JP2000131800A - Substrate for silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a substrate for a silver halide photographic sensitive material which can be used even in a camera designed for a 135 type or brownie type photographic film, in development after photographing and in printing on photographic paper without causing transport trouble and can be produced without using a solvent. SOLUTION: The substrate for a silver halide photographic sensitive material having at least one hydrophilic colloidal layer on at least one surface of the substrate is a polyester film having 350-480 kg/mm2 Young's modulus, 20-180% breaking extension and 105-125 μm thickness. The sensitive material is for 135 type or brownie type cameras.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is widely used as a silver halide photographic film for general cameras.
The present invention relates to a photographic film support that can be used for a 35-type or brownie type photographic film.

[0002]

2. Description of the Related Art In general, typical examples of silver halide photographic light-sensitive materials (photographic films) include those in sheet form such as X-ray film, plate making film and cut film, and roll-like form. There are things.
Typical examples of the roll film include a color film or a black-and-white negative film which is mounted in a patrone with a width of 35 mm or less and is used for photographing by being loaded into a general camera. Roll film such as a wide-type brownie film with a backing paper (e.g., 120 type). 3
A photographic film having a width of 5 mm is generally used as a 135-type film as a general negative film or positive film for a camera.

[0003] Conventionally, cellulose triacetate (TA) has been used as a support for 135 type or brownie type films.
C) A film is used. The features of the TAC film as a photographic support are that it has no optical anisotropy and high transparency, and that it also has excellent properties in decurling after development processing. The TAC film is obtained by dissolving cellulose triacetate in an organic solvent such as methylene chloride, casting the resulting solution on a metal belt or the like, and drying. The organic solvent used for dissolving the cellulose triacetate, particularly a chlorine-based solvent such as methylene chloride, tends to be toxic to the human body and has problems in working environment.

On the other hand, as a material capable of forming a film without using a solvent, polyethylene terephthalate (PE)
T), polyethylene-2,6-naphthalate (PEN)
And the like are known. PET film is
Usually, it is obtained by melt-extruding PET and then biaxially stretching. Such PET films have been conventionally used as supports for X-ray films and lith films. However, when this PET film is used for a 135-type or brownie-type film support, that is, when used in a roll state, it is easy to cause curling, and thus, for example, a transport trouble with a camera, a developing process or a photographic printing paper after development. Problems such as generation of scratches in a printing step for forming an image and jamming at the time of conveyance occur.

[0005] Polyethylene-2,6-naphthalate (P
EN) is known to give strong hard films. This PEN film has been studied and put to practical use as a material for forming a thin support that can be used for a new camera system, the Advanced Photo System (APS) or a photographic film of an integrated camera (European Patent No. 60).
No. 6,070A1, JP-A-7-72584). Also,
WO 94/19722 discloses a PEN film having various physical properties and a thickness of 40 to 120 μm, which is hardly curled, and which is excellent in transparency and slipperiness. However, when these PEN films are used as a support for conventional 135-type or brownie-type films, troubles often occur when the film is automatically loaded or wound onto a camera, and 135-type or brownie-type films are often used. Consideration has not been given to the direction of application to films.

[0006] Therefore, in JP-A-9-281648, JP-A-10-69027 and JP-A-10-207008, a PEN film is made into a derivative or a mixture with a derivative, and further, optimization of production conditions, physical properties of a support, and the like. Optimization attempts to make up for the shortcomings. However, in the method using the PEN film, although curl is hard to be formed, once curl is formed, for example, when stored at a high temperature, the curl resolving property after the development processing is not sufficient, and the printing paper is printed. It was not enough to solve the problem of transportability during printer work.

Further, JP-A-6-11795, JP-A-6-202280, JP-A-6-240020 and the like alleviate the drawbacks of PET films by combining the polymer composition, lamination structure, curl degree, strength and the like. Considerations have been made. However, these techniques are all directed to a thin film base corresponding to the miniaturization of a camera, and there is no description about use for a 135 type or brownie type film.

[0008] Further, the 135 type film is often cut in the apparatus or in the pre-processing and post-processing steps because the development and baking processes have been automated, but the method using a polyester film, especially a PEN film, has a high strength. Was too strong, it could not be cut by the cutter of the automatic developing device. Furthermore, in the method using a thin film base in which the composition of the PET film was partially changed, it was considered that cutting properties were advantageous in terms of strength. With the cutter, the film was pinched between the upper blade and the lower blade, and it did not cut well.

Further, a part of a brownie type film or a 135 type film may be developed by a hanger.
When a polyester film was used, there was a problem that weight nails did not stick into the film.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a 135 type or brownie type support for a silver halide photographic light-sensitive material which can be produced without using a solvent.

More specifically, the silver halide photographic photosensitive material for 135-type or brownie-type silver halide photographic photosensitive material which has excellent cutting properties and has an improved resistance to stabbing of a nail with a hanger developed and which can be produced without using a solvent. In order to provide a support for the material, furthermore, a camera designed for 135 type, brownie type photographic film, and a solvent which can be used without trouble in the developing process of the photographed film and the printing paper printing operation. An object of the present invention is to provide a support for a silver halide photographic light-sensitive material for a 135 type or a brownie type, which can be produced without performing the above steps.

[0012]

The above object of the present invention is attained by the following constitutions.

1. A support for a silver halide photographic material having at least one hydrophilic colloid layer on at least one surface of the support, wherein the support has a Young's modulus of 350 to 4
A 135 type or brownie type silver halide photographic light-sensitive material support, characterized by being a polyester of 80 kg / mm ² , a breaking elongation of 20 to 180% and a film thickness of 105 to 125 μm.

2. A support for a silver halide photographic material having at least one hydrophilic colloid layer on at least one surface of the support, wherein the support has a curl degree after heat treatment of 135 m ^-1 or less and a curl degree in warm water. 50 m ^-1 or less, recovery curl after warm water treatment is 40 m ^-1 or less, width curl is 3 to 20 m ^-1 , Young's modulus is 350 to 480 kg /
mm ^2, the Young's modulus immediately after immersion in water is 250 kg / mm ² or more, for silver halide photographic light-sensitive material for type 135, wherein the thickness loop stiffness is 10~30g heavy is a polyester of 105~125μm Support.

3. A support for a silver halide photographic material having at least one hydrophilic colloid layer on at least one surface of the support, wherein the support has a curl degree after heat treatment of 130 m ^-1 or less and a curl degree in warm water. 45 m ^-1 or less, recovery curl after warm water treatment is 35 m ^-1 or less, width curl is 3 to 20 m ^-1 , Young's modulus is 350 to 480 kg /
mm ^2, the Young's modulus immediately after immersion in water is 250 kg / mm ² or more, for silver halide photographic light-sensitive material for brownie-type, wherein the thickness loop stiffness is 10~25g heavy is a polyester of 105~125μm Support.

4. 4. The support for a silver halide photographic light-sensitive material according to any one of claims 1 to 3, wherein the main component of the polyester is polyethylene terephthalate.

5. The support is a polyester obtained by laminating at least two layers of polyester,
4. The support for a silver halide photographic light-sensitive material according to any one of claims 2 to 3, wherein the laminated structures on both sides thereof are asymmetric with respect to a position where the thickness is bisected.

6. 6. The support for a silver halide photographic light-sensitive material according to 5, wherein adjacent layers of the laminated polyester have different moisture contents.

[7] Any one of 1 to 6, wherein the polyester contains a monomer containing at least one selected from a sulfonic acid group and a salt thereof as a copolymer component in an amount of 1 to 10 mol% based on all ester bond units. A support for a silver halide photographic light-sensitive material according to claim 1 or 2.

8. (1) The polyester according to any one of (1) to (6), wherein the polyester contains a monomer containing a polyalkylene glycol unit as a copolymer component in an amount of 0.1 to 10% by weight based on the total weight of the polyester as a reaction product. The support for a silver halide photographic light-sensitive material according to the above item.

9. The polyester is 0.35 to 0.5.
9. The support for a silver halide photographic light-sensitive material according to any one of 2 to 8, wherein the support has an intrinsic viscosity in the range of 65 and a Tg of 55 ° C. or higher.

10. 10. The support for a silver halide photographic material according to any one of 1 to 9, wherein the hydrophilic colloid layer applied to the support has a thickness of 25 μm or less.

Hereinafter, the present invention will be described in detail.

The 135 type photographic film of the present invention is JIS
K 7519-1982, "135-type film patrone". The 135-type (Leica) photographic film has the dimensions specified above, can be easily filled in the patrone specified above, and is a camera designed for 135-type photographic film as described above. It is required that the film can be used without any trouble, and that there is no problem in the processing of developing and printing photographic paper. In addition, the brownie type photographic film of the present invention is JIS K
7512-1994 "120-type and 220-type film". Brownie type photographic films are mainly 120 type (61.5 x 806 mm, with backing paper) and 220 type (61.5 x 1651 mm, with light-shielding leader paper, with trailer paper, and wound around a fine shaft). In addition, 620, 828, 616, 116
The type is known. 135 brownie type photographic films
Like a photographic film, it can be used without trouble with a camera designed for brownie photographic film,
Furthermore, it is required that there is no problem in the development processing of the photographed film and the printing paper printing processing operation.

In general, polyester has poor cutting properties as compared with TAC. In addition, in the hanger development, there is a problem that a weight nail is difficult to stab well in a film. In contrast, as a result of various studies, poor cutting of the polyester support has two cases: a case where the support is hard and cannot be cut, and a case where the film is not cut between the upper blade and the lower blade of the cutter. Understand, Young's modulus 350-480kg /
mm ² , elongation at break is 20 to 180%, and film thickness is 105 to 1
It was found that the polyester support having a thickness of 25 μm did not cause cutting failure, and it was possible to improve the difficulty of stabbing a hanger developing weight with a nail. Young's modulus is 350kg / mm
^{When the} elongation at break is ² or less, or the elongation at break is 180% or more, or the film thickness is 105 μm or less, the film is caught between the upper blade and the lower blade of the cutter, making it difficult to cut, and the film is deformed even when a weight for hanger development is applied. The nails are difficult to stick because they are easy to do. When the Young's modulus is 480 kg / mm ² or more or the film thickness is 125 μm or more, the support is hard and hard to cut, and the weight nail of the hanger development is hard to stick. Further, when the elongation at break is not more than 20%, the support is cut so as to be broken, burrs are generated on the cut surface, and the film is broken even when a weight for hanger development is applied.

Next, in the operation of the camera, the developing process, and the photographic paper baking process, it is necessary that there is no defective transport, no abrasion due to the transport trouble, and no defocusing.

The thickness of the polyester support used in the present invention, which is free from poor transport or scratches due to poor transport, depends on the above-mentioned cutting properties and the problem of focusing with a camera, and the problem of filling into a patrone for 135 type photographic film. From 105 to 125
μm. Further, the polyester support used in the present invention basically has a curl unlike the case of using PET or PEN which does not easily have a curl, but still has an appropriate strength,
Having TAC removal properties after development
The same handling can be performed.

The physical properties of the polyester support used in the present invention, which does not cause a poor conveyance due to a camera or a developing machine or a scratch due to a poor conveyance, will be described. In addition, since the area of the brownie type film is large, physical property conditions are more severe than that of the 135 type film.

The curl degree after heat treatment is 135 m ^-1 or less in the case of a 135 type film, preferably 130 m ^-1.
It is less than ^-1 . 130m for brownie type film
It is less than ^-1 . In the case where the degree of curl is higher than this, a trouble may occur in which a camera or a developing processor causes abrasion due to poor transport or poor transport.

The degree of curl in warm water is not more than 50 m ^-1 , preferably not more than 45 m ^-1 for a 135 type film. In the case of a brownie type film, it is 45 m ^-1 or less. If the degree of curl in hot water is higher than this, trouble may occur during processing in a hanger type automatic developing machine.

The degree of recovery curl after the warm water treatment is 40 m ^-1 or less for a 135 type film, and 35 m ^-1 or less for a brownie type film. If it is less than this, there will be no trouble caused by the film during the printing operation on the photographic paper after the development processing.

The width curl degree of the 135 type film and the brownie type film is 3 to 20 m ^-1 . In the case of more or less than that, the width of the curl after the application of the hydrophilic colloid layer becomes large, which may cause a problem of causing abrasion during transportation.

The Young's modulus of both the 135 type film and the brownie type film is 350 to 480 kg / mm ² .
The loop stiffness is 10 to 30 g weight for a 135 type film, and 10 to 30 g for a brownie type film.
It weighs 25 g. Outside of this range, in addition to the above-described troubles at the time of cutting, troubles at the time of automatic loading and winding of a film to a camera, transporting troubles in developing processing and printing paper printing processing operations may occur.

The Young's modulus immediately after immersion in water is at least 250 kg / mm ^{2 for} both 135 type film and brownie type film. Below this, a problem that the film breaks during the developing process may occur.

In the present invention, the hydrophilic colloid layer has a thickness of 25 μm or less. If the thickness exceeds 25 μm, it is necessary to reset the above physical properties.

The polyester support used in the present invention is obtained by laminating at least two layers of polyester resin. The number of layers constituting the support may be any number of layers as long as it is two or more layers, but generally two or three layers are preferable from the viewpoint of complicated production equipment.

In the polyester support used in the present invention, the laminated structures on both sides thereof are asymmetric with respect to the position where the thickness is divided into two equal parts.

The term “asymmetric” as used herein means a difference physically, mechanically, or chemically. For example, polyesters having different thicknesses of constituent layers, different main components constituting polyester, and different amounts of polyester. This includes different copolymerization components and their amounts, or different intrinsic viscosities, and also different water absorption and elastic modulus.

As a method for confirming the asymmetry of the laminated support, various analytical instruments can be used, and there is no particular limitation. The layer structure can be confirmed by microscopic observation of the cross section of the support. Alternatively, the support may be scraped from the top and bottom until the surface is divided into halves to obtain the upper and lower analytes, hydrolyzed, and subjected to liquid chromatography, NMR analysis, and GPC analysis. In addition, the intrinsic viscosity measurement, water absorption rate, and elastic modulus measurement of the upper and lower analytes may be performed.

Further, in the polyester support used in the present invention, adjacent layers of the laminated polyester have different moisture contents. The water content of each layer is 0.2 to 8% by weight, preferably 0.3 to 5% by weight. The difference in moisture content between adjacent layers of the laminated polyester is 0.05 to 5
%, Preferably 0.1 to 3% by weight.

The polyester used in the present invention is a polyester having an aromatic dibasic acid and a glycol as main components. Examples of the dibasic acid include terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid. Glycols include ethylene glycol, propylene glycol, butanediol, neopentyl glycol, 1,
4-cyclohexanedimethanol, diethylene glycol, p-xylylene glycol and the like. Among them, polyethylene terephthalate containing terephthalic acid and ethylene glycol as main components is preferable.

In the present invention, the term “main component is polyethylene terephthalate” means that a copolymer having a repeating unit of polyethylene terephthalate of 80 mol% or more,
Alternatively, when blended, it means that polyethylene terephthalate is contained in an amount of 80% by weight or more.

The polyester support used in the present invention preferably has at least one laminated layer containing a sulfonic acid group and / or a salt thereof, and an aromatic dicarboxylic acid having a sulfonic acid group and / or a salt thereof is preferred. , 5-sodium sulphoisophthalic acid, 2-sodium sulphoisophthalic acid, 4-sodium sulphoisophthalic acid, 4-sodium sulpho-2,6-naphthalenedicarboxylic acid or its ester-forming derivatives, and these sodiums with other metals ( For example, a compound substituted with potassium, lithium or the like is used.

The copolymerization ratio of the aromatic dicarboxylic acid component having a metal sulfonate group is from 1 to 10 mol% with respect to all the ester bond units. If it exceeds 10 mol%, the stretchability is poor and the mechanical strength is poor, which is not preferable.

Further, at least one of the laminated polyester supports used in the present invention preferably contains a polyalkylene glycol as a copolymerization component.
The polyalkylene glycol is contained in an amount of 0.1 to 10% by weight, preferably 0.2 to 8% by weight, based on the total weight of the reaction product polyester. If the amount of the polyalkylene glycol is less than 0.1% by weight, sufficient curling-releasing property cannot be obtained. On the other hand, if it exceeds 10% by weight, the Young's modulus immediately after immersion in water decreases, resulting in poor mechanical strength.

As the polyalkylene glycol, polyethylene glycol, polytetramethylene glycol and the like can be used. Of these, polyethylene glycol is preferable, and the molecular weight is not particularly limited, but is preferably 300 to 300.
20,000 is preferable, and 600 to 10 is more preferable.
000, especially 1000 to 5000 are preferably used.

The copolymerized polyester used for the photographic support of the present invention has a range of not impairing the effects of the present invention.
Further, other components may be copolymerized, or other polymers may be blended.

Examples of the dibasic acids other than those described above that can be used in the present invention include terephthalic acid, isophthalic acid, phthalic acid, sodium isophthalic acid sulfonate (sodium sulfoisophthalic acid) and lower alkyl esters thereof. (An ester-forming derivative such as an anhydride or a lower alkyl ester) can be used. Other dicarboxylic acids other than the above or derivatives thereof include aromatic dicarboxylic acids such as 2,7-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, and diphenyletherdicarboxylic acid, and lower alkyl esters thereof (anhydrides, Derivatives capable of forming esters such as lower alkyl esters); Alicyclic dicarboxylic acids such as cyclopropanedicarboxylic acid, cyclobutanedicarboxylic acid and hexahydroterephthalic acid and derivatives thereof (derivatives capable of forming esters such as anhydrides and lower alkyl esters) And aliphatic dicarboxylic acids such as adipic acid, succinic acid, oxalic acid, azelaic acid, sebacic acid and dimer acid and derivatives thereof (derivatives capable of forming an ester such as anhydrides and lower alkyl esters) of all dibasic acids. Not more than mol% It may be used.

The dihydric alcohol other than ethylene glycol which can be used in the present invention includes propylene glycol, trimethylene glycol, diethylene glycol, triethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, p -Xylene glycol, 1,4-cyclohexanedimethanol, bisphenol A, p, p'-
Dihydroxyphenylsulfone, 1,4-bis (β-
Hydroxyethoxyphenyl) propane, polyalkylene (eg, ethylene, propylene) glycol, and p-
Phenylenebis (dimethylolcyclohexane) and the like can be mentioned. These are 10 of the dihydric alcohols.
It may be used in an amount of at most mol%.

The above-mentioned polyester may be obtained by blocking a terminal hydroxyl group and / or a carboxyl group with a monofunctional compound such as benzoic acid, benzoylbenzoic acid, benzyloxybenzoic acid, methoxypolyalkylene glycol, or For example, it may be modified with a very small amount of a trifunctional or tetrafunctional ester-forming compound such as glycerin or pentaerythritol as long as a substantially linear copolymer can be obtained.

The copolymerization of the copolyester used in the present invention can be carried out by a commonly known method. That is, after transesterification of the dicarboxylic acid component and the glycol component, polycondensation can be performed at a high temperature under reduced pressure to obtain a copolymerized polyester. In this case, an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component or polyethylene is obtained. Glycol is added after the transesterification reaction to perform polycondensation.

The polyester resin used in the present invention has an intrinsic viscosity in the range of 0.35 to 0.65. Below this range, the fragility is insufficient, and above this range, the mechanical strength is too strong.

The polyester resin used in the present invention has a Tg of 55 ° C. or higher, preferably 60 ° C. or higher. If the temperature is 55 ° C. or lower, the curl of the curl becomes too large, and the curl of the curl by the development processing is insufficient.

As a method for producing the photographic support of the present invention, for example, the polyester of each layer to be laminated is melt-extruded from a separate extruder, and then joined in a laminar flow in a conduit of a molten polymer or an extrusion die. Extruded, cooled and solidified on a cooling drum, biaxially stretched after obtaining an unstretched film, and co-extrusion method of heat setting, or melt-extruding polyester from an extruder and cooling and solidifying on a cooling drum an unstretched film or The unstretched film is uniaxially stretched, and the surface of the uniaxially oriented film is coated with an anchoring agent, an adhesive and the like, if necessary, and then the copolymer polyester is extrusion-laminated thereon. Although there is an extrusion lamination method for fixing, etc., a co-extrusion method is preferred from the viewpoint of simplicity of the process.

The stretching conditions of the film are not particularly limited, but it is generally preferable to appropriately adjust the conditions of the polyester layer.
Stretch ratio of 2.5 to 2 in the biaxial direction in a temperature range of 0 ° C.
It is preferable to carry out in the range of 6.0 times. The heat setting can be performed in a temperature range of 150 ° C to 240 ° C.

The photographic support of the present invention comprises at least one silver halide emulsion layer on at least one side to constitute a silver halide photographic light-sensitive material. The silver halide emulsion layer may be coated directly on the support, or may be coated via another layer such as a hydrophilic colloid layer containing no silver halide emulsion.

At this time, various surface treatments such as a corona discharge treatment, a glow discharge treatment, an ultraviolet treatment, a flame treatment, a discharge plasma treatment in an atmospheric pressure gas, and a chemical treatment are required for improving the adhesiveness of the photographic support. Can be applied accordingly. Further, an undercoat layer may be applied to improve the adhesion.

The silver halide constituting the silver halide emulsion layer used in the present invention may have any composition. For example, there are silver chloride, silver chlorobromide, silver chloroiodobromide, pure silver bromide and silver iodobromide.

A sensitizing dye, a plasticizer, an antistatic agent, a surfactant, a hardener and the like can be added to the silver halide photographic material.

To develop a silver halide photographic light-sensitive material, for example, H. James The Theory of the Photographic Process 4th Edition (The
Theory of the Photograph
ic Process, Fourth Edition
n) Pages 291-334 and Journal of the
American Chemical Society (Journal)
of the American Chemical
Society, 73, 3,100 (195
Developers such as those described under 1) can be used.

[0061]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

(Synthesis Example 1) Dimethyl terephthalate 100
0.1 part by weight of calcium acetate hydrate was added to 64 parts by weight of ethylene glycol and 64 parts by weight of ethylene glycol, and a transesterification reaction was carried out by a conventional method. 39 parts by weight of an ethylene glycol solution of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid (concentration: 35% by weight) (7 mol% / total acid component) and polyethylene glycol (number average molecular weight: 3,000) were added to the obtained product. 5.8 parts by weight (5% by weight / polymer),
0.05 parts by weight of antimony trioxide and 0.13 parts by weight of trimethyl phosphate were added. Then gradually raise the temperature,
The pressure was reduced and polymerization was carried out at 280 ° C. and 0.5 mmHg to obtain a copolymerized polyester A. The water content was 4.5% and the intrinsic viscosity was 0.41.

(Synthesis Example 2) 22 parts by weight (4 mol% / total acid component) of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid in ethylene glycol solution (concentration 35% by weight), polyethylene glycol ( (Number average molecular weight 3000) 0.6 parts by weight (0.5% by weight / polymer)
Was obtained in the same manner as in Synthesis Example 1 except that the above was changed. The water content is 2.8% and the intrinsic viscosity is 0.4
It was 5.

(Synthesis Example 3) 5.5 parts by weight (1 mol% / total acid component) of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid in ethylene glycol solution (concentration 35% by weight), polyethylene Copolymer Polyester C was obtained in the same manner as in Synthesis Example 1 except that glycol (number average molecular weight 3000) was not added. The moisture content is 0.
8% and the intrinsic viscosity was 0.55.

(Synthesis Example 4) An addition amount of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid in an ethylene glycol solution (concentration: 35% by weight) was 22 parts by weight (4 mol% / total acid component), polyethylene glycol ( A copolymer polyester D was obtained in the same manner as in Synthesis Example 1 except that the number average molecular weight was changed to 12.2 parts by weight (10.5% by weight / polymer). The water content was 3.7% and the intrinsic viscosity was 0.38.

The water content and the intrinsic viscosity were measured according to the following measuring methods.

<Water content> The copolymerized polyester was heated at 23 ° C.
After leaving it in a room conditioned at a relative humidity of 20% for 4 hours or more, it is immersed in distilled water at 23 ° C. for 24 hours, and then a trace moisture meter (for example, Model CA-20 manufactured by Mitsubishi Chemical Corporation) is put on. The drying temperature was measured at 150 ° C.

<Intrinsic Viscosity> The intrinsic viscosity was measured using an Ubbelohde viscometer. The weight ratio is about 55:45 (flowing time 42.0 ±
Phenol) and 1,1,2,2-
Using a mixed solvent with tetrachloroethane, the sample was dissolved to prepare a solution (temperature: 20 ° C.) having a concentration of 0.2, 0.6, or 1.0 (g / dl). The specific viscosity (ηsp) at each concentration was determined with an Ubbelohde viscometer,
The intrinsic viscosity was determined by extrapolating to a concentration of zero. The unit of intrinsic viscosity is d
1 / g.

Example 1 (Preparation of Support) These copolymerized polyesters were prepared and dried in vacuum at 150 ° C., respectively, and then melted at 285 ° C. using one or three extruders when laminating. When extruding and laminating, the three layers were joined in layers in a T-die so as to be composed of the materials shown in Table 1, and quenched and solidified on a cooling drum to obtain a laminated unstretched film. At this time, the extrusion amount of each material was adjusted, and the thickness of each layer was changed as shown in Table 1. Next, the film was stretched 3.5 times in the vertical direction at 85 ° C.
After stretching 3.5 times in the horizontal direction at 5 ° C., it was heat-set at the temperature shown in Table 1 to obtain a biaxially stretched polyester support. Further, PET and PEN supports were prepared. Also, Japanese Patent Application Laid-Open
The support of Example No. 0-207008, No. 1 was prepared according to the method described. The contents of the produced support are as shown in Table 1. The support having a laminated structure is denoted by d1, d2 and d3 from the side on which the emulsion layer is coated.

Next, the Young's modulus and elongation at break of the prepared support were measured according to the following measuring methods. The results are as shown in Table 1.

<Young's modulus and elongation at break>
After leaving for more than 4 hours in a room adjusted to 55 ° C. and a relative humidity of 55%, the sample was cut into 10 mm in width and 150 mm in length.
A tensile test was performed. The Young's modulus was calculated from the tangent at the rising portion of the obtained load-elongation curve. Also, (elongation at break, mm) / (initial chuck distance, 100 m
m) × 100 (%) to determine the elongation at break.

(Preparation of silver halide photographic light-sensitive material) Both surfaces of each prepared support were subjected to a corona discharge treatment of 12 W · min / m ² , and a subbing coating solution B-
1 was applied to a dry film thickness of 0.4 μm, and a corona discharge treatment of 12 W · min / m ² was applied thereon, and a subbing coating solution B-2 was applied to a dry film thickness of 0.06 μm. did.

On the other surface, an undercoating coating solution B-3 was applied to a dry film thickness of 0.2 μm, and 12 W · m
in / m ² corona discharge treatment, and the conductive layer coating solution A
-1 was applied to a dry film thickness of 0.2 μm.

<Undercoat Coating Solution B-1> A copolymer latex solution (solid content: 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) 30 g) 50 g Compound (UL-1) 0.2 g Hexamethylene-1,6-bis (ethylene urea) 0.05 g Finish with water 1000 ml <Undercoat coating solution B-2> Gelatin 10 g Compound (UL-1) 0 0.2 g Compound (UL-2) 0.2 g Silica particles (average particle size 3 μm) 0.1 g Hardener (UL-3) 1 g Finish with water 1000 ml <Undercoat coating solution B-3> Epocross K-2020E (solid 40% (manufactured by Nippon Shokubai Co., Ltd.) 50 g Compound (UL-1) 0.2 g Finish with water 1000 ml <Conductive layer coating solution A-1> Gelatin 10 g Conductive agent (antimony-doped crystalline tin oxide) SN100D (manufactured by Ishihara Sangyo Co., Ltd., solid content: 30 wt%) 150 g Compound (UL-1) 0.4 g Hardener (UL-3) 0.75 g Finish with water 1000 ml

[0075]

Embedded image

Each layer was dried at 110 ° C. for 10 seconds after application, and subsequently heat-treated at 110 ° C. for 2 minutes.

Next, the following coating solution M-1 was applied on the surface coated with the conductive layer coating solution A-1 so as to have a dry film thickness of 0.8 μm, and a sliding layer O-1 was further dried thereon. It was applied to a thickness of 0.2 μm. After each application, each layer is
It was dried for 0 seconds and subsequently heat treated at 90 ° C. for 2 minutes.

<Coating Liquid M-1> Cellulose diacetate 82 g Silica (average particle size 0.2 μm) 0.5 g Tolylene diisocyanate trimethylolpropane (TDI / TMP) 15 g Acetone 990 g Cyclohexanone 110 g For 1 hour to obtain a coating solution M-1.

<Sliding Layer Coating Solution O-1> Carnauba Wax 7 g Toluene 700 g Methyl Ethyl Ketone 300 g Further, the same photographic emulsion layer as a commercially available color negative film Konica Color JX400 manufactured by Konica Co., Ltd. was coated with a subbing coating solution B-2. Coating was performed on the coated surface to obtain silver halide photographic materials 1 to 18.

The cutability of the silver halide photographic light-sensitive material thus obtained and the ease of stabbing of a nail with a hanger developing weight were evaluated by the following methods. Table 1 shows the results.

<Cutability> The obtained silver halide photographic light-sensitive material was cut into dimensions specified in JIS K 7519-1982, “135-type film patrone”, and mounted on a patrone. 20 of these films were purchased from Konica Corporation.
The film was passed through an automatic development processor CL-KP50QA, and the cutability of the film edge was evaluated according to the following criteria. It must be level A.

A: All pieces were cut B: One or two pieces could not be cut or the cut face had an abnormality C: Two or more pieces could not be cut or the cut face had an error <Hanger Easiness of piercing of developing weight nail> The obtained silver halide photographic light-sensitive material is used in accordance with JIS K 7512-199.
4 The film was cut into dimensions specified in “120-type and 220-type films”, and a weight of a hanger development for a brownie type was attached to ten of the films, and the ease of attachment was evaluated according to the following criteria. Must be level B or higher. A is more desirable.

A: Attached easily B: A little hard to touch but could be mounted C: Very hard to touch or no touch

[0084]

[Table 1]

As can be seen from Table 1, the support had a Young's modulus of 350 to 480 kg / mm ² and a breaking elongation of 20 to 180.
%, When the film thickness is 105 to 125 μm, the cutability is good, and the ease of stabbing the nail with the weight of the hanger development is also improved. The polyester is PE
Those containing T as a main component are preferable, and those containing a monomer containing a sulfonic acid group and / or a salt thereof and a polyalkylene glycol unit as a copolymerization component are more preferable.

Example 2 A support shown in Table 2 was obtained in the same manner as in Example 1. The physical properties of these supports were evaluated by the following evaluation methods. Table 2 shows the results
As shown in FIG.

<Heat Curl Degree after Heat Treatment>
mm (horizontal method at the time of manufacture) x 120 mm (vertical direction at the time of manufacture) and cut into a core having a diameter of 10.8 mm after leaving for 1 day at a temperature of 23 ° C and a relative humidity of 55%. Was wound. At this time, if the support has a wide curl, the support is wound so that the concave surface of the support is outside. Then, at a temperature of 55 ° C. and a relative humidity of 20%,
Heat treatment was performed for a time.

After the heat treatment, the core was allowed to cool for 30 minutes at a temperature of 23 ° C. and a relative humidity of 55%, and then released from the core.
After a lapse of minutes, the curl degree of curl of the support is measured. The degree of curl is represented by 1 / r, and r represents the radius of curvature of the curled support, and the unit is m. Therefore, the unit of the curl degree is 1 / m.

<Degree of curl in hot water> The support was cut into a strip of 35 mm (horizontal method at the time of manufacture) x 2 mm (vertical direction at the time of manufacture), and immersed in warm water at 38 ° C for 30 minutes. Measure the degree of curl.

<Recovery Curl Degree After Warm Water Treatment> Heat treatment is performed in the same manner as the curl curl degree after heat treatment. After the heat treatment, the core was released from the core, and a load of 70 g was applied to one end of the support.
10 minutes in warm water. Then, it is dried for 3 minutes with a hot air dryer at 55 ° C. while applying a load. The load was removed, the support was placed on its side, and the temperature was 23 ° C. and the relative humidity was 55.
%, The curl degree at the center of the film is measured.

<Width Curl Degree> The support was cut into a band of 35 mm (horizontal method at the time of manufacture) × 2 mm (vertical direction at the time of manufacture), and left at a temperature of 23 ° C. and a relative humidity of 55% for one day. After that, the degree of curl in the width direction is measured.

<Young's modulus and Young's modulus immediately after immersion in water> The Young's modulus was measured in the same manner as in Example 1, and the Young's modulus immediately after immersion in water was measured similarly immediately after immersing the support in water at 25 ° C for 30 minutes. did.

<Loop stiffness> The support is 35 mm
The film was cut into a strip having a size of × 180 mm, a loop was formed at a portion having a length of 100 mm near the center of the film, and the load applied when the loop was pushed 10 mm from the outside was measured. This measurement was performed using "Loop Stiffness Tester" (manufactured by Toyo Seiki Seisaku-sho, Ltd.).

<Tg (Glass Transition Temperature)> 50 mg of the obtained copolymerized polyester was measured by a differential scanning calorimeter (DSC-5).
0 (manufactured by Shimadzu Corporation) at a heating rate of 10 ° C./min in a nitrogen stream. The glass transition temperature was the temperature at which the slope at the beginning of the peak representing the glass transition decreased (the temperature at which the graph was broken).

(Preparation of silver halide photographic light-sensitive material) Silver halide photographic light-sensitive material samples 101 to 115 were obtained in exactly the same manner as in Example 1 except that the obtained support was used. The obtained silver halide photographic material was subjected to JIS K
The film was cut to the size specified in “135-type film patrone” of No. 7519-1982 and attached to the patrone. In the same manner, the 120 film specified in “120 type and 220 type film” of JIS K 7512-1994.
It was processed into a mold film (61.5 × 806 mm, with backing paper). The film thus obtained was heat-treated at a temperature of 80 ° C. and a relative humidity of 20% for 2 hours, and then its transportability was confirmed by the following method. Table 3 shows the results.

<Transportability by Camera (135 type)> The patrone loaded with the obtained photographic film was loaded into a camera (using Big Mini manufactured by Konica Corporation), and automatic loading and automatic winding were performed. During these operations, the occurrence of jamming (clogging) and the occurrence of scratches on the film were observed.

A: No occurrence of jamming and scratches B: No occurrence of jamming but occurrence of scratches C: Occurrence of jamming <Conveyability in laboratory processing (135 type)> Development and printing using the obtained photographic film Work (using Konica's NPS-808) and jam (jam)
And the occurrence of scratches on the film were observed.

A: No jamming and no scratches occurred B: No jamming occurred, but scratches occurred C: Jamming occurred <Transportability with camera (Brownie type)> The obtained photographic film was transferred to a camera (Asahi Optical Co., Ltd.) ) PENTAX 6
45 used) and photographed. During these operations, the occurrence of jamming (clogging) and the occurrence of scratches on the film were observed.

A: No jamming and no scratches occurred B: No jamming occurred, but scratches occurred C: Jamming occurred <Transportability in lab processing (Brownie type)> Using the obtained photographic film, developing (Noritsu) A hanger type developing machine HM-55S manufactured by Koki Co., Ltd. was used, and a printing operation was performed (KCP-1045 manufactured by Konica Corp.), and the occurrence of jamming (clogging) and the occurrence of scratches on the film were observed.

A: No jamming and no scratches occurred B: No jamming occurred, but scratches occurred C: Jamming occurred

[0101]

[Table 2]

[0102]

[Table 3]

As is clear from Tables 2 and 3, the silver halide photographic light-sensitive materials having the physical properties of the support within the range of the present invention were photographed with a camera designed for 135-type and brownie-type photographic films and photographed. It can be seen that the film can be used without trouble in the film developing process and the printing paper printing operation.

[0104]

According to the present invention, there is provided a support for a 135 type or brownie type silver halide photographic light-sensitive material which can be produced without using a solvent.

More specifically, the silver halide photographic light-sensitive material for 135-type or brownie-type, which is excellent in cutting properties and improved in the resistance to stabbing of the weight nail of the hanger development, can be produced without using a solvent. To provide a support for the material, and to use a camera designed for 135-type and brownie type photographic film, and a solvent that can be used in the processing of the photographed film and the printing paper printing operation without any trouble in transport. Thus, a support for a silver halide photographic light-sensitive material for a 135 type or a brownie type, which can be produced without any problem, was provided.

Claims (10)

[Claims] 1. A support for a silver halide photographic material having at least one hydrophilic colloid layer on at least one side of the support, wherein the support has a Young's modulus of 350 to 48.
0 kg / mm ² , elongation at break 20-180%, film thickness 1
A support for a 135-type or brownie-type silver halide photographic light-sensitive material, which is a polyester having a thickness of from 0.5 to 125 µm. 2. A support for a silver halide photographic material having at least one hydrophilic colloid layer on at least one surface of the support, wherein the support has a curl curl degree after heat treatment of 135 m ^-1 or less. The degree of curl in hot water is 50m ^-1 or less,
Recovery curl after hot water treatment is 40 m ^-1 or less, width curl is 3 to 20 m ^-1 , Young's modulus is 350 to 480 kg / mm.
^2. Young's modulus immediately after immersion in water is 250 kg / mm ² or more,
A film having a loop stiffness of 10 to 30 g weight and a film thickness of 10
A support for a 135-type silver halide photographic light-sensitive material, which is a polyester having a size of 5 to 125 µm. 3. A support for a silver halide photographic material having at least one hydrophilic colloid layer on at least one surface of the support, wherein the support has a curl degree after heat treatment of 130 m ^-1 or less. The degree of curl in hot water is 45m ^-1 or less,
Recovery curl degree after warm water treatment is 35 m ^-1 or less, width curl degree is 3 to 20 m ^-1 , Young's modulus is 350 to 480 kg / mm.
^2. Young's modulus immediately after immersion in water is 250 kg / mm ² or more,
A film having a loop stiffness of 10 to 25 g weight and a film thickness of 10
A support for a brownie type silver halide photographic material, which is a polyester having a thickness of 5 to 125 [mu] m. 4. The polyester according to claim 1, wherein a main component of said polyester is polyethylene terephthalate.
A support for a silver halide photographic light-sensitive material according to any one of the above. 5. The support according to claim 1, wherein the support is a polyester formed by laminating at least two layers of polyester, and the laminated structures on both sides thereof are asymmetric with respect to a position where the thickness is divided into two equal parts. The support for a silver halide photographic light-sensitive material according to any one of claims 2 to 3, wherein 6. The laminated polyester according to claim 5, wherein adjacent layers of the polyester have different moisture contents.
The support for the silver halide photographic light-sensitive material described above. 7. The polyester according to claim 1, wherein the polyester contains a monomer containing at least one selected from a sulfonic acid group and a salt thereof as a copolymer component in an amount of 1 to 10 mol% based on all ester bond units. A support for a silver halide photographic light-sensitive material according to any one of claims 1 to 6. 8. The polyester according to claim 1, wherein a monomer containing a polyalkylene glycol unit is contained as a copolymer component in an amount of 0.1 to 10% by weight based on the total weight of the polyester as a reaction product. 7. The support for a silver halide photographic light-sensitive material according to any one of items 1 to 6. 9. The method according to claim 9, wherein the polyester is 0.35 to 0.6.
9. The support for a silver halide photographic light-sensitive material according to claim 2, having an intrinsic viscosity in the range of 5 and a Tg of 55 [deg.] C. or more. 10. The hydrophilic colloid layer applied to the support is 25 μm or less.
10. The support for a silver halide photographic light-sensitive material according to any one of items 9 to 9.