EP0566094A2

EP0566094A2 - Support for photographic material

Info

Publication number: EP0566094A2
Application number: EP93106077A
Authority: EP
Inventors: Hideyuki Kobayashi; Takatoshi Yajima; Kenji Nakanishi; Yoshioki Okubo; Tetsutaro Hashimura; Hiroshi Naito
Original assignee: Konica Minolta Inc
Current assignee: Konica Minolta Inc
Priority date: 1992-04-15
Filing date: 1993-04-14
Publication date: 1993-10-20
Also published as: EP0566094A3

Abstract

There are disclosed a support for a photographic material, which comprises a copolymerized polyester containing an aromatic dicarboxylic acid having a metal sulfonate group as a monomer unit and an antioxidant, and having an L value which is an index of color of 93 or more and a b value which is an index of a color of 3 or less, and also a support for a photographic material which has a haze of 1.5 % or less, a center line average roughness of 0.0025 µm or more and a thickness of 50 to 100 µm.

Description

BACKGROUND OF THE INVENTION

This invention relates to a support for a photographic material, more specifically to a support for a photographic material suitable for a light-sensitive silver halide photographic material, having various excellent photographic characteristics that roll set curl can be easily resolved, photographic characteristics of photographs using the support are excellent and no bad influence is exerted on color reproducibility of a positive type light-sensitive material using said support. This invention also relates to a support for a photographic material suitable for a photographic film (hereinafter sometimes referred to as "light-sensitive photographic material") which can be loaded in a miniature or compact camera.
In recent years, miniature cameras have been generally used for various purposes. In the points of portability and easy handling of the miniature cameras, further miniaturization of the miniature cameras has been demanded. In order to miniaturize the miniature cameras as little as possible, it is indispensable to make a housing space of a photographic film to be loaded more compact.
In general, a photographic film is loaded in a miniature camera in a state of being wound around a spool. Therefore, in order to make a housing space of a miniature camera more compact and yet keep a certain number of exposure to be photographed, it is necessary to make a thickness of a photographic film thinner. Whereas a thickness of a photographic film support which has been used in recent days is about 120 to 125 µm, the thickness is considerably thicker than a thickness (20 to 30 µm) of a light-sensitive layer formed on the surface thereof. Thus, it is the most effective means for making a whole thickness of a photographic film thinner to make the thickness of the photographic film support thinner.
As a photographic film support which has been conventionally used, there may be mentioned representatively a triacetyl cellulose (hereinafter sometimes abbreviated as "TAC") film, but mechanical strength of the TAC film is inherently poor. When this TAC film is made thinner, conveyability and handling property in a photographing device and in subsequent development processing steps are worsened. Thus, the conventional TAC film as a photographic film support cannot be made thinner than that of presently used.
On the other hand, polyester has been also conventionally known as a support and has been frequently used for an X-ray film and a process film. When a polyester film is used as a support for a photographic material, its mechanical strength is excellent, but there is a drawback that roll set curl once formed can hardly be straightened even after development processing of a photographic film.
When the roll set curl is tight, there are problems that a film cannot be conveyed in various automatic conveyor, abrasion marks are formed on a negative type light-sensitive material and a print becomes out of focus.
In Japanese Provisional Patent Publication No. 244446/1989, as a polyester mainly composed of polyethylene terephthalate (PET), there has been disclosed a polyester in which an aromatic dicarboxylic acid having a metal sulfonate group and an aliphatic dicarboxylic acid as acid components are copolymerized with a diol component. It has been known that when this polyester is used as a support for a photographic material, roll set curl of a photographic film can be easily resolved whereas sliding property thereof is slightly poor.
When this polyester is used as a support for a photographic material, photographic characteristics, particularly storability at high temperature are lowered, whereby it cannot stand practical use. Further, such a support having slightly poor sliding property is made thinner, there are serious problems that when the support is wound up in a preparation step, it is wrinkled, and when a photographic film using the support is developed by an automatic processor, conveyability in the automatic processor is worsened, whereby the photographic film may be jammed or cut in the automatic processor. As the support is made thinner, these problems become more remarkable. Thus, sliding property of a support is an important factor when a thin support is prepared or when a photographic film using a thin support is developed.
As a method of solving the above problems, there may be considered a method for improving sliding property by adding inert particles to a support to form projections on the surface thereof. However, when projections are formed on the surface, there is another problem that transparency of the support is lowered.
As described above, in a transparent film such as a support for a photographic material, transparency and easy sliding property are characteristics which are incompatible with each other. Therefore, when transparency is demanded, a surface becomes smooth, but sliding property is extremely lowered, which is not preferred in preparation. To the contrary, when easy sliding property is tried to be imparted, transparency is lowered, which is not preferred as a photographic characteristic.
As a method for preparing a polyester, there may be mentioned a direct polymerization method in which an acid and a glycol are subjected to direct esterification and then polycondensation, and an transesterification (hereinafter referred to as "EI": ester interchange) method in which an ester of an acid and a glycol are subjected to transesterification reaction and then polycondensation. In the direct polymerization method, esterification can proceed sufficiently without a catalyst, but in the EI reaction, it is difficult to proceed the reaction within an economical time when an EI catalyst is not used.
As the above EI catalyst, there may be generally used a compound of calcium, magnesium, manganese, zinc, cobalt or titanium. The resulting polyester is used for preparing a support for a photographic material so that less coloring is important. From such a standpoint, calcium has been preferably used in the prior art.
In preparation of a modified polyester support to which hydrophilicity is imparted, when a calcium catalyst is used, a support having excellent sliding property can be obtained. However, transesterification ability of calcium is low so that a large amount of calcium should be used, whereby there is a problem that transparency of a support is lost.
In Japanese Patent Publication No. 28336/1982, it has been described that a copolyester in which a polyester mainly composed of polyethylene terephthalate is copolymerized with an aromatic dicarboxylic acid having a metal sulfonate group and polyethylene glycol is used as an element for a photographic material. Although roll set curl of this copolyester can be easily resolved, a photographic film using this copolyester as a support for a photographic material has poor photographic characteristics, particularly storability at high temperature, whereby it has problems in practical use.
A light-sensitive photographic material is prepared generally by coating functional layers such as an adhesive layer, an antistatic layer and a lubricating layer on a film such as PET and TAC, and further coating light-sensitive photographic layers thereon. Such functional layers are principally provided by coating aqueous coating solutions for the functional layers in the points of safety and environment.
In general, an aqueous coating solution for a functional layer is required to be treated by heat at high temperature for drying the aqueous coating solution, as compared with a solvent type coating solution for a functional layer. Further, in order to improve productivity, heat treatment tends to be carried out at higher temperature. Thus, a support for a photographic material is required to have heat resistance which can stand such high temperature.
Further, when flatness of a support for a photographic material is lowered, various coating failures are caused in subsequent steps. Thus, it is also an important characteristic required for a support for a photographic material that flatness is not lowered even by heat treatment at high temperature.
As another important property required for a support for a photographic material, it is required to prevent halation caused by absorbing long wavelength light which causes halation particularly easily, i.e. spectral red light and a near infrared region in a negative light-sensitive material in which a silver halide emulsion for a negative film is coated (antihalation characteristic) . Further, long wavelength light is easily transmitted from a side of a film pulled out from a magazine and exposed at the end of a leader to an inner portion thereof, whereby fog may be likely caused. Thus, a support for a photographic material is required to prevent halation effectively.
Further, it is desired that after completion of development processing and drying, a support for a photographic material absorbs less light at a short wavelength region (about 400 to 550 nm) . This is because if a support for a photographic material absorbs light at this region, since a positive type light-sensitive material such as a printing paper and a positive type light-sensitive material for X-ray photographs have light-sensitive regions at this short wavelength region, when the positive type light-sensitive material such as a printing paper is printed, there is a drawback that color development of a yellow layer which is light-sensitive mainly at a short wavelength region is suppressed, whereby a photograph in which magenta color and cyan color are ill balanced is obtained, and in the positive type light-sensitive material for X-ray photographs, there is a drawback that a filter desensitization action is caused at photography, whereby a turbid photograph like a fogged photograph is obtained.
Even if wavelength dependency of spectral characteristics is tried to be alleviated by means of dyeing by adding a dye to a support for a photographic material in order to solve various problems described above, addition of a dye in an amount required to alleviate light absorption specificity at a short wavelength region will greatly lower transmittance at a middle wavelength region, and in the positive type light-sensitive material such as a printing paper, not only color balance is not substantially improved, but also whole color density is lowered, whereby there is a fear that a preferred photograph cannot be obtained as a result.
Also, in the positive type light-sensitive material for X-ray photographs, decreased transmittance of a base leads to lowering of image quality, whereby such a material cannot stand practical use.
In order to cope with such drawbacks, there may be considered means such as increase of a silver halide amount in an emulsion layer of the positive type light-sensitive material and change of a system including photography in the positive type light-sensitive material for X-ray photographs. However, in the positive type light-sensitive material such as a printing paper, an attempt to compensate decreased transmittance of a film by making longer an exposure time during printing is a significant demerit under the present situation that shortening of time is required in consideration of a large number of printing papers to be processed.
Further, increase of a silver halide amount causes a problem of increase of cost due to an expensive price of silver halide, in other words, a problem of an additional equipment required to be installed for recovering silver, and also causes a significant pollutional problem against environment of silver halide which is flown out into a processing solution during development processing and fixing processing. Also, change of setting of processing steps in an automatic processor is practically impossible in consideration of the present worldwide market.
In consideration of various problems as described above, when a support for a photographic material does not have specific spectral characteristics or necessary colors, the support involves numerous problems in practical use and cannot be used.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a support for a photographic material which can solve the above problems and has excellent photographic characteristics that roll set curl can be easily resolved (roll set curl resolving property) and no bad influence is exerted on color reproducibility of a positive type light-sensitive material and emulsion characteristics of photographs due to deterioration by heat.
Another object of the present invention is to provide a support for a photographic material which has excellent mechanical strength and also recovering property from roll set curl after development processing, in which flatness is not lowered even by heat treatment at high temperature, has sufficient transparency as a support for a photographic material and excellent sliding property.
The first invention in order to accomplish the above object is a support for a photographic material, which comprises a copolymerized polyester containing an aromatic dicarboxylic acid having a metal sulfonate group as a monomer unit and an antioxidant, and having an L value which is an index of color of 93 or more and a b value which is also an index of color of 3 or less.
The second invention is the support described above wherein the above copolymerized polyester contains a polyalkylene glycol or a polyalkylene oxy dicarboxylic acid as a monomer unit and contains an aromatic dicarboxylic acid having a metal sulfonate group detected by hydrolyzing the above copolymerized polyester in an amount of 2 to 7 mole % based on all ester bond units and the above polyalkylene glycol or a polyalkylene oxy dicarboxylic acid in an amount of 3 to 10 % by weight based on the weight of all reaction products.
The third invention is the support described above wherein the above copolymerized polyester contains an aliphatic dicarboxylic acid as a monomer unit and contains an aliphatic dicarboxylic acid detected by hydrolyzing the above copolymerized polyester in an amount of 3 to 25 mole % based on all ester bond units.
The fourth invention is a support for a photographic material which comprises a film comprising, as a starting material, a copolymerized polyester containing an aromatic dicarboxylic acid having a metal sulfonate group as a monomer unit and containing diethylene glycol in an amount of 5 mole % or less based on all ester bond units.
The fifth invention is the support described above wherein the above copolymerized polyester further contains an aliphatic dicarboxylic acid having 4 to 20 carbon atoms as a monomer unit.
The sixth invention is the support described above wherein the above copolymerized polyester is obtained by adding at least one selected from the group consisting of sodium acetate, sodium hydroxide and tetraethylhydroxy ammonium at transesterification and/or polymerization.
The seventh invention is a support for a photographic material which comprises a copolymerized polyester containing terephthalic acid and ethylene glycol as monomer units and further containing an aromatic dicarboxylic acid having a metal sulfonate group detected by hydrolysis and a polyalkylene glycol as a starting material, and has a haze of 1.5 % or less, a center line average roughness of 0.0025 µm or more and a thickness of 50 to 100 µm.
The eighth invention is the support described above wherein the above copolymerized polyester contains an aromatic dicarboxylic acid having a metal sulfonate in an amount of 2 to 7 mole % based on all ester bond units and a polyalkylene glycol or a polyalkylene oxy dicarboxylic acid in an amount of 3 to 10 % by weight based on the total weight of the copolymerized polyester as monomer units.
The ninth invention is the support described above wherein the above copolymerized polyester is obtained by polymerization using a manganese compound in an amount of 0.5 x 10⁻² to 11.0 x 10⁻² mole %/all ester bond units and a calcium compound in an amount of 0.5 x 10⁻² to 5.0 x 10⁻² mole %/all ester bond units in combination as transesterification catalysts.
The tenth invention is the support described above wherein the above copolymerized polyester is obtained by using a manganese compound in an amount of 0.5 x 10⁻² to 11.0 x 10⁻² mole %/all ester bond units as a transesterification catalyst and also using an inert inorganic particle having an average particle size of 0.05 to 0.5 µm in an amount of 0.01 to 2.0 % by weight based on the above copolymerized polyester to be produced.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

In the following, the present invention is described in detail.
The support of the present invention comprises a copolymerized polyester obtained by transesterifying an aromatic dibasic acid having no metal sulfonate group and a glycol, in the presence or absence of an aromatic dicarboxylic acid having a metal sulfonate group, a polyalkylene glycol, an aliphatic dicarboxylic acid and other copolymerizable monomer; and an antioxidant, and subjecting the above mixture to polycondensation reaction in the presence of an aromatic dicarboxylic acid having a metal sulfonate group and an antioxidant, and if necessary, a polyalkylene glycol, an aliphatic dicarboxylic acid and other copolymerizable monomer. The copolymerized polyester is then dried, melt extruded and quenched, and if necessary, stretched to prepare a support for photographic material.
As a preferred example of the copolymerized polyester in the present invention, there may be mentioned a copolymerized polyester comprising an aromatic dicarboxylic acid having a metal sulfonate group as a copolymer component, and an aromatic dibasic acid and a glycol as main constitutional components. It is more preferred to contain a polyalkylene glycol or a polyalkyleneoxy dicarboxylic acid as another copolymer component, particularly preferably to contain a polyalkylene glycol.
As the aromatic dibasic acid, there may be mentioned terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid, and as the above glycol, there may be mentioned ethylene glycol, propylene glycol, butanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, diethylene glycol and p-xylylene glycol. Among them, terephthalic acid or 2,6-naphthalenedicarboxylic acid is preferred as the aromatic dibasic acid, and ethylene glycol is preferred as the glycol. These aromatic dibasic acid and glycol as main constitutional components are preferably contained in amounts of 70 to 98 mole %, more preferably 85 to 98 mole %, particularly preferably 90 to 95 mole % based on the whole ester bonds.
As the above aromatic dicarboxylic acid having a metal sulfonate group, there may be mentioned 5-sodium sulfoisophthalic acid, 2-sodium sulfoisophthalic acid, 4-sodium sulfoisophthalic acid, 4-sodium sulfo-2,6-naphthalenedicarboxylic acid, ester-forming derivatives shown below:

wherein X represents

-CH₂-, -SO₂- or -O-;
and R and R' each represent -(CH₂)_n- where n represents an integer of 1 to 20, preferably 2 to 4,

wherein R and R' each represent -(CH₂)_n- where n represents an integer of 1 to 20, preferably 2 to 4,
and a compound in which each of these sodiums is substituted by another metal such as potassium and lithium.
The copolymerized polyester in the present invention preferably contains a polyalkylene glycol and/or an aliphatic dicarboxylic acid having 4 to 20 carbon atoms as a copolymer component(s).
As the above polyalkylene glycol, there may be mentioned polyethylene glycol and polytetramethylene glycol, and among them, polyethylene glycol is preferred. Its molecular weight is not particularly limited, but it may be 300 to 20,000, preferably 600 to 10,000, more preferably 1,000 to 5,000 in terms of a number average molecular weight. Also, when the polyalkylene oxy dicarboxylic acid or a derivative thereof is used in place of the polyalkylene glycol, a polyethylene oxy dicarboxylic acid or a polytetraethylene oxy dicarboxylic acid is preferably used, and polyethylene oxy dicarboxylic acid is more preferably used.
As the aliphatic dicarboxylic acid having 4 to 20 carbon atoms, there may be mentioned succinic acid, adipic acid and sebacic acid, and among them, adipic acid is preferred.
In order to obtain a support for a photographic material in which heat resistance is excellent, roll set curl can be recovered sufficiently and mechanical strength is excellent, the copolymerized polyester containing an aromatic dicarboxylic acid having a metal sulfonate group as a monomer unit in the present invention preferably contains an aromatic dicarboxylic acid having a metal sulfonate group detected by hydrolyzing said polyester in an amount of 2 to 7 mole %, more preferably 3 to 6 mole % based on all ester bond units and preferably contains the above polyalkylene glycol in an amount of 3 to 10 % by weight, more preferably 4 to 8 % by weight based on the weight of all reaction products.
Further, when the copolymerized polyester containing an aromatic dicarboxylic acid having a metal sulfonate group as a monomer unit in the present invention also contains an aliphatic dicarboxylic acid as a monomer unit, the amount of the aliphatic dicarboxylic acid detected by hydrolyzing this copolymerized polyester is generally 0 to 25 mole %, preferably 3 to 25 mole % based on all ester bond units. When the aliphatic dicarboxylic acid as a monomer unit is contained in the copolymerized polyester in an amount within the above range, roll set curl of a photographic film can be easily resolved, and also heat resistance in practical use can be imparted to a support for a photographic material.
The copolymerized polyester in the present invention preferably contains diethylene glycol in an amount of 5 mole % or less, preferably 3 mole % or less based on all ester bond units. The amount of diethylene glycol is a value detected by hydrolyzing the copolymerized polyester. When diethylene glycol is contained in an amount of 5 mole % or less based on all ester bond units, the support for a photographic material of the present invention has excellent recovering property from roll set curl, and even when various aqueous coating solutions are coated on the surface of the support for a photographic material and treated by heat at high temperature, lowering of flatness of the support for a photographic material can be prevented.
The copolymerized polyester to be used in the present invention may contain other kinds of monomer units unless the effect of the present invention is impaired.
A method for preparing the copolymerized polyester containing an aromatic dicarboxylic acid having a metal sulfonate group as a monomer unit is not particularly limited, but the copolymerized polyester may be preferably prepared by, for example, subjecting a dicarboxylic acid component and a glycol component to transesterification preferably at a temperature of 200 to 250 °C, more preferably 220 to 240 °C under ambient pressure, followed by polycondensation at high temperature under reduced pressure, preferably at 250 to 300 °C, more preferably 270 to 285 °C under about 134 Pa or less, particularly 20 to 80 Pa. During this process, a copolymer component such as an aromatic dicarboxylic acid having a metal sulfonate group or polyethylene glycol may be added during transesterification reaction or may be added during polycondensation after transesterification reaction. Also, after adding these copolymer components, transesterification may be carried out and then after distillation under reduced pressure, melt polymerization may be carried out to obtain a polymer. In the present invention, it is preferred to add these copolymer components after transesterification and then polymerization is carried out.
As a catalyst to be used at this transesterification, there may be mentioned an acetate, an aliphatic acid salt and a carbonate of a metal such as manganese, calcium, zinc and cobalt. Among them, preferred are a manganese compound or a combination of a manganese compound and a calcium compound, for example, a hydrate of manganese acetate and a hydrate of calcium acetate, and more preferred is a combination of them.
In order to proceed transesterification reaction sufficiently and prevent too large haze of the copolymerized polyester obtained, the preferred amount of the manganese compound to be used as a catalyst is 0.5 x 10⁻² to 11.0 x 10⁻² mole %/all ester bond units and that of the calcium compound is 0.5 x 10⁻² to 5.0 x 10⁻² mole %/all ester bond units.
During the above transesterification and/or polycondensation, a hydroxide, a metal salt of an aliphatic dicarboxylic acid or quaternary ammonium may be effectively added within the range which does not inhibit reaction nor color a polymer. Among them, preferred are sodium hydroxide, sodium acetate and tetraethylhydroxy ammonium, and particularly preferred is sodium acetate. The amounts of these additives to be added are preferably 1 x 10⁻² to 20 x 10⁻² mole % based on all acid components.
The copolymerized polyester to be used in the present invention may contain phosphoric acid, phosphorous acid and esters thereof, and an inert inorganic particle which are optionally mixed during polymerization, and the above inert inorganic particle may be added optionally after polymerization.
The above inert inorganic particle is not particularly limited unless transparency of the support for a photographic material is impaired, and there may be preferably used, for example, silica, kaolin, calcium carbonate, calcium phosphate and titanium dioxide. When the copolymerized polyester is prepared by using a manganese compound as a transesterification catalyst, in order to obtain excellent transparency and easy sliding property of the support for a photographic material, the above inert inorganic particle preferably having an average particle size of 0.05 to 0.5 µm, more preferably 0.08 to 0.4 µm is preferably added to a polymerization system during polymerization in an amount of 0.01 to 2 % by weight, preferably 0.03 to 1.8 % by weight based on the copolymerized polyester obtained.
In order to obtain transparency of the support and excellent operatability of the support due to sufficient sliding, it is preferred that the content of the inert inorganic particle is within the above range. If the average particle size of the inert inorganic particle exceeds 0.5 µm, transparency of the support for a photographic material may be lowered, while if it is less than 0.05 µm, an effect of easy sliding property may not be exhibited sufficiently. Further, if the content of the inert inorganic particle exceeds 2 % by weight, transparency of the support may be lowered, while if the content of the inert inorganic particle is less than 0.01 % by weight, sliding property is insufficient, whereby operatability may be lowered.
To the copolymerized polyester, a dye, a UV absorber or an antioxidant may be suitably added without any problem at any stage of during polymerization and after polymerization. That is, the support for a photographic material can be prepared only from the above copolymerized polyester according to a method described below, or may contain conventionally used other additives, for example, a matting agent, an antistatic agent, a surfactant, a stabilizer, a dispersant, a plasticizer, a UV absorber, a conductive substance, a tackifier, a softening agent, a fluidity-imparting agent, a thickener, an antioxidant or a dye within the range which does not impair the effect of the present invention. These additives may be added during polymerization for preparing the copolymerized polyester, or may be blended with the copolymerized polyester prepared. Further, during polymerization, phosphoric acid, phosphorous acid and esters thereof may be contained.
The support for a photographic material of the present invention comprises a specific copolymerized polyester and an antioxidant.
The antioxidant is not particularly limited, and may specifically include a hindered pnenol type compound, an arylamine type compound, a phosphor type compound and a sulfur type antioxidant. Among them, a hindered phenol type compound is preferred. As the hindered phenol type compound, compounds represented by Compounds No. 1 and No. 2 shown below are preferred.
In order to prevent increase of turbidity of the copolymerized polyester and obtain excellent photographic characteristics, the content of the antioxidant in the support for a photographic material is generally preferably 0.01 to 2 % by weight, more preferably 0.1 to 0.5 % by weight based on the copolymerized polyester in the points of photographic characteristics and turbidity of the copolymerized polyester. The antioxidants may be used singly or may be used in combination of two or more kinds.
In the following, structures of the antioxidants which can be used in the present invention are shown.

·Hindered phenol type antioxidant

1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.

·Arylamine type antioxidant

29.
30.
31.
32.
33.

·Phosphor type antioxidant

34.
35. (C₁₃H₂₇O)₃P
36. (C₁₀H₂₁O)₃P
37. [CH₃(CH₂)₁₁·S]₃P
38.
39.
40.
41.
42.
43.
44.
45.
46.

·Sulfur type antioxidant

47. S(CH₂CH₂COOC₁₂H₂₅)₂
48. S(CH₂CH₂COOC₁₈H₃₇)₂
49.
50. S(CH₂CH₂COOC₁₄H₂₉)₂
51.
52.
53.
54. (H₂₅C₁₂SCH₂CH₂COOCH₂)₄C

In order to obtain the support for a photographic material having the L value and b value which are indexes of color as described above, the polymerization temperature during polymerization for obtaining the copolymerized polyester is preferably set as low as possible within the range which can provide a necessary polymerization degree (said degree can be evaluated by intrinsic viscosity), preferably in the range of 270 to 285 °C. This is because the b value tends to be increased when the polymerization temperature is high. Also, by using a manganese compound and a calcium compound in combination as transesterification catalysts, colors of the support for a photographic material can be controlled to have the above index values.
In the support for a photographic material according to the present invention, a dye is preferably contained for the purpose of preventing light piping phenomenon (edge fog) caused when light is incident from an edge upon the support for a photographic material on which a photographic emulsion layer is provided by coating. The dye which is contained for such a purpose is not particularly limited, but a dye having excellent heat resistance is preferred for a film-forming step, and, for example, an anthraquinone type chemical dye may be included. From the point of a color tone of the support for a photographic material, a gray dye used in a common light-sensitive material is preferred, and one dye or a mixture of two or more dyes may be used. As such dyes, there may be used dyes such as SUMIPLAST (trade name) produced by Sumitomo Kagaku Kogyo Kabushiki Kaisha, Diaresin (trade name) produced by Mitsubishi Kasei Corporation and MACROLEX (trade name) produced by BAYER AG singly or in suitable combination.
The support for a photographic material of the present invention can be prepared by, for example, sufficiently drying the above copolymerized polyester or a copolymerized polyester composition comprising the copolymerized polyester and an antioxidant which is formulated, if necessary, or at least one selected from the group consisting of sodium acetate, sodium hydroxide and tetraethylhydroxy ammonium, then melt extruding it through an extruder, a filter or a mouthpiece which is controlled at a temperature range of 260 to 320 °C to be made into a sheet, setting the resulting melt polymer by cooling on a rotary cooling drum to obtain an unstretched film, then biaxially stretching the unstretched film in the longitudinal direction and the lateral direction and thermally fixing the film.
A method of obtaining the unstretched sheet is not particularly limited, and may be a known method, for example, a method in which a resulting resin is dried sufficiently and melt extruded through an extruder, a filter or a mouthpiece to be made into a sheet, and the sheet is cast on a rotary cooling drum to be set by cooling.
As a method of stretching the resulting sheet biaxially, there may be mentioned, for example, the following processes (A) to (C).

(A) A method in which an unstretched sheet is first stretched in the longitudinal direction and then stretched in the lateral direction.
(B) A method in which an unstretched sheet is first stretched in the lateral direction and then stretched in the longitudinal direction.
(C) A method in which an unstretched sheet is stretched in the longitudinal direction by a single step or multiple steps, stretched again in the longitudinal direction and then stretched in the lateral direction.

In the above stretchings, an unstretched film is preferably stretched by 4 to 16-fold in terms of an area ratio in order to obtain satisfactory mechanical strength and dimensional stability of the support for a photographic material.
Stretching conditions vary depending on the copolymer composition of the copolymerized polyester and cannot be determined uniformly, but may be a stretching ratio of 2.5 to 6.0-fold in the longitudinal direction at a temperature range of glass transition temperature (Tg) of the copolymerized polyester to Tg + 100 °C and a stretching ratio of 2.5 to 4.0-fold in the lateral direction at a temperature range of Tg + 5 °C to Tg + 50 °C. The biaxially stretched film obtained as described above is thermally fixed generally at 150 to 240 °C and cooled. At that time, the film may be relaxed in the longitudinal direction and/or the lateral direction, if necessary.
The copolymerized polyester in the present invention preferably has an intrinsic viscosity measured at 20 °C in a mixed solution of phenol and 1,1,2,2-tetrachloroethane (weight ratio: 60 : 40) of 0.4 to 1.0, more preferably 0.5 to 0.8.
The support for a photographic material of the present invention may be a single layer film or sheet prepared by means as described above, or may have a multilayer structure in which a film or sheet of another material and the film or sheet prepared by means as described above are laminated by a co-extrusion method or a lamination method.
In the present invention, the haze of the support for a photographic material obtained preferably has preferably 1.5 % or less, more preferably 0.3 to 1.5 %, particularly preferably 0.3 to 0.8 %. If the haze of the support is more than 1.5 %, transparency is poor, whereby the support is not preferred as a support for a photographic material.
The haze of the support for a photographic material can be controlled to 1.5 % or less by, for example, using a manganese compound as the above transesterification catalyst, reducing the amount of the above inert inorganic particle to be added or using a particle having a particle size within the above specific range.
In the present invention, the center line average roughness of the support for a photographic material obtained is preferably 0.0025 µm or more, more preferably 0.0030 µm or more. If the center line average roughness is a value less than 0.0025 µm, sliding property is poor, whereby particularly when the support for a photographic material which has been made thinner to have a thickness of 100 µm or less is wound up in a preparation step, it may be wrinkled undesirably.
The center line average roughness of the support for a photographic material can be made within the above specific range by controlling the particle size of the inert inorganic particle to be added during polymerization or controlling the particle size of the inert inorganic particle to be blended with the copolymerized polyester obtained. When the particle size of the inert inorganic particle to be added is not controlled, the center line average roughness of the support for a photographic material can be made within the above specific range by controlling the amount of the inert inorganic particle to be added. As a matter of course, in the present invention, a means of making the center line average roughness of the support for a photographic material within the above specific range is not limited to the above methods, and other desired methods may be employed.
The thickness of the support for a photographic material of the present invention is generally 40 to 150 µm, preferably 50 to 100 µm, more preferably 60 to 90 µm. If the film thickness of the support for a photographic material is more than 150 µm, mechanical strength is excellent whereby winding property is excellent, but it is impossible to make a housing space of a photographic film more compact while keeping a certain number of photographings. If the film thickness is less than 40 µm, sliding property is good, but mechanical strength is lowered, whereby winding wrinkles are formed to lower winding property, and rigidity is lost. Thus, such a support cannot be difficultly used as a support.
The support for a photographic material of the present invention is particularly suitable as a support for a photographic film used in a rolled state.
The photographic film has the following layer structure by using the support for a photographic material of the present invention.
That is, the photographic film has at least one silver halide emulsion layer on at least one surface of the support for a photographic material of the present invention. In other words, at least one silver halide emulsion layer may be provided on one surface of the support for a photographic material, or at least one silver halide emulsion layer may be provided on both surfaces of the support for a photographic material. Further, the silver halide emulsion may be provided directly on the support for a photographic material by coating, or may be provided by coating through another layer, for example, a hydrophilic colloid layer containing no silver halide emulsion, and further a hydrophilic colloid layer as a protective layer may be provided on the silver halide emulsion layer by coating. The silver halide emulsion layer may be provided by coating silver halide emulsion layers with different sensitivities, i.e. high sensitivity and low sensitivity separately. In that case, an intermediate layer may be provided between the respective silver halide emulsion layers. That is, an intermediate layer comprising hydrophilic colloid may be provided, if necessary. Further, between the silver halide emulsion layer and a protective layer, a non-light-sensitive hydrophilic colloid layer such as an intermediate layer, a protective layer, an antihalation layer and a backing layer may be provided.
As silver halide to be used in the silver halide emulsion, silver halide having any composition may be used. For example, silver chloride, silver chlorobromide, silver chloroiodobromide, pure silver bromide or silver iodobromide may be included.
In the silver halide emulsion, a sensitizing dye, a plasticizer, an antistatic agent, a surfactant or a hardener may be contained.
When the photographic film using the support for a photographic material of the present invention is subjected to development processing, developers as described in, for example, T.H. James "The Theory of the Photographic Process, Fourth Edition", p. 291 to p. 334, and "Journal of the American Chemical Society", Vol. 73, p. 3 and p. 100 (1951) can be used.

EXAMPLES

Example 1

A. Preparation of supports

To 100 parts by weight of dimethyl terephthalate and 64 parts by weight of ethylene glycol were added a hydrate of calcium acetate and a hydrate of manganese acetate as transesterification catalysts in terms of the molar ratio of 2 x 10⁻⁴ (i.e. 2 x 10⁻² mole %) based on the amount of dimethyl terephthalate, respectively, and the mixture was subjected to transesterification reaction according to a conventional manner.
To the resulting product were added an ethylene glycol solution of 5-sodium sulfo-di(β-hydroxyethyl)isophthalate (abbreviation: SIP) (concentration: 35 % by weight) and polyethylene glycol (abbreviation: PEG) (number average molecular weight: 3,000) in amounts controlled so as to obtain polymer composition ratios shown in Table 3. Then, to the mixtures were added 0.05 part by weight of antimony trioxide, 0.13 part by weight of trimethyl phosphate and Irganox 1010 (registered trademark, produced by CIBA-GEIGY AG) represented by Compound No. 2 mentioned above as an antioxidant in an amount of 0.4 % by weight based on the produced polymer. Subsequently, the temperature of each mixture was gradually elevated and the pressure thereof was gradually reduced. Then, the mixtures were polymerized at 270 °C or 275 °C (see Table 3) and 0.5 mmHg, respectively, to obtain 5 kinds of copolymerized polyesters (No. 1 to No. 5 in Table 3).
These copolymerized polyesters were dried under vacuum at 150 °C, melt extruded at 280 °C and set by quenching on a cooling drum to prepare unstretched films. The unstretched films were stretched by 3.3-fold in the longitudinal direction at 80 °C, stretched by 3.3-fold in the lateral direction at 90 °C and then thermally fixed at 220 °C for 30 seconds to obtain biaxially stretched films having a thickness of 70 µm. These biaxially stretched films were used as the supports for a photographic material of the present invention.

B. Preparation of light-sensitive materials

The both surfaces of each biaxially stretched film described above were subjected to corona discharge treatment of 8 W/(m²·min). On one surface of the biaxially stretched film, Coating solution B-3 shown below was coated so as to have a dried film thickness of 0.8 µm to form Subbing layer B-3, and on the other surface of the biaxially stretched film, Coating solution B-4 shown below was coated so as to have a dried film thickness of 0.8 µm to form Subbing layer B-4.

〈Coating solution B-3〉

Copolymer latex solution (solid component: 30 %) comprising 30 % by weight of butyl acrylate, 20 % by weight of t-butyl acrylate, 25 % by weight of styrene and 25 % by weight of 2-hydroxyethyl acrylate	270 g
Compound (UL-1)	0.6 g
Hexamethylene-1,6-bis(ethylene urea)	0.8 g
made up to 1 liter with water.

〈Coating solution B-4〉

Copolymer latex solution (solid component: 30 %) comprising 40 % by weight of butyl acrylate, 20 % by weight of styrene and 40 % by weight of glycidyl acrylate	270 g
Compound (UL-1)	0.6 g
Hexamethylene-1,6-bis(ethylene urea)	0.8 g
made up to 1 liter with water.

Further, Subbing layer B-3 and Subbing layer B-4 were subjected to corona discharge of 8 W/(m²·min). On Subbing layer B-3, Coating solution B-5 shown below was coated so as to have a dried film thickness of 0.1 µm to form Subbing layer B-5, and on Subbing layer B-4, Coating solution B-6 shown below was coated so as to have a dried film thickness of 0.8 µm to form Subbing layer B-6 having antistatic function.

〈Coating solution B-5〉

Gelatin	10 g
Compound (UL-1)	0.2 g
Compound (UL-2)	0.2 g
Compound (UL-3)	0.1 g
Silica particle having an average particle size of 3 µm	0.1 g
made up to 1 liter with water.

〈Coating solution B-6〉

Water-soluble conductive polymer (UL-4)	60 g
Latex solution (solid component: 20 %) containing Compound (UL-5)	80 g
Ammonium sulfate	0.5 g
Hardener (UL-6)	12 g
Polyethylene glycol (weight average molecular weight: 800)	6 g
made up to 1 liter with water.

Structures of the compounds used are put together and shown below.
Subbing layer B-5 was subjected to corona discharge of 25 W/(m²·min), and Subbing layer B-6 was subjected to corona discharge of 8 W/(m²·min). On the surface of Subbing layer B-5 described above, emulsion layers and other layers shown below were formed successively from the side of the support for a photographic material to prepare a multilayer light-sensitive color photographic material.

〈Emulsion layers and other layers〉

First layer: Antihalation layer (HC)
Black colloidal silver	0.15 g
UV absorber (UV-1)	0.20 g
Compound (CC-1)	0.02 g
High boiling point solvent (Oil-1)	0.20 g
High boiling point solvent (Oil-2)	0.20 g
Gelatin	1.6 g

Second layer: Intermediate layer (IL-1)
Gelatin	1.3 g

Third layer: Low sensitivity red-sensitive emulsion layer (R-L)
Silver iodobromide emulsion (average grain size: 0.3 µm) (average iodine content: 2.0 mole %)	0.4 g
Silver iodobromide emulsion (average grain size: 0.4 µm) (average iodine content: 8.0 mole %)	0.3 g
Sensitizing dye (S-1)	3.2 x 10⁻⁴ (mole/mole of Ag)
Sensitising dye (S-2)	3.2 x 10⁻⁴ (mole/mole of Ag)
Sensitizing dye (S-3)	3.2 x 10⁻⁴ (mole/mole of Ag)
Cyan coupler (C-1)	0.50 g
Cyan coupler (C-2)	0.13 g
Colored cyan coupler (CC-1)	0.07 g
DIR compound (D-1)	0.006 g
DIR compound (D-2)	0.55 g
High boiling point solvent (Oil-1)	0.55 g
Gelatin	1.0 g

Fourth layer: High sensitivity red-sensitive emulsion layer (R-H)
Silver iodobromide emulsion (average grain size: 0.7 µm) (average iodine content: 7.5 mole %)	0.9 g
Sensitizing dye (S-1)	1.7 x 10⁻⁴ (mole/mole of Ag)
Sensitizing dye (S-2)	1.6 x 10⁻⁴ (mole/mole of Ag)
Sensitizing dye (S-3)	0.1 x 10⁻⁴ (mole/mole of Ag)
Cyan coupler (C-2)	0.23 g
Colored cyan coupler (CC-1)	0.03 g
DIR compound (D-2)	0.02 g
High boiling point solvent (Oil-1)	0.25 g
Gelatin	1.0 g

Fifth layer: Intermediate layer (IL-2)
Gelatin	0.8 g

Sixth layer: Low sensitivity green-sensitive emulsion layer (G-L)
Silver iodobromide emulsion (average grain size: 0.4 µm) (average iodine content: 8.0 mole %)	0.6 g
Silver iodobromide emulsion (average grain size: 0.3 µm) (average iodine content: 2.0 mole %)	0.2 g
Sensitizing dye (S-4)	6.7 x 10⁻⁴ (mole/mole of Ag)
Sensitizing dye (S-5)	0.8 x 10⁻⁴ (mole/mole of Ag)
Magenta coupler (M-1)	0.17 g
Magenta coupler (M-2)	0.43 g
Colored magenta coupler (CM-1)	0.10 g
DIR compound (D-3)	0.02 g
High boiling point solvent (Oil-2)	0.7 g
Gelatin	1.0 g

Seventh layer: High sensitivity green-sensitive emulsion layer (G-H)
Silver iodobromide emulsion (average grain size: 0.7 µm) (average iodine content: 7.5 mole %)	0.9 g
Sensitizing dye (S-6)	1.1 x 10⁻⁴ (mole/mole of Ag)
Sensitizing dye (S-7)	2.0 x 10⁻⁴ (mole/mole of Ag)
Sensitizing dye (S-8)	0.3 x 10⁻⁴ (mole/mole of Ag)
Magenta coupler (M-1)	0.30 g
Magenta coupler (M-2)	0.13 g
Colored magenta coupler (CM-1)	0.04 g
DIR compound (D-3)	0.004 g
High boiling point solvent (Oil-2)	0.35 g
Gelatin	1.0 g

Eighth layer: Yellow filter layer (YC)
Yellow colloidal silver	0.1 g
Additive (HS-1)	0.07 g
Additive (HS-2)	0.07 g
Additive (SC-1)	0.12 g
High boiling point solvent (Oil-2)	0.15 g
Gelatin	1.0 g

Ninth layer: Low sensitivity blue-sensitive emulsion layer (B-L)
Silver iodobromide emulsion (average grain size: 0.3 µm) (average iodine content: 2.0 mole %)	0.25 g
Silver iodobromide emulsion (average grain size: 0.4 µm) (average iodine content: 8.0 mole %)	0.25 g
Sensitizing dye (S-9)	5.8 x 10⁻⁴ (mole/mole of Ag)
Yellow coupler (Y-1)	0.6 g
Yellow coupler (Y-2)	0.32 g
DIR compound (D-1)	0.003 g
DIR compound (D-2)	0.006 g
Gelatin	1.3 g

Tenth layer: High sensitivity blue-sensitive emulsion layer (B-H)
Silver iodobromide emulsion (average grain size: 0.8 µm) (average iodine content: 8.5 mole %)	0.5 g
Sensitizing dye (S-10)	3 x 10⁻⁴ (mole/mole of Ag)
Sensitizing dye (S-11)	1.2 x 10⁻⁴ (mole/mole of Ag)
Yellow coupler (Y-1)	0.18 g
Yellow coupler (Y-2)	0.10 g
High boiling point solvent (Oil-2)	0.05 g
Gelatin	1.0 g

Eleventh layer: First protective layer (PRO-1)
Silver iodobromide (average grain size: 0.08 µm)	0.3 g
UV absorber (UV-1)	0.07 g
UV absorber (UV-2)	0.10 g
Additive (HS-1)	0.2 g
Additive (HS-2)	0.1 g
High boiling point solvent (Oil-1)	0.07 g
High boiling point solvent (Oil-3)	0.07 g
Gelatin	0.8 g

Twelfth layer: Second protective layer (PRO-2)
Compound A	0.04 g
Compound B	0.004 g
Polymethyl methacrylate (average grain size: 3 µm)	0.02 g
Copolymer of methyl methacrylate:ethyl methacrylate:methacrylic acid = 3:3:4 (weight ratio)(average grain size: 3 µm)	0.13 g
Gelatin	0.5 g

Preparation of silver iodobromide emulsion

The silver iodobromide emulsion used in the tenth layer was prepared by the following method.
By using a monodispersed silver iodobromide grain having an average grain size of 0.33 µm (iodide content: 2 mole %) as a seed crystal, the silver iodobromide emulsion was prepared according to a double jet method.
While Solution 〈G-1〉 having a composition shown below was maintained at a temperature of 70 °C, pAg 7.8 and pH 7.0 and stirred well, a seed emulsion in an amount corresponding to 0.34 mole was added thereto.

(Formation of phase of which inner portion has high iodine content "core phase")

Thereafter, while maintaining a flow ratio of 1 : 1, Solution 〈H-1〉 having a composition shown below and Solution 〈S-1〉 having a composition shown below were added over 86 minutes at an accelerated flow rate (flow rate at completion of addition was 3.6-fold of initial flow rate).

(Formation of phase of which outer portion has low iodine content "shell phase")

Subsequently, while maintaining pAg 10.1 and pH 6.0, Solution 〈H-2〉 having a composition shown below and Solution 〈S-2〉 having a composition shown below were added over 65 minutes at a flow ratio of 1 : 1 and an accelerated flow rate (flow rate at completion of addition was 5.2-fold of initial flow rate).
During formation of grains, pAg and pH were controlled by using a potassium bromide aqueous solution and a 56 % acetic acid aqueous solution. After formation of grains, the grains were washed with water according to a conventional flocculation method and then dispersed again by adding gelatin, and pH and pAg were controlled to 5.8 and 8.06, respectively, at 40 °C.
The resulting emulsion was a monodispersed emulsion containing an octahedral silver iodobromide grain having an average grain size of 0.80 µm, a distribution width of 12.4 % and a silver iodide content of 8.5 mole %.

〈G-1〉

Ossein gelatin	100.0 g
10 % By weight methanol solution of Compound-I	25.0 ml
28 % Aqueous ammonia	440.0 ml
56 % Acetic acid aqueous solution	660.0 ml
made up to 5,000.0 ml with water.

〈H-1〉

Ossein gelatin	82.4 g
Potassium bromide	151.6 g
Potassium iodide	90.6 g
made up to 1,030.5 ml with water.

〈S-1〉

Silver nitrate	309.2 g
28 % Aqueous ammonia	Equivalent amount
made up to 1,030.5 ml with water.

〈H-2〉

Ossein gelatin	302.1 g
Potassium bromide	770.0 g
Potassium iodide	33.2 g
made up to 3,776.8 ml with water.

〈S-2〉

Silver nitrate	1,133.0 g
28 % Aqueous ammonia	Equivalent amount
made up to 3,776.8 ml with water.

In the same manner except for changing an average grain size of a seed grain, temperature, pAg, pH, flow rate, addition time and halide composition, the above respective silver iodobromide emulsions used in the emulsion layers other than the tenth layer, having different average grain sizes and silver iodide contents were prepared.
All emulsions were core/shell type monodispersed emulsions having a distribution width of 20 % or less. The respective emulsions were subjected to optimum chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate, and a sensitizing dye, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and 1-phenyl-5-mercaptotetrazole were added.
In the light-sensitive material described above, Compounds Su-1 and Su-2, a viscosity controller, Hardeners H-1 and H-2, Stabilizer ST-1, Antifoggants AF-1 and AF-2 (having weight average molecular weights of 10,000 and 1,100,000), Dyes AI-1 and AI-2 and Compound DI-1 (9.4 mg/m²) were further contained.

(Evaluation methods)

For the light-sensitive photographic materials prepared as described above, evaluations as described below were made, and the results are shown in Table 3.

〈Storability at high temperature〉

The light-sensitive photographic material treated by heat at 55 °C for 5 days and the light-sensitive photographic material stored at room temperature for 5 days were subjected to white exposure through a stepwedge for sensitometry and to film development processing as shown in Table 1. Measured were increase of fog (ΔFog) of the above heat-treated light-sensitive photographic material compared with fog of the above untreated light-sensitive photographic material and relative sensitivity (S) of the heat-treated light-sensitive photographic material when sensitivity of the above untreated light-sensitive photographic material was defined as 100.

〈Recovering property from roll set curl〉

A film with a width of 35 mm and a length of 12 cm was wound around a core with a diameter of 10 mm, and the wound film was maintained as such at 55 °C and 20 % RH (relative humidity) for 72 hours. Thereafter, the film was released from the core, and one end of the film was loaded with 50 g. The loaded film was dipped in a water bath at 38 °C for 15 minutes and then dried for 15 minutes by means of a hot air dryer at 55 °C. The vertical length of the film hung naturally after the load was removed was measured and evaluated based on ratio to its original length by using the following three standards. As property of a support for a photographic material, grades " ⃝" and "△" are preferred.

Evaluation standards

⃝:: 70 % or more
△:: 50 to 70 %
X:: less than 50 %

〈Colorimetric values of film: L and b〉

From transmittance obtained by measuring the support for a photographic material by using C light source with each 5 nm and a transmission system according to JIS standard, lightness (L value) and chromaticity (b value) were measured. The device used was Hitachi Spectrophotometer U-3200 (trade name, manufactured by Hitachi Ltd.). The values were obtained by obtaining three stimulation values (two degree visula field) X, Y and Z defined in JIS Z8722 (1982) and calculated from Hunter's color difference equation described in JIS Z8730 (1980).
After preparation of the light-sensitive material, even when the silver halide emulsion layers and/or the gelatin backing layers and others provided on both surface of the support of the light-sensitive material by coating were peeled off by using pancreatin or a sodium hypochlorite aqueous solution and the resulting support was cut and evaluated in the same manner as described above, substantially the same colorimetric values were obtained. Thus, after peeling of the layers after preparation of the light-sensitive material, colorimetric values of the film may be measured.

〈Color reproducibility and ΔL and Δb〉

The light-sensitive photographic material was loaded in a camera and charts of three colors (yellow, magenta and cyan) shown in Macbeth Color Checker (trade name, produced by Kollmorgen Co.) were photographed.
After the light-sensitive photographic material was subjected to film development processing described below, said material was printed on a commercially available color paper by using an automatic printing development processor, and printing processing under conditions shown below was carried out to obtain a color print for evaluation.
Colorimetric values (L and b) were calculated from reflectance of the print measured under C light source by using a reflection system and Hitachi Color Analyzer Model 607 (trade name, manufactured by Hitachi Ltd.) according to JIS standard.
The respective difference ΔL and Δb between the L value and b value obtained above and those obtained by processing a commercially available color film (a triacetate film) for comparison in the same manner were determined. When an absolute value of the difference is 1 or more, it can be regarded as a significant difference. The respective relative color reproducibilities of yellow, magenta and cyan were evaluated by using the following three standards. As color reproducibility, the grade " ⃝" is required as a matter of course.

Evaluation of color reproducibility

⃝:: no color with a difference of 1 or more
△:: 1 or 2 color(s) with a difference of 1 or more
X:: Color(s) with a difference of 2 or more

(Film development processing)

Evaluation of color reproducibility

(Film development processing)

Table 1

Processing step	Processing time	Processing temperature (°C)	Replenished amount* (ml)
Color development	3 min 15 sec	38 ± 0.3	780
Bleaching	45 sec	38 ± 2.0	150
Fixing	1 min 30 sec	38 ± 2.0	830
Stabilizing	60 sec	38 ± 5.0	830
Drying	1 min	55 ± 5.0	-

*: the replenished amount is a value per 1 m² of the light-sensitive photographic material.

The following color developing solution, bleaching solution, fixing solution, stabilizing solution and replenishing solutions thereof were used.

〈Color developing solution〉

Water	800 ml
Potassium carbonate	30 g
Sodium hydrogen carbonate	2.5 g
Potassium sulfite	3.0 g
Sodium bromide	1.3 g
Potassium iodide	1.2 mg
Hydroxylamine sulfate	2.5 g
Sodium chloride	0.6 g
4-Amino-3-methyl-N-ethyl-N-(β-hydroxylethyl)aniline sulfate	4.5 g
Diethylenetriaminepentaacetic acid	3.0 g
Potassium hydroxide	1.2 g
made up to 1 liter with addition of water, and adjusted to pH 10.06 by using potassium hydroxide or 20 % sulfuric acid.

〈Color developing replenishing solution〉

Water	800 ml
Potassium carbonate	35 g
Sodium hydrogen carbonate	3 g
Potassium sulfite	5 g
Sodium bromide	0.4 g
Hydroxylamine sulfate	3.1 g
4-Amino-3-methyl-N-ethyl-N-(β-hydroxylethyl)aniline sulfate	6.3 g
Potassium hydroxide	2 g
Diethylenetriaminepentaacetic acid	3.0 g
made up to 1 liter with addition of water, and adjusted to pH 10.18 by using potassium hydroxide or 20 % sulfuric acid.

〈Bleaching solution〉

Water	700 ml
Iron (III) ammonium 1,3-diaminopropanetetraacetate	125 g
Ethylenediaminetetraacetic acid	2 g
Sodium nitrate	40 g
Ammonium bromide	150 g
Glacial acetic acid	40 g
made up to 1 liter with addition of water, and adjusted to pH 4.4 by using aqueous ammonia or glacial acetic acid.

〈Bleaching replenishing solution〉

Water	700 ml
Iron (III) ammonium 1,3-diaminopropanetetraacetate	175 g
Ethylenediaminetetraacetic acid	2 g
Sodium nitrate	50 g
Ammonium bromide	200 g
Glacial acetic acid	56 g
adjusted to pH 4.0 by using aqueous ammonia or glacial acetic acid, and then made up to 1 liter with addition of water.

〈Fixing solution〉

Water	800 ml
Ammonium thiocyanate	120 g
Ammonium thiosulfate	150 g
Sodium sulfite	15 g
Ethylenediaminetetraacetic acid	2 g
adjusted to pH 6.2 by using aqueous ammonia or glacial acetic acid, and then made up to 1 liter with addition of water.

〈Fixing replenishing solution〉

Water	800 ml
Ammonium thiocyanate	150 g
Ammonium thiosulfate	180 g
Sodium sulfite	20 g
Ethylenediaminetetraacetic acid	2 g
adjusted to pH 6.5 by using aqueous ammonia or glacial acetic acid, and then made up to 1 liter with addition of water.

(Printing processing step)

Conditions of the printing processing are shown in Table 2. Table 2

Processing step Temperature Time

Color development 35.0 ± 0.3 °C 45 sec

Bleach-fixing 35.0 ± 0.5 °C 45 sec

Stabilizing 30 to 40 °C 90 sec

Drying 60 to 80 °C 60 sec

〈Color developing solution〉

Pure water	800 ml
Triethanolamine	10 g
N,N-diethylhydroxylamine	5 g
Potassium bromide	0.02 g
Potassium chloride	2 g
Potassium sulfite	0.3 g
1-Hydroxyethylidene-1,1-diphosphonic acid	1.0 g
Ethylenediaminetetraacetic acid	1.0 g
Disodium catechol-3,5-disulfonate	1.0 g
Diethylene glycol	10 g
N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate	4.5 g
Fluorescent brightener (4,4'-diaminostilbenesulfonic acid derivative)	1.0 g
Potassium carbonate	27 g
made up to 1 liter in total with addition of water, and adjusted to pH 10.10.

〈Bleach-fixing solution〉

Ferric ammonium ethylenediaminetetraacetate dihydrate	60 g
Ethylenediaminetetraacetic acid	3 g
Ammonium thiosulfate (70 % aqueous solution)	100 ml
Ammonium sulfite (40 % aqueous solution) 27.5 ml made up to 1 liter in total with addition of water, and adjusted to pH 5.7 by using potassium carbonate or glacial acetic acid.

〈Stabilizing solution〉

5-Chloro-2-methyl-4-isothiazolin-3-one	0.2 g
1,2-Benzisothiazolin-3-one	0.3 g
Ethylene glycol	1.0 g
1-Hydroxyethylidene-1,1-diphosphonic acid	2.0 g
o-Phenylphenol sodium	1.0 g
Ethylenediaminetetraacetic acid	1.0 g
Ammonium hydroxide (20 % aqueous solution)	3.0 g
Fluorescent brightener (4,4'-diaminostilbenesulfonic acid derivative)	1.5 g
made up to 1 liter in total with addition of water, and adjusted to pH 7.0 by using sulfuric acid or potassium hydroxide.

Example 2

To 100 parts by weight of dimethyl terephthalate and 64 parts by weight of ethylene glycol were added 22 parts by weight (4 mole %/all ester bond units) of an ethylene glycol solution of 5-sodium sulfo-di(β-hydroxyethyl)isophthalate (abbreviation: SIP) (concentration: 35 % by weight), 11 parts by weight (8.5 parts by weight/polymer) of polyethylene glycol (abbreviation: PEG) (number average molecular weight: 1,000), 0.05 part by weight of sodium acetate, 0.13 part by weight of trimethyl phosphate and Irganox 1010 (trade name, produced by CIBA-GEIGY AG) represented by Compound No. 2 mentioned above as an antioxidant in an amount of 0.5 % by weight based on the produced polymer. Subsequently, while stirring, to the mixture were added a hydrate of manganese acetate and a hydrate of calcium acetate as catalysts in terms of the molar ratio of 2 x 10⁻⁴ based on the amount of dimethyl terephthalate, respectively, and 0.05 part by weight of antimony trioxide was further added to the mixture.
After the temperature of the mixture was gradually elevated, methanol was evaporated at 170 °C under nitrogen atmosphere, and then the pressure of the mixture was reduced. The mixture was polymerized at 270 °C and 0.5 mmHg to obtain a copolymerized polyester having an intrinsic viscosity of 0.41 shown in Table 3 (No. 5' in Table 3). After a support having a film thickness of 70 µm was prepared in the same manner as in Example 1, emulsion layers and subbing layers were provided by coating in the same manner as in Example 1 to prepare a light-sensitive material. The light-sensitive material was evaluated in the same manner as in Example 1. The results are shown in Table 3.
From the results in Table 3, it can be understood that even if melt polymerization is carried out by using a mixture to which copolymer components are added before transesterification, intrinsic viscosity is as low as 0.41 and the molecular weight of polyethylene glycol is different, when the color index values are within the range specified in the present invention, the support is useful as a support for a photographic material.

Example 3

In the same manner as in Example 1 except for using polytetramethylene glycol (PTG) (number average molecular weight: 3,000) in place of PEG in Example 1 and changing polymerization temperature to 270 °C, a copolymerised polyester having a composition ratio shown in Table 3 was obtained (No. 6 in Table 3). After a support for a photographic material was prepared in the same manner as in Example 1, subbing layers and emulsion layers were provided by coating in the same manner as in Example 1 to prepare a light-sensitive photographic material. The light-sensitive photographic material was evaluated in the same manner as in Example 1. The results are shown in Table 3.

Comparative example 1

In the same manner as in Example 1 except for changing polymerization temperature (see Table 3), copolymerized polyesters having copolymer composition ratios shown in Table 3 were obtained (No. 7 to No. 11 in Table 3). In the same manner as in Example 1, supports for a photographic material were prepared, and then emulsion layers and backing layers were provided by coating to prepare light-sensitive materials. The light-sensitive materials were evaluated in the same manner as in Example 1. The results are shown in Table 3.
From the results in Table 3, it can be understood that the supports for a photographic material having the L value and b value within the range specified in the present invention have excellent color reproducibility and good recovering property from roll set curl and have excellent mechanical strength even when they are made thinner so that they can be automatically developed by using a conventional automatic processor, and therefore the supports for a photographic material of the present invention are extremely excellent.
By referring to the results of No. 1 to No. 6 of Example 1, it can be understood that the supports containing SIP in an amount of 2 to 7 mole % (based on all ester bond units) and containing a polyalkylene glycol, particularly polyethylene glycol in an amount of about 3 to 10 % by weight (based on polymer) are particularly effective as a support for a photographic material.
On the other hand, by referring to the results of No. 7, No. 9 and No. 10 of Comparative example 1, it can be understood that the supports for a photographic material having the L value and b value outside the range specified in the present invention have poor color reproducibility, and by referring to the results of No. B and No. 11 of Comparative example 1, it can be understood that they have recovering property from roll set curl which is apparently inferior to that of the supports for a photographic material of the present invention.
As a result of evaluation of storability at high temperature, in No. 1 to No. 6 of Example 1, the respective increases of fog are all 0.01 to 0.04 and decreases of sensitivities are small since the relative sensitivities are about 95 to 90, both of which do not cause problems in practical use. Thus, it can be confirmed that no bad influence is exerted on emulsion characteristics.

Example 4

To 100 parts by weight of dimethyl terephthalate and 70 parts by weight of ethylene glycol was added dimethyl adipate in amounts controlled so as to obtain polymer composition ratios shown in Table 4, and 0.1 part by weight of a hydrate of calcium acetate was added thereto. The mixtures were subjected to transesterification reaction according to a conventional manner.
To the respective resulting products was added an ethylene glycol solution of 5-sodium sulfo-di(β-hydroxyethyl)isophthalate (concentration: 35 % by weight) in amounts controlled so as to obtain polymer composition ratios shown in Table 4, and 0.05 part by weight of antimony trioxide and 0.13 part by weight of trimethyl phosphate were added thereto.
Further, as in Example 1, to the respective mixtures was added Irganox 1010 (trade name, produced by CIBA-GEIGY AG) in an amount of 0.4 % by weight based on the produced polymer. Subsequently, the temperature of each mixture was gradually elevated and the pressure thereof was gradually reduced. Then, the mixtures were polymerized at 280 °C and 0.5 mmHg, respectively, to obtain copolymerised polyesters (No. 12 to No. 15 in Table 4).
These copolymerised polyesters were dried under vacuum at 150 °C, melt extruded at 280 °C and set by quenching on a cooling drum to prepare unstretched films. The unstretched films were stretched by 3.3-fold in the longitudinal direction at 80 °C, stretched by 3.3-fold in the lateral direction at 90 °C and then thermally fixed at 180 °C for 30 seconds to obtain biaxially stretched films having a thickness of 70 µm.
By using these biaxially stretched films as supports for a photographic material, light-sensitive photographic materials were prepared in the same manner as in Example 1 and evaluated according to the same evaluation methods as in Example 1. The results are shown in Table 4.

Comparative example 2

In the same manner as in Example 3 except for changing polymerisation temperature and the amount of dimethyl adipate (DMA) used in Example 4 (see Table 4), copolymerised polyesters having copolymer composition ratios shown in Table 4 were obtained (No. 16 and No. 17 in Table 4). After supports for a photographic material were prepared in the same manner as in Example 3, emulsion layers and backing layers were provided by coating to prepare light-sensitive materials. The light-sensitive materials were evaluated in the same manner as in Example 1. The results are shown in Table 4.
From the results in Table 4, it can be understood that the supports for a photographic material having the L value and b value within the range specified in the present invention have excellent color reproducibility and good recovering property from roll set curl and are extremely excellent as a support for a photographic material.
From the results of No. 12 to No. 14 of Example 4, it can be understood that the supports containing SIP in an amount of about 2 to 7 mole % (based on all ester bond units) and containing dimethyl adipate in an amount of about 3 to 25 mole % (based on polymer) are particularly effective as a support for a photographic material.
On the other hand, from the results of No. 16 of Comparative example 2, it can be understood that the support for a photographic material having the L value and b value outside the range specified in the present invention has poor color reproducibility, and from the results of No. 15 of Comparative example 2, it can be understood that the support which is outside the scope of the present invention does not contain an SIP component so that it has recovering property from roll set curl which is apparently inferior to that of the supports of the present invention.

Example 5

In the same manner as in Example 1 except for adding 0.2 % by weight of Irganox 245 (trade name, produced by CIBA-GEIGY AG) represented by Compound No. 1 mentioned above as an antioxidant in place of the antioxidant Irganox 1010 (trade name, produced by CIBA-GEIGY AG) of Example 1, copolymerized polyesters having copolymer composition ratios shown in Table 5 were obtained (No. 17 and No. 18 in Table 5). By using these copolymerised polyesters, supports for a photographic material were prepared in the same manner as in Example 1, and by using the supports, light-sensitive photographic materials were obtained in the same manner as in Example 1. The light-sensitive photographic materials were evaluated according to the same evaluation methods as in Example 1. The results are shown in Table 5.

From the results in Table 5, it can be understood that the supports for a photographic material having the L value and b value within the range specified in the present invention have excellent color reproducibility and good recovering property from roll set curl even when the kind of the antioxidant and its amount are changed. As a result of evaluation of storability at high temperature, the respective increases of fog and changes of relative sensitivities are extremely small, both of which do not cause problems in practical use. Thus, it can be confirmed that no bad influence is exerted on emulsion characteristics. It can be understood that the supports for a photographic material do not exert bad influence on emulsion characteristics and photographic characteristics and therefore are extremely excellent as a support for a light-sensitive photographic material.

Example 6

In the same manner as in Example 1 except for changing the amounts of the transesterification catalysts as shown in Table 6, adding SIP in an amount of 5 mole % based on acid components and PEG in an amount of 7.5 % by weight based on all ester bond units as copolymer components and carrying out polymerisation at 270 °C, copolymerized polyesters were obtained (No. 19 to No. 21 in Table 6) . By using these copolymerized polyesters, support for a photographic material were prepared in the same manner as in Example 1, and by using the supports, light-sensitive photographic materials were prepared in the same manner as in Example 1. The light-sensitive photographic materials were evaluated according to the same evaluation methods as in Example 1. The results are shown in Table 6.

Comparative example 3

In the same manner as in Example 6, polymers having composition ratios shown in Table 6 were obtained (No. 22 and No. 23 in Table 6). In the same manner as in Example 1, films were prepared, and then emulsion layers and backing layers were provided by coating to prepare light-sensitive materials. The light-sensitive materials were evaluated in the same manner as in Example 1. The results are shown in Table 6.
From the results in Table 6, it can be understood that the supports for a photographic material having the L value and b value within the range specified in the present invention have excellent color reproducibility and good recovering property from roll set curl even when the amounts of the transesterification catalysts are changed, and the supports are extremely excellent as a support for a light-sensitive photographic material.

Example 7

To the same copolymerized polyester as No. 4 of Example 1 was added a dye MACROLEX (Blue RR, trade name) produced by Bayer Co. so as to have a concentration of 1,500 ppm based on the copolymerized polyester, and a masterbatch was prepared by a biaxial kneader. The masterbatch and the above copolymerized polyester not containing the above dye were so mixed that the weight ratio became 1:9, to make a desired dye concentration 150 ppm, and then the mixture was processed in the same manner as in Example 1 to prepare a biaxially stretched film. Thereafter, a light-sensitive photographic material was prepared in the same manner as in Example 1 and evaluated according to the same evaluation methods as in Example 1. The results are shown in Table 7.
In Example 7, light piping of the light-sensitive photographic material was evaluated as described below.

〈Light piping〉

The prepared unexposed light-sensitive material was placed in a patrone with 2 cm of the end of said material being outside the patrone, and then exposed for 2 minutes under light source of 7,000 lux. Then, the film development processing described above was carried out, and a distance from the end portion of the patrone to a position where change of density (fog) was observed was measured. As a support for a photographic material, the distance is preferably as small as possible, but there is no problem if it is about 15 mm or less. In a commercially available color film, the distance is about 8 mm.

Comparative example 4

In the same manner as in Example 7 except for using a copolymerised polyester having the same composition ratio as that of No. 9 of Comparative example 1, a support for a photographic material was prepared. Then, a light-sensitive photographic material was prepared in the same manner as in Example 7 and evaluated in the same manner as in Example 7. The results are shown in Table 7.

Table 7

	No.	Polymerization temperature °C	Yellow		Magenta		Cyan		Color reproducibility	Light piping mm
			ΔL	Δb	ΔL	Δb	ΔL	Δb
Example 7	25	270	-0.1	0.0	-0.3	0.2	-0.2	0.2	⃝	11
Comparative example 4	26	280	-0.4	-0.5	-1.2	0.7	-0.6	0.3	△	9

From the results in Table 7, it can be understood that the support for a photographic material having the L value and b value within the range specified in the present invention has excellent color reproducibility and good recovering property from roll set curl, and there is no practical problem of light piping even when a dye is added, and the support is extremely excellent as a support for a light-sensitive photographic material.
On the other hand, it can be understood that the support using the copolymerized polyester having the L value and b value outside the range specified in the present invention (No. 10 of Comparative example 1) also has poor color reproducibility even when a dye is added, and the support has a problem in practical use as a support for a photographic material.

Example 8

To 100 parts by weight of dimethyl terephthalate and 64 parts by weight of ethylene glycol was added 0.1 part by weight of a hydrate of calcium acetate as a transesterification catalyst, and the mixture was subjected to transesterification reaction according to a conventional manner.
To the resulting product were added 28 parts by weight of an ethylene glycol solution of 5-sodium sulfo-di(β-hydroxyethyl)isophthalate (concentration: 35 % by weight), 8 parts by weight of polyethylene glycol (number average molecular weight: 3,000), 0.05 part by weight of antimony trioxide, 0.13 part by weight of trimethyl phosphate and 0.02 part by weight of sodium hydroxide. Subsequently, the temperature of the mixture was gradually elevated and the pressure thereof was gradually reduced. Then, the mixture was polymerized at 280 °C and 0.5 mmHg to obtain a copolymerized polyester. In the copolymer, diethylene glycol which was by-produced during the above polymerization reaction was contained as an acid component.
The copolymerized polyester was dried under vacuum at 150 °C, melt extruded at 280 °C and set by quenching on a cooling drum to prepare an unstretched film. The unstretched film was stretched by 3.3-fold in the longitudinal direction at 80 °C, stretched by 3.3-fold in the lateral direction at 90 °C and then thermally fixed at 220 °C for 30 seconds to obtain a biaxially stretched film having a thickness of 80 µm. For the biaxially stretched film, its diethylene glycol content was measured according to the following recipe and its flatness and recovering property from roll set curl were evaluated according to the following evaluation methods. The results are shown in Table 1. The film was slightly colored, but such a coloring degree was not a problem in practical use. As can be clearly seen from Table 1, the diethylene glycol content was 4 mole %, and both of the flatness and the recovering property from roll set curl were good.

〈Diethylene glycol content〉

To 50 ml of a methanol solution of 1N potassium hydroxide was added 2 g of the crushed film, and the mixture was heated to 230 °C while stirring. After 90 minutes, 10 ml of pure water was added, and the mixture was further heated continuously for 30 minutes. Thereafter, 7 g of terephthalic acid was added, and the mixture was cooled to room temperature. To the mixture was added 5 ml of a methanol solution of 1 % by volume of tetraethylene glycol dimethyl ether, and the mixture was stirred for 5 minutes. The solution thus obtained was filtered, and the filtrate was analyzed by gas chromatography to determine a diethylene glycol content by using a previously prepared calibration curve.

〈Flatness〉

After the film was humidified under conditions of 23 °C and a relative humidity of 55 % for more than 4 hours, the film was cut into 120 mm x 150 mm and subjected to heat treatment at 150 °C for 30 minutes in a hot air oven without stretching. The film after the heat treatment was humidified at 23 °C and a relative humidity of 55 %, and then a lenticulation degree was evaluated visually with naked eyes and ranked according to the following standard. Utilizability in the ranking is determined by acceptability as a support for a photographic material, and Ranks 3 to 5 are regarded as no problem in practical use.

(Ranking and explanation thereof)

5:: Extremely good
4:: Good
3:: Lenticulation is found by careful observation
2:: Moderate lenticulation
1:: Remarkable lenticulation

〈Recovering property from roll set curl〉

A film of 12 cm x 35 mm was wound around a core with a diameter of 10 mm, and the wound film was left to stand at 55 °C and 20 % RH (relative humidity) for 3 days to form roll set curl of the film. Thereafter, the film was released from the core and dipped in pure water of 38 °C for 15 minutes. Thereafter, the film was loaded with 50 g and dried for 3 minutes by means of a hot air dryer at 55 °C. After 3 minutes, the load was removed from the film and the film was hung perpendicularly. The distance between both ends of the hung film was measured and a recovering rate from roll set curl based on the original length of 12 cm was evaluated. As a support for a photographic material, the recovering rate is preferably 50 % or more, particularly 80 % or more in practical use. If the value is within the above range, there is no problem as a photographic film.

Example 9

In the same manner as in Example 8 except for adding 0.07 % by weight of tetraethylhydroxy ammonium in place of sodium hydroxide used in Example 8, a biaxially stretched film having a thickness of 80 µm was obtained. The film was evaluated in the same manner as in Example 8, and the results are shown in Table 8. The film was slightly colored similarly as in Example 8, but such a coloring degree was not a problem in practical use. As can be clearly seen from Table 8, the diethylene glycol content was 5 mole %, and there was no practical problem in both of the flatness and the recovering property from roll set curl.

Example 10

In the same manner as in Example 8 except for adding 0.04 % by weight of sodium acetate in place of sodium hydroxide used in Example 8 at transesterification reaction, a biaxially stretched film having a thickness of 80 µm was obtained. The film was evaluated in the same manner as in Example 8, and the results are shown in Table 8. The film was slightly colored similarly as in Example 8, but such a coloring degree was not a problem in practical use. As can be clearly seen from Table 8, the diethylene glycol content was 3 mole %, and there was no practical problem in both of the flatness and the recovering property from roll set curl.
A photographic film prepared by providing light-sensitive photographic layers on the film according to a known method did not have any particular problem in practical use and had good characteristics.

Example 11

To 100 parts by weight of dimethyl terephthalate, 70 parts by weight of ethylene glycol and 10 parts by weight of dimethyl adipate was added 0.1 part by weight of a hydrate of calcium acetate as a transesterification catalyst , and the mixture was subjected to transesterification reaction according to a conventional manner.
To the resulting product were added 32 parts by weight of an ethylene glycol solution of 5-sodium sulfo-di(β-hydroxyethyl)isophthalate (concentration: 35 % by weight), 0.05 part by weight of antimony trioxide, 0.13 part by weight of trimethyl phosphate and 0.04 part by weight of sodium acetate. Subsequently, the temperature of the mixture was gradually elevated and the pressure thereof was gradually reduced. Then, the mixture was polymerized at 280 °C and 0.5 mmHg to obtain a copolymerized polyester.
The copolymerized polyester was dried under vacuum at 150 °C, melt extruded at 280 °C and set by quenching on a cooling drum to prepare an unstretched film. The unstretched film was stretched by 3.3-fold in the longitudinal direction at 80 °C, stretched by 3.3-fold in the lateral direction at 90 °C and then thermally fixed at 200 °C for 30 seconds to obtain a biaxially stretched film having a thickness of 80 µm. For the biaxially stretched film, its diethylene glycol content was measured in the same manner as in Example 8 and its flatness and recovering property from roll set curl were evaluated according to the same evaluation methods as in Example 8. The results are shown in Table 8. The film was colorless and transparent. As can be clearly seen from Table 8, the diethylene glycol content was 3 mole %, and both of the flatness and the recovering property from roll set curl were good.

Example 12

To 100 parts by weight of dimethyl terephthalate and 64 parts by weight of ethylene glycol were added 10 parts by weight of 5-sodium dimethyl sulfoisophthalate, 8 parts by weight of polyethylene glycol (number average molecular weight: 1,000), 0.1 part by weight of calcium acetate, 0.04 part by weight of sodium acetate, 0.05 part by weight of antimony trioxide and 0.5 part by weight of Irganox 1010 (trade name, produced by CIBA-GEIGY AG), and the mixture was subjected to transesterification reaction according to a conventional manner. To the resulting product was added 0.1 part by weight of trimethyl phosphate. Subsequently, the temperature of the mixture was gradually elevated and the pressure thereof was gradually reduced. Then, the mixture was polymerized at 280 °C and 0.5 mmHg to obtain a copolymerized polyester having an intrinsic viscosity of 0.50.
The copolymerized polyester was dried under vacuum at 150 °C, melt extruded at 280 °C and set by quenching on a cooling drum to prepare an unstretched film. The unstretched film was stretched by 3.3-fold in the longitudinal direction at 80 °C, stretched by 3.3-fold in the lateral direction at 90 °C and then thermally fixed at 180 °C for 30 seconds to obtain a biaxially stretched film having a thickness of 100 µm. The biaxially stretched film was evaluated in the same manner as in Example 8, and the results are shown in Table 8. The film was colored in yellow and its quality as a support for a photographic material was inferior to those of the films obtained in Examples 8 to 11, but it could be used practically. As can be clearly seen from Table 8, the diethylene glycol content was 5 mole %, and both of the flatness and the recovering property from roll set curl were good.

Comparative example 5

To 100 parts by weight of dimethyl terephthalate and 64 parts by weight of ethylene glycol was added 0.1 part by weight of a hydrate of calcium acetate as a transesterification catalyst, and the mixture was subjected to transesterification reaction according to a conventional manner.
To the resulting product were added 28 parts by weight of an ethylene glycol solution of 5-sodium sulfo-di(β-hydroxyethyl)isophthalate (concentration: 35 % by weight), 8 parts by weight of polyethylene glycol (number average molecular weight: 3,000), 0.05 part by weight of antimony trioxide and 0.13 part by weight of trimethyl phosphate. Subsequently, the temperature of the mixture was gradually elevated and the pressure thereof was gradually reduced. Then, the mixture was polymerized at 280 °C and 0.5 mmHg to obtain a copolymerized polyester.
The copolymerized polyester was dried under vacuum at 150 °C, melt extruded at 280 °C and set by quenching on a cooling drum to prepare an unstretched film. The unstretched film was stretched by 3.3-fold in the longitudinal direction at 80 °C, stretched by 3.3-fold in the lateral direction at 90 °C and then thermally fixed at 200 °C for 30 seconds to obtain a biaxially stretched film having a thickness of 80 µm. For the biaxially stretched film, its diethylene glycol content was measured in the same manner as in Example 8 and its flatness and recovering property from roll set curl were evaluated according to the same evaluation methods as in Example 8. The results are shown in Table 8. The film had no problem in its appearance, but as can be clearly seen from Table 8, the diethylene glycol content was 8 mole % and the flatness was poor.

Comparative example 6

In the same manner as in Comparative example 5 except for changing the thermal fixing temperature to 220 °C, a biaxially stretched film was obtained. The film was slightly turbid and its transparency was poor, and also as can be clearly seen from Table 8, the flatness was poor.

Comparative example 7

To 100 parts by weight of dimethyl terephthalate, 70 parts by weight of ethylene glycol and 10 parts by weight of dimethyl adipate was added 0.1 part by weight of a hydrate of calcium acetate as a transesterification catalyst, and the mixture was subjected to transesterification reaction according to a conventional manner.
To the resulting product were added 32 parts by weight of an ethylene glycol solution of 5-sodium sulfo-di(β-hydroxyethyl)isophthalate (concentration: 35 % by weight), 0.05 part by weight of antimony trioxide and 0.13 part by weight of trimethyl phosphate. Subsequently, the temperature of the mixture was gradually elevated and the pressure thereof was gradually reduced. Then, the mixture was polymerized at 280 °C and 0.5 mmHg to obtain a copolymerized polyester.
The copolymerized polyester was dried under vacuum at 150 °C, melt extruded at 280 °C and set by quenching on a cooling drum to prepare an unstretched film. The unstretched film was stretched by 3.3-fold in the longitudinal direction at 80 °C, stretched by 3.3-fold in the lateral direction at 90 °C and then thermally fixed at 180 °C for 30 seconds to obtain a biaxially stretched film having a thickness of 80 µm. For the biaxially stretched film, its diethylene glycol content was measured in the same manner as in Example 8 and its flatness and recovering property from roll set curl were evaluated according to the same evaluation methods as in Example 8. The results are shown in Table 8. The film was colorless and transparent, but as can be clearly seen from Table 8, the diethylene glycol content was 9 mole % and the flatness was poor.

Comparative example 8

In the same manner as in Comparative example 7 except for changing the thermal fixing temperature to 220 °C, a biaxially stretched film was obtained. The film was partially turbid and could not stand practical use.

Table 8

	Appearance of film	Diethylene glycol content (mole %)	Flatness	Recovering rate from roll set curl (%)
Comparative example 5	Good	8	2	90
Comparative example 6	Slightly turbid	8	1	80
Example 8	Slightly colored	4	4	90
Example 9	Slightly colored	5	3	90
Example 10	Good	3	4	95
Example 11	Good	3	3	70
Example 12	Colored in yellow	5	3	60
Comparative example 7	Good	9	1	90

Examples 13 to 17 and Comparative examples 9 to 11

To 100 parts by weight of dimethyl terephthalate and 64 parts by weight of ethylene glycol were added 0.02 part by weight of a hydrate of calcium acetate and 0.02 part by weight of a hydrate of manganese acetate, and the mixture was subjected to transesterification reaction according to a conventional manner. To the resulting product were added 5 to 58 parts by weight of an ethylene glycol solution of 5-sodium sulfo-di(β-hydroxyethyl)isophthalate (concentration: 35 % by weight), 2 to 16 parts by weight of polyethylene glycol (number average molecular weight: 3,000), 0.05 part by weight of antimony trioxide and 0.13 part by weight of trimethyl phosphate. Subsequently, the temperature of each mixture was gradually elevated and the pressure thereof was gradually reduced. Then, the mixtures were polymerised at 280 °C and 0.5 mmHg to obtain copolymerised polyesters.
The copolymerized polyesters were dried under vacuum at 150 °C, melt extruded at 280 °C and set by quenching on a cooling drum to prepare unstretched films having a thickness of 980 µm.
Then, the unstretched films were stretched by 3.5-fold in the lateral direction at 80 °C, stretched by 3.5-fold in the longitudinal direction at 90 °C and then thermally fixed at 200 °C to obtain biaxially stretched films having a thickness of 80 µm.

Example 18

To 100 parts by weight of dimethyl terephthalate, 64 parts by weight of ethylene glycol, 28 parts by weight (5 mole %/all ester bond units) of an ethylene glycol solution of 5-sodium sulfo-di(β-hydroxyethyl)isophthalate (concentration: 35 % by weight) and 6 parts by weight (5 % by weight/ polymer) of polyethylene glycol (number average molecular weight: 1,000) were added 0.02 part by weight of a hydrate of calcium acetate, 0.02 part by weight of a hydrate of manganese acetate and 0.05 part by weight of antimony trioxide, and the mixture was subjected to transesterification according to a conventional manner. To the resulting product was added 0.13 part by weight of trimethyl phosphate. Subsequently, the temperature of the mixture was gradually elevated and the pressure thereof was gradually reduced. Then, the mixtures were polymerized at 280 °C and 0.5 mmHg to obtain a copolymerized polyester. By using the copolymerized polyester, a biaxially stretched film was obtained in the same manner as in Example 13.

Examples 19 to 22 and Comparative examples 12 and 13

In the same manner as in Example 13 except for changing the amounts of the transesterification catalysts as shown in Table 10, biaxially stretched films were obtained.

Examples 23 to 27 and Comparative examples 14 to 17

In the same manner as in Example 13 except for changing the transesterification catalysts to manganese acetate (its amount added is shown in Table 11) and adding silica having a particle size as shown in Table 11 in an amount as shown in Table 11, biaxially stretched films were obtained.

Comparative example 18

In the same manner as in Example 13 except for changing the thickness of the unstretched sheet to 1,960 µm, biaxially stretched film was obtained.
Evaluation methods of the films are described below.

〈Transparency〉

Haze of the film was measured according to JIS K-6714. As property of a support for a photographic material, 1.5 % or less is preferred in practical use.

〈Center line average roughness〉

Surface roughness of a 250 µm square of the support surface was measured with an object lens of 40 magnifications by using a non-contact type surface roughness meter TOPO-3D (trade name) manufactured by WYKO Co.
If the center line average roughness is a value less than 0.0025 µm, there may be obstacles in handling.

〈Recovering rate from roll set curl〉

A film having a sample size of 15 cm x 35 mm was wound around a core with a diameter of 10.8 mm, and the wound film was treated at 55 °C and 30 % RH (relative humidity) for 4 hours. Thereafter, the film was released from the core, loaded with 50 g, dipped in a water bath of 40 °C for 15 minutes, dried for 3 minutes by means of a hot air dryer at 55 °C and hung perpendicularly. Its length was measured to evaluate a recovering degree based on the original length of 15 cm.

⃝:: Recovering rate from roll set curl is 60 % or more
△:: Recovering rate from roll set curl is more than 40 % and less than 60 %
X:: Recovering rate from roll set curl is 40 % or less

〈Winding property〉

Whether a support was wrinkled or not when the support was wound up in a preparation step was observed visually with naked eyes according to the following standard.

⃝:: The support is not wrinkled at all
△:: Wrinkles of the support are found by careful observation
X:: Wrinkles of the support are found at a glance

〈Fracture strength〉

A film was left to stand for more than 4 hours in a room humidified at 23 °C and a relative humidity of 55 %, and then cut to have a sample width of 10 mm and a length of 200 mm. A tensile test in the longitudinal direction was conducted at a tensile rate of 100 mm/min with a distance between chucks being 100 mm, and fracture strength was determined by dividing a load when the film was cut by an initial area.

If the fracture strength is less than 10 kg/mm², the film has problems in practical use as a support for a photographic material.

Table 10

	Transesterification catalyst
	Mn: x10⁻² (mole %/all acid components	Ca: x10⁻² (mole %/all acid components	Haze (%)	Center line average roughness (µm)	Winding property
Example 19	0.5	2.0	1.2	0.0033	⃝
Example 20	0.5	0.5	0.6	0.0025	⃝
Example 21	11.0	0.5	1.0	0.0032	⃝
Example 22	11.0	5.0	1.5	0.0040	⃝
Comparative example 12	0.0	6.0	2.9	0.0055	⃝
Comparative example 13	12.0	2.2	1.8	0.0040	⃝

Table 11

	Mn: x10⁻² (mole %/all all acid component	Particle size silica (µm)	Amount of of silica (%)	Haze (%)	Center line average roughness (µm)	Winding property
Example 23	3	0.25	0.1	0.8	0.0041	⃝
Example 24	3	0.05	0.01	0.7	0.0028	⃝
Example 25	3	0.05	2.0	1.3	0.0050	⃝
Example 26	3	0.5	0.01	0.8	0.0042	⃝
Example 27	3	0.5	2.0	1.5	0.0055	⃝
Comparative example 14	3	0.7	0.1	1.9	0.0045	⃝
Comparative example 15	3	0.25	0.005	0.8	0.0021	△
Comparative example 16	3	0.25	3.0	2.0	0.0054	⃝
Comparative example 17	12	0.25	0.1	1.7	0.0055	⃝

Table 12

	Film thickness (µm)	Center line average roughness (µm)	Winding property	Haze (%)
Example 13	80	0.0035	⃝	1.4
Comparative example 18	120	0.0033	⃝	1.9

According to the present invention, there can be provided a support for a photographic material suitable for a light-sensitive silver halide photographic material, having excellent photographic characteristics that roll set curl can be easily resolved, and no bad influence is exerted on emulsion characteristics of photographs and color reproducibility of a positive type light-sensitive material.
Also, there can be provided a support for a photographic material having excellent recovering property from roll set curl after development processing while maintaining strength.
Further, there can be provided a support for a photographic material having excellent transparency, easy sliding property and recovering property from roll set curl.

Claims

A support for a photographic material, which comprises a copolymerized polyester containing an aromatic dicarboxylic acid having a metal sulfonate group as a monomer unit and an antioxidant, and having an L value which is an index of color of 93 or more and a b value which is an index of a color of 3 or less.
The support of Claim 1 wherein the copolymerized polyester contains a polyalkylene glycol or a polyalkylene oxy dicarboxylic acid as a monomer unit and contains an aromatic dicarboxylic acid having a metal sulfonate group detected by hydrolyzing the above copolymerized polyester in an amount of 2 to 7 mole % based on all ester bond units and the above polyalkylene glycol or polyalkylene oxy dicarboxylic acid in an amount of 3 to 10 % by weight based on the weight of all reaction products.
The support of Claim 1 wherein the copolymerized polyester contains an aliphatic dicarboxylic acid as a monomer unit and contains an aliphatic dicarboxylic acid detected by hydrolyzing the above copolymerized polyester in an amount of 3 to 25 mole % based on all ester bond units.
The support of Claim 1 wherein the L value and the b value measured by a color analyzer using C light source are 93 to 100 and 3.0 to -2.0, respectively.
The support of Claim 1 wherein the copolymerized polyester contains diethylene glycol in an amount of 5 mole % or less based on all ester bond units.
The support of Claim 5 wherein the copolymerized polyester contains a polyalkylene glycol or a polyalkylene oxy dicarboxylic acid as a monomer unit.
The support of Claim 5 wherein the copolymerized polyester further contains an aliphatic dicarboxylic acid having 4 to 20 carbon atoms as a monomer unit.
The support of Claim 5 wherein the copolymerized polyester is obtained by adding at least one selected from the group consisting of sodium acetate, sodium hydroxide and tetraethylhydroxy ammonium at transesterification and/or polymerization.
The support of Claim 1 wherein the has a haze of 1.5 % or less, a center line average roughness of 0.0025 µm or more and a thickness of 50 to 100 µm.
The support of Claim 1 wherein the copolymerized polyester contains an aromatic dicarboxylic acid having a metal sulfonate in an amount of 2 to 7 mole % based on all ester bond units and a polyalkylene glycol or a polyalkylene oxy dicarboxylic acid in an amount of 3 to 10 % by weight based on the total weight of the copolymerized polyester as copolymer components
The support of Claim 1 wherein the copolymerized polyester is obtained by polymerization using a manganese compound in an amount of 0.5 x 10⁻² to 11.0 x 10⁻² mole %/all ester bond units and a calcium compound in an amount of 0.5 x 10⁻² to 5.0 x 10⁻² mole %/all ester bond units in combination as transesterification catalysts.
The support of Claim 1 wherein the copolymerized polyester is obtained by using a manganese compound in an amount of 0.5 x 10⁻² to 11.0 x 10⁻² mole %/all ester bond units as a transesterification catalyst and also using an inert inorganic particle having an average particle size of 0.05 to 0.5 µm in an amount of 0.01 to 2.0 % by weight based on the above copolymerized polyester to be produced.
The support of Claim 1 wherein the copolymerized polyester is obtained by copolymerizing a material comprising
(a) an aromatic dibasic acid having no metal sulfonate group selected from the group consisting of terephthalic acid and 2,6-naphthalenedicarboxylic acid,

(b) a glycol selected from the group consisting of ethylene glycol, propylene glycol, butanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, diethylene glycol and p-xylylene glycol in an amount of 5 mole % or less based on all ester units,

(c) an aromatic dicarboxylic acid having a metal sulfonate group in an amount of 2 to 7 mole % based on all ester units,

(d) a polyalkylene glycol having a number average molecular weight of 300 to 20,000 or a polyalkylene oxy dicarboxylic acid in an amount of 3 to 10 % by weight based on the weight of all reaction products, or
an aliphatic dicarboxylic acid having 4 to 20 carbon atoms in an amount of 3 to 25 mole % based on all ester units,

(e) an antioxidant in an amount of 0.01 to 2 % by weight based on the copolymerized polyester,
in the presence of a manganese compound in an amount of 0.5 x 10⁻² to 11.0 x 10⁻² mole %/all ester units and a calcium compound in an amount of 0.5 x 10⁻² to 5.0 x 10⁻² mole %/all ester units in combination as transesterification catalysts.
The support of Claim 13 wherein the support has the L value and the b value measured by a color analyzer using C light source are 93 to 100 and 3.0 to -2.0, respectively, a haze of 1.5 % or less, a center line average roughness of 0.0025 µm or more and a thickness of 50 to 100 µm.
The support of Claim 13 wherein the copolymerization is carried out at 270 to 285 °C.
A support for a photographic material which comprises a film comprising, as a starting material, a copolymerized polyester containing an aromatic dicarboxylic acid having a metal sulfonate group as a monomer unit and containing diethylene glycol in an amount of 5 mole % or less based on all ester bond units.
A support for a photographic material which comprises a copolymerized polyester containing terephthalic acid and ethylene glycol as monomer units and further containing an aromatic dicarboxylic acid having a metal sulfonate group detected by hydrolysis and a polyalkylene glycol as a starting material, and has a haze of 1.5 % or less, a center line average roughness of 0.0025 µm or more and a thickness of 50 to 100 µm.