% RH at the time of development were measured.

The results are shown in the table.

Example 2

In Example 1, operation similar to Example 1 was performed except having used the material containing 10 weight% of atactic polystyrene (HH-30E by Idemitsu Sekiyu Kagaku Co., Ltd.) at the time of base film preparation. It was.

The results are shown in the table.

Example 3

In Example 1, operation similar to Example 1 was performed except having used the styrene-type polymer of manufacture example 3.

The results are shown in the table.

Example 4

A base film was prepared in the same manner as in Example 1, and a simulated diazo photosensitive film having a photosensitive layer on one side and an anti-kering layer on the other side was prepared in the following manner.

40 ml of 15% by weight ethyl acetate solution of cellulose butyric acid (EAB-171, Eastman Co., Ltd.), 4-diazo-N, N'-diethylaniline chloride zinc chloride salt 1.5g, tartaric acid 1.5g, β-resorcinic acid 1.2 g of ethanolamine, 0.01 g of oil blue, and 60 ml of methanol were mixed, applied to a base film, and dried at 100 ° C. for 3 minutes to obtain a diazo photosensitive layer having a thickness of 6 μm.

As an anti-caling agent, only cellulose butyric acid was apply | coated to the other side, and it dried similarly.

The manuscript was brought into close contact with the photosensitive layer of the obtained diazo photosensitive film, and the resultant was immersed in a 10% aqueous solution of monoethanolamine for development for 2 seconds.

The results are shown in the table.

Comparative Example 1

In Example 1, it carried out similarly to Example 1 except having extended | stretched to 135 degreeC using the polymer of manufacture example 2.

The results are shown in the table.

Comparative Example 2

In Example 1, a film was prepared in the same manner as in Example 1 except that the melting temperature was set to 220 ° C. using atactic polystyrene (manufactured by Idetsu Seiki Oil Co., Ltd., HH-30E). And photographic films were prepared.

The results are shown in the table.

Comparative Example 3

Polyethylene terephthalate (traded product, Testosterone, OP3, 75 µm) was used as in Example 1.

The results are shown in the table.

[table]

1) SPS: Syndiotactic Polystyrene

aPS: Atactic Polystyrene

coSPS: Syndiotactic (styrene-p-methylstyrene) interpolymer

PET: Polyethylene Terephthalate

2) measured by JIS K705

3) Developing characteristics

Before treatment (after development)

Good: Al diffraction point is clear

Poor: Higher Al diffraction point is unclear.

After treatment (Treatment at 90 ℃, 85% RH or less for 12 hours)

Good: Same as immediately after development.

Poor: The image may be worn out due to film overturning or shrinkage.

Modulus of elasticity: measured at 30 ° C with a solid viscoelastic device (spectrometer)

Good: More than 40,000kg / ㎠

Available: 25,00-40,000kg / ㎠

Poor: 25,000kg / ㎠ or less

Claims (14)

(A) A stretched film layer composed of a styrene polymer having a syndiotactic structure and having a thickness of 20-500 µm and having a haze of 3% or less and a humidity expansion coefficient of 1 × 10 ^-6 /% RH or less (B) Photo film consisting of a photosensitive layer. The photographic film of claim 1, wherein the weight average molecular weight of the styrene-based polymer is 10,000-3,000,000. The photographic film of claim 1, wherein the weight average molecular weight of the styrenic polymer is 50,000-1,500,000. Photo film with weight average molecular weight / number average molecular weight 1.5-8. The photographic film of claim 1, wherein the layer (A) contains 70-1% by weight of the compatible resin. The photographic film of claim 1, wherein the layer (A) contains 50-2% by weight of the compatible resin. The photographic film of claim 1, wherein layer (A) contains 50-2% by weight of incompatible resin. The photographic film of claim 1, wherein the layer (A) contains 0.001-5% by weight of the compatible resin. The photographic film of claim 1, further comprising an inorganic filler, an antioxidant, an antistatic agent, or a dye. The photographic film of claim 1, wherein the residual styrene monomer content in the styrene polymer is 7,000 ppm or less. The photographic film of Claim 1 adjusted so that the absolute value of birefringence of (A) layer film may be 40x10 <^-3> or less. The photographic film of claim 1, comprising (A) a base film, (B) a photosensitive layer, and a gelatin emulsion layer, a protective layer, a rear coating layer, and a lower coating layer. The thicknesses of the layers (A), (B) photosensitive layer, protective layer, rear coating layer and lower coating layer are 20-500 µm, 1-50 µm, 0.01-10 µm, 0.01-20 µm and 10, respectively. Photo film of less than or equal to μm. The photographic film of claim 1, wherein (B) the photosensitive layer is composed of a silver salt photosensitive material, a diazo photosensitive material, a photochromic photosensitive material, or a photoconductive material.