JP2005062782A - Photographic sensitive material excellent in suitability to cutting - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material having improved suitability to cutting by controlling an average intrinsic viscosity of polyester films constituting a laminated polyester support to a specified numeric value or below. <P>SOLUTION: In the silver halide photographic sensitive material excellent in suitability to cutting and having at least one silver halide emulsion layer on a laminated polyester support in which one polyester layer of mutually different polyester layers contains, as copolymerized components, an aromatic dicarboxylic acid having a metal sulfonate group in an amount of 2-7 mol% based on all ester linkages and polyalkylene glycols and/or a saturated aliphatic dicarboxylic acid in an amount of 3-10 wt.% based on the total weight of the reaction product, an average intrinsic viscosity of the support is ≤0.55 (dl/g). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

Detailed Description of the Invention

The present invention relates to a photographic light-sensitive material. More specifically, the present invention relates to a silver halide photographic light-sensitive material having excellent cutting properties.

As a plastic film support conventionally used, a triacetate film such as triacetyl cellulose (hereinafter sometimes abbreviated as TAC) is representative, but TAC uses methylene chloride during film production. It is used in a large amount, and from the viewpoint of environmental protection, it is not preferable because many auxiliary facilities such as a recovery device are necessary and the cost is increased.

On the other hand, polyethylene terephthalate is conventionally known as a support, and has been used for X-ray films and plate-making films. Due to its excellent strength, it can be applied to color negative films. However, although the polyethylene terephthalate support is excellent in strength, there is a drawback in that it is inferior in curling resolving properties, in that it can hardly be wound once after development processing.

From the viewpoint of environmental protection, it is preferable to use a thermoplastic resin that does not use an organic solvent. From the viewpoint of eliminating curling, JP-A-6-240020 discloses that different polyesters are laminated, and any one polyester layer is hydrophilic. It proposes a technique for improving a laminated polyester comprising a copolymerized polyester obtained by copolymerizing the components, and mentions that it is possible to improve the wrapping resolving property after development processing to the same extent as TAC.

By the way, in the present photographic industry, a large number of films are rejoined by a splicer processor, developed with a cine type automatic developing processor, and then cut and separated. However, such a photographic light-sensitive material having a silver halide emulsion layer on a laminated polyester support retains the mechanical strength inherent to polyester, so that it does not work well with TAC films. However, some of the blades were not able to be cut because the blades entered the middle halfway, so that they could not withstand practicality, and improvements were demanded.

Problems to be solved by the invention

The present invention has been made in order to solve the above-mentioned problems, and the object thereof is to support a thermoplastic resin which is easy to handle and is easy to cut without being particularly difficult to wind without using an organic solvent. The object is to provide a silver halide photographic light-sensitive material comprising a body.

Means for solving the problem

In a photographic light-sensitive material comprising a silver halide emulsion layer on a laminated polyester support comprising different polyester layers and containing a specific proportion of water-absorbing copolymer component, the intrinsic viscosity and average intrinsic property of each polyester layer constituting the support This is achieved by a silver halide photographic light-sensitive material characterized in that the viscosity is not more than a specific value.

That is, the invention according to claim 1 for solving the above-described problem is that any one of the polyester layers different from each other has an aromatic dicarboxylic acid having a metal sulfonate group as a copolymer component as a total ester bond. On a laminated polyester support containing at least 2 to 7 mol% and containing 3 to 10 wt% of polyalkylene glycols and / or saturated aliphatic dicarboxylic acids based on the total weight of the reaction product, A photographic light-sensitive material having a silver halide emulsion layer, wherein the support has an average intrinsic viscosity of 0.55 (dl / g) or less, and is excellent in cutting property. It is.

The invention according to claim 2 is the invention according to claim 1, wherein the support is formed by laminating three polyester layers, and the two copolyester layers positioned on both sides of the central layer are different in thickness. A silver halide photographic light-sensitive material having excellent cutting properties.

The invention according to claim 3 is characterized in that the average intrinsic viscosity of the support is 0.52 (dl / g) or less, and the silver halide having excellent cutting properties according to claim 1 or 2 Photosensitive material.

The invention according to claim 4 is a silver halide photographic photosensitive material having excellent cutting properties according to any one of claims 1 to 3, wherein the tear strength in the longitudinal direction of the support is 0.75 kg / mm or less. material.

The invention according to claim 5 is a silver halide photographic photosensitive material having excellent cutting properties according to any one of claims 1 to 3, wherein the tear strength in the longitudinal direction of the support is 0.50 kg / mm or less. material.

The present invention is described in detail below.

The measuring method of the film physical property value in this invention is described below.

<Intrinsic viscosity> It was carried out using an Ubbelohde viscometer. Using a mixed solvent of phenol and 1,1,2,2-tetrachloroethane having a weight ratio of about 55:45 (adjusted to a flow time of 42.0 ± 0.1 seconds), the sample was dissolved to a concentration of 0.2 , 0.6, 1.0 (g / dl) solutions (temperature 20 ° C.) were prepared. The specific viscosity (ηsp) at each concentration (C) was determined with an Ubbelohde viscometer, and extrapolated to zero concentration according to the following equation to determine the intrinsic viscosity [η]. The unit of intrinsic viscosity [η] is dl / g.

<Tear strength> Using a light-load tear tester, similar to the method described in JIS P 8116, cut a test piece of 63.5 mm (tear direction) × 50 mm as shown in the figure below, and tear and tear one by one. The force required sometimes is expressed in units of weight and converted per unit thickness, and the unit is Kg / mm. The thickness of the laminated polyester support is measured at 7 points using a micrometer, the maximum value and the minimum value are excluded, and the thickness of each measurement sample is an average value of 5 points in mm units. expressed. The force required for tearing (tear strength; unit Kg / mm) is shown as an average value of 5 points.

-Film forming material-The film of the present invention has a polyester layer and / or a copolymerized polyester layer.

--Polyester--The polyester as the material for forming the polyester layer refers to those having a repeating unit of dicarboxylic acid and diol as the main constituent, preferably a repeating unit of aromatic dibasic acid and glycol. Mention may be made of polyester as the main constituent.

Examples of the dibasic acid include terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acids. Examples of the diol or glycol include ethylene glycol, propylene glycol, butanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, and diethylene glycol. And p-xylene glycol. Of these, polyethylene terephthalate containing terephthalic acid and ethylene glycol as main constituents and polyethylene-2,6-naphthalate containing 2,6-naphthalenedicarboxylic acid and ethylene glycol as main constituents are preferable.

In addition, the main repeating unit may be a copolymer of 85 mol% or more, preferably 90 mol% or more, as long as the original excellent properties of the polyester are not impaired, and other polymers are blended. Also good.

The preferred intrinsic viscosity of the polyester is that the photographic material having at least one silver halide emulsion layer on the laminated polyester support can be cut easily, that is, can be easily cut, and the working efficiency and productivity can be improved. In view of the above, the average intrinsic viscosity of the laminated support is preferably 0.55 (dl / g) or less. Preferably, the average intrinsic viscosity of the laminated support is 0.52 (dl / g) or less. Here, the average intrinsic viscosity is none other than the intrinsic viscosity of the laminated polyester support, but since additivity is established in the intrinsic viscosity, the composition ratio (weight) to the intrinsic viscosity of each polyester layer constituting the laminated support. It is also possible to calculate by multiplying.

-Copolyester-Copolyester used to form the copolyester layer comprises an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component, and the main component is a repeating unit of dicarboxylic acid and diol. As a component, a copolyester having an aromatic dibasic acid and glycol as main components can be mentioned. Furthermore, in this invention, the blend of the said copolyester and the said polyester can also be mentioned as copolyester.

Examples of the dibasic acid include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acids, and examples of the glycol include ethylene glycol, propylene glycol, butanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, diethylene glycol, p -Xylene glycol and the like. Among the copolymer polyesters, there are copolymer polyethylene terephthalate having terephthalic acid and ethylene glycol as main components, and copolymer polyethylene-2,6-naphthalate having 2,6-naphthalenedicarboxylic acid and ethylene glycol as main components. preferable.

Further, the preferred intrinsic viscosity of the copolyester is that the photographic material having at least one silver halide emulsion layer on the laminated polyester support can be cut easily, that is, can be easily cut, work efficiency, production From the viewpoint of improving the property, the intrinsic viscosity of the copolymerized polyester support is preferably 0.35 to 0.57 (dl / g) or less. Preferably, it is 0.35 to 0.54 (dl / g) or less.

The aromatic dicarboxylic acid containing a metal sulfonate group as a copolymerization component in the copolymerized polyester includes 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 4-sodium sulfoterephthalic acid, 4-sodium sulfo-2, Examples thereof include 6-naphthalenedicarboxylic acid or ester-forming derivatives represented by the following chemical formula 1, and compounds obtained by substituting these sodium with other metals such as potassium and lithium.

The copolymer polyester preferably contains a polyalkylene glycol and / or a saturated aliphatic dicarboxylic acid as a copolymer component as long as the effects of the present invention are not impaired.

Examples of the polyalkylene glycols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and derivatives thereof. The molecular weight of polyalkylene glycols that can be used is not particularly limited, but is preferably 300 to 20,000, more preferably 600 to 10,000, and particularly preferably 1,000 to 5,000. Polyalkylene glycol is particularly preferable, and among these, polyethylene glycol represented by the formula (a) is particularly preferable.

H (O-CH2CH2) n-OH (a)
Polyalkylene glycols include polyethyleneoxydicarboxylic acid represented by the formula (b) in which the terminal -H of polyethylene glycol is substituted with -CH2COOR (R: H or an alkyl group having 1 to 10 carbon atoms, n: positive The same effect can be obtained by using a polyether dicarboxylic acid (R ′: H or an alkylene group having 2 to 10 carbon atoms, n: a positive integer) as represented by the formula (c). .

ROOCCH2- (O-CH2CH2) n-OCH2COOR (b)
ROOCCH2- (OR ') n-OCH2COOR (C)
In any case of the compound represented by the formula (b) and the compound represented by the formula (c), the molecular weight is preferably 300 to 20,000, more preferably 600 to 10,000, and particularly 1,000 to 5, 000 is preferably used.

As the saturated aliphatic dicarboxylic acid, for example, an ester-forming derivative thereof is preferable, and adipic acid, dimethyl adipate, dimethyl sebacate and the like that are esters of adipic acid and sebacic acid are used. Preferred is dimethyl adipate.

In the copolymerized polyester used in the present invention, other components may be further copolymerized or other polymers may be blended as long as the effects of the present invention are not impaired. In particular, an alicyclic hydrocarbon dicarboxylic acid ester that contributes to easy cleavability, such as 1,4-cyclohexanedimethanol, may be copolymerized in an amount of 10 to 40% by weight, or cyclohexanedimethanol polymer. May be blended in an amount of 10 to 40% by weight.

-Production of polyester and copolymer polyester-Both polyester and copolymer polyester used in the present invention are phosphoric acid, phosphorous acid and esters thereof and inorganic particles (silica, kaolin, calcium carbonate, calcium phosphate, Titanium dioxide, etc.), organic crosslinked particles (polymethylmethacrylate, etc.) may be contained, and inorganic particles may be blended with the polymer after polymerization. Further, a pigment, an ultraviolet absorber, an antioxidant, or the like may be added as appropriate at any stage of polymerization or after polymerization.

In order to obtain a copolymerized polyester, the acid component and the glycol component may be transesterified, and then the above-described copolymerized component may be added to perform melt polymerization. Alternatively, the copolymerized component may be added before transesterification. Then, melt polymerization may be performed after transesterification, or a known synthesis method such as solid-phase polymerization of a polymer obtained by melt polymerization may be employed.

Examples of the catalyst used in the transesterification include acetates, fatty acid salts, carbonates and the like of metals such as manganese, calcium, zinc, and cobalt. Of these, hydrates of manganese acetate and calcium acetate are preferable, and a mixture of these is preferable. It is also effective to add a hydroxide, a metal salt of an aliphatic carboxylic acid, a quaternary ammonium salt, etc. within a range that does not inhibit the reaction or color the polymer during the transesterification and / or polymerization. Sodium hydroxide, sodium acetate, tetraethylhydroxyammonium and the like are preferable, and sodium acetate is particularly preferable.

The polyester or copolymer polyester for forming the film of the present invention may contain various additives. For example, a mixture of dyes may be used.

-Layer structure of film-The film of the present invention contains a polyester layer and / or a copolyester layer as described above, and the layer structure has any number such as two layers, three layers, four layers, etc. A laminated structure in which these layers are laminated may be used. The “layer” constituting the film of the present invention is not limited to the one having a thickness of 2 microns or more, and the undercoat layer having a thickness of less than 2 microns, for example, is not regarded as the “layer” constituting the film.

-Film of laminated structure-When the film of the present invention has a laminated structure of two or more layers, generally, the thickness of each layer is appropriately determined according to the polyester and copolymer polyester to be used according to the application. The ratio of the total thickness d2 of the copolymerized polyester layer to the total thickness d1 of the polyester layer is preferably about 0.7 ≦ d2 / d1 ≦ 3.

Although the sum total of the film thickness of a laminated structure is not specifically limited, About 6-150 micrometers is preferable and especially 60-125 micrometers is preferable.

Moreover, the laminated structure of four or more layers may be sufficient including the case where the laminated structure in a film is two layers and three layers.

In a two-layer film, the thickness of each layer may be the same or different. Further, it is preferable that the types of main constituent components or the contents of main constituent components of the polyester or copolymer polyester in the two layers are different, or the types of copolymer components or the contents of the copolymer components are different. For example, the film having a two-layer structure is not particularly limited, and may be composed of a polyester layer and a copolyester layer, or a copolyester layer and a copolyester layer. The copolymer polyester in the copolymer polyester layer preferably contains an aromatic dicarboxylic acid having a metal sulfonate group as a copolymer component, and further preferably contains a polyalkylene glycol and / or a saturated aliphatic dicarboxylic acid. The content of the aromatic dicarboxylic acid having a metal sulfonate group is preferably 2 to 7 mol% based on the total ester bond, and the content of the polyalkylene glycol and / or the saturated aliphatic dicarboxylic acid It is preferably 3 to 10% by weight relative to the total weight of the product.

In the case of a film having a two-layer structure, the curl degree in the width direction of the film can be adjusted to a predetermined value by appropriately adjusting the above items.

The curl degree in the width direction can also be adjusted by laminating a polyester layer and a copolyester layer. In this case, the copolyester layer side is concave. In a film in which copolyester layers are laminated, the curl degree in the width direction can be adjusted by appropriately adjusting the film thickness and the composition amount.

When the copolyester layer and the polyester layer are laminated, the copolyester layer side is usually concave and curls. When the polyester layer and the copolyester layer are laminated, the ratio of the thickness d4 of the copolyester layer to the thickness d3 of the polyester layer is 0.7 ≦ d4 / d3 ≦ 3, more preferably 1 ≦ d4 / d3 ≦. When two different types of copolyester layers are laminated, the copolyester layer having a high content of the copolymer component is usually concave and curled.

When the film of the present invention has a three-layer structure, the outer two layers are either a combination of a polyester layer and a copolymerized polyester layer, or both outer layers are a combination of a copolymerized polyester layer.

In the case of a three-layer structure, the thickness of the outer layer may be the same or different, but the thickness of the outer layer is preferably different. The thickness of the inner thick outer layer is dA, and the thickness of the thinner outer layer is dB. Then, the ratio dA / dB is not particularly limited, but 1.1 ≦ dA / dB ≦ 5, preferably 1, 3 ≦ dA / dB ≦ 3.

By varying the thickness of the outer layer, the curl or roll curl degree and recovery curl degree in the lateral direction can be adjusted to predetermined values.

In the case of a three-layer structure, the polyester and copolymer polyester forming the upper and lower layers, which are the outer layers of the laminated film, are different in main component or main component amount, copolymer component or copolymer component amount. It is preferred that they are different and further have different intrinsic viscosities. In this case, as a copolymerization component in the copolymerized polyester to be used, aromatic dicarboxylic acid having a metal sulfonate group is contained in an amount of 2 to 10 mol%, preferably 2 to 7 mol%, based on all ester bonds. Further, it is particularly preferable to contain polyalkylene glycols and / or saturated aliphatic dicarboxylic acids as copolymerization components in a proportion of 3 to 10% by weight based on the total weight of the reaction product.

In the case of three layers, the above-mentioned items can be appropriately adjusted to give the laminated film curl in the lateral direction, curl curl or recovery curl. For example, when the two outer layers are copolymer polyester layers and the content or intrinsic viscosity of the copolymer component of the copolymer polyester of the two outer layers is substantially the same, the side of the copolymer polyester layer having the larger film thickness is concave. Curl. Further, when the thicknesses of the two copolyester layers of the outer layer are substantially the same, the copolyester layer side having a large intrinsic viscosity or a high content of the copolymer component becomes concave and curls. When the outer two layers are copolyester layers and their intrinsic viscosities are different, the intrinsic viscosity difference ΔIV is preferably 0.02 to 0.2. When the difference ΔIV in intrinsic viscosity is within the above range, when the outer layer is a combination of the copolyester layers when the film thickness of the two outer layers is not significantly different, the outer layer having a large intrinsic viscosity is preferably concave. A hand curl can be realized. When the outer layer is a combination of a polyester layer and a copolyester layer, the copolyester layer usually has a concave curl. Further, when the two outer layers are the same copolymerized polyester layer, the center layer is also a copolymerized polyester layer, and the copolymer component of the center layer contains more than the outer layer, the film thickness of both outer layers The small copolyester layer side usually becomes concave and curls. When both outer layers of the central layer are copolymerized polyester layers and the copolymerization component of the central layer is less than the outer layer, the larger copolymer polyester layer side of both outer layers is usually concave and curls. .

As one of preferred embodiments of the film having a laminate structure of three or more layers of the present invention as a photographic support, aromatic dicarboxylic acid having a metal sulfonate group is used as a copolymerization component in an amount of 2 to 7 with respect to all ester bonds. A co-polymer containing 3 to 10% by weight, preferably 3 to 6% by mole, and 3 to 10% by weight, preferably 4 to 8% by weight, based on the total weight of the reaction product of polyalkylene glycols and / or saturated aliphatic dicarboxylic acids. The polymerized polyester layer constitutes one or both surfaces of a polyester layer formed of a plurality of layers.

The film of the present invention having a laminated structure of two or more layers can be produced as follows. That is, for example, polyester and copolymer polyester are melt-extruded from separate extruders, then extruded in a laminar flow in a molten polymer conduit or extrusion cap, extruded, and electrostatically applied on a cooling drum After cooling and solidifying to obtain an unstretched film, biaxial stretching and heat setting, or polyester or copolymer polyester alone and laminated film are melt-extruded from an extruder and electrostatically applied on a cooling drum After cooling and solidifying the unstretched film or the surface of the uniaxially oriented film obtained by uniaxially stretching the unstretched film, an anchor agent, an adhesive, or the like is coated as necessary, and then a polyester or copolymer polyester alone and a laminated film Extrusion laminating, and then biaxial stretching is completed, and then the heat surface is set There include John lamination method, from the ease of process, the coextrusion method is preferable.

In this case, the stretching condition of the film is that the unstretched amorphous film made of the laminated polyester film is stretched in the first stage at a magnification of 2.7 to 5.0 times, and then the first stage stretching direction. On the other hand, when second-stage stretching is performed at a magnification of 1.2 to 5.0 times in the direction perpendicular to the first-stage stretching temperature, the film surface of the copolyester film constituting one or both surfaces after the first-stage stretching is used. The refractive index in the direction perpendicular to the stretching direction is selected to be 1.573 or less, and the second-stage stretching temperature is higher than the glass transition temperature Tg ° C. of the polyester constituting the laminated polyester, and (Tg + 35) ° C. or less. Stretch with. When both surfaces of the laminated polyester film are composed of copolymerized polyesters having different copolymerization ratios, it is necessary to select both surfaces to be 1.573 or less. Compared with the above-mentioned copolymer polyester having a small copolymerization ratio, the copolymer polyester having a large copolymerization ratio is largely oriented in the direction perpendicular to the first-stage stretching direction in the film plane by the second-stage stretching. Because. This is presumed to be because the copolyester is oriented in the longitudinal direction in the first-stage stretching, and the molecular orientation formed in the longitudinal direction is brittlely broken in the second-stage stretching and is oriented in the width direction. Is done. Therefore, to suppress the tendency to more orient molecules in the width direction, and to balance the mechanical and thermal properties in both the vertical and horizontal directions, the molecular orientation as much as possible in the longitudinal direction in the first stage stretching, In the second stage of stretching, it is preferable that the molecular orientation is suppressed in the width direction.

As a result of intensive studies to eliminate these disadvantages, the present inventor has (1) a copolyester film constituting an unstretched amorphous film made of a laminated polyester film constituting one or both surfaces after first-stage stretching. If the stretching temperature is selected so that the refractive index in the direction perpendicular to the stretching direction in the film plane is 1.573 or less and the first stage stretching is performed, the stretching in the stretching direction is high because the stretching is performed at a low temperature. And, when the orientation structure becomes strong and the stretching temperature is high (conventional method), this is the same as increasing the substantial stretching ratio. As the stretching temperature is lowered, the refractive index in the direction perpendicular to the stretching direction in the film plane after the first stage stretching tends to decrease, so that the refractive index is 1.573 or less. It is good to draw at the lowest possible temperature.

If the temperature at which the upper limit of the refractive index of the copolymerized polyester film constituting one or both surfaces is 1.573 and the lower limit is about 1.525 is selected, the stretched portion and the unstretched portion of the laminated polyester film can be seen. Film that does not mix with the part can be obtained. The low-temperature stretching limit temperature at which no stretch spots are mixed depends on the copolymer type, component ratio, laminated polyester composition ratio, stretch ratio, etc., and varies, but the stretching temperature at which the refractive index is 1.573 or less is approximately It is 120 degreeC and a minimum is 80 degreeC or more.

Uniaxial with a refractive index in the direction perpendicular to the stretching direction in the film surface of the copolyester film constituting one or both surfaces of the laminated polyester film after the first-stage stretching stretched by the above method is uniaxial. Next, the oriented laminated polyester film is second-stage stretched in a direction perpendicular to the stretching direction at a stretching temperature of 80 ° C. or more and less than 120 ° C. and a magnification of 1.2 to 5.0 times.

Adopting such a low temperature for the second stage stretching temperature is because the uniaxially stretched film has a very low crystallinity, and the orientation structure by the first stage stretching is not lost by stretching at such a low temperature. This is because an oriented structure can be formed by second-stage stretching, so that a film having a balance between longitudinal and lateral mechanical strength and Young's modulus can be produced. In addition, from the viewpoint of production in a factory, there are advantages that stretching is performed smoothly in continuous production, no breakage occurs, and that thick and thin spots are extremely small.

Furthermore, another reason is that it is not necessary to make the second stage draw ratio larger than the first stage draw ratio, and a film having an arbitrary degree of orientation in the vertical and horizontal directions can be easily obtained.

When the second stage stretching temperature is less than 80 ° C., the film is cut. When the temperature is 120 ° C. or more, the first stage stretching direction is considerably lost, and the second stage stretching direction is also gained. Since there is no film, both vertical and horizontal mechanical strength and Young's modulus are low. At this time, thick and thin spots in the width direction become large, which is not preferable.

Therefore, the second-stage stretching (performed in a direction perpendicular to the first-stage stretching direction) is the second-stage stretching while maintaining the structure sufficiently even if the structure formed by the first-stage stretching is slightly destroyed. Therefore, it is possible to produce a film having a balance between vertical and horizontal mechanical strength and Young's modulus.

At this time, as a biaxial stretching method, for example, the following processes (A) to (C) can be employed. (A) A method in which an unstretched sheet is first stretched in the longitudinal direction and then stretched in the transverse direction. (B) A method in which an unstretched sheet is first stretched in the transverse direction and then stretched in the longitudinal direction. (C) A method in which an unstretched sheet is stretched in the longitudinal direction in one or more stages, then stretched in the longitudinal direction again, and then stretched in the transverse direction. In order to implement the above-described contents in the processes (A), (B), and (C), it is only necessary to employ a low-temperature stretching temperature and a high stretching ratio in the first-stage stretching, and then in the second-stage stretching. If a high stretching temperature and a low stretching ratio are employed, the desired copolymerized laminated polyester film can be obtained.

The stretching is preferably performed in an area ratio of 4 to 16 times in order to satisfy the mechanical strength and dimensional stability of the film support. Thereafter, the laminated polyester film is heat-fixed in a temperature range of 150 to 240 ° C.

Needless to say, longitudinal heat relaxation, lateral heat relaxation treatment, and the like may be performed as necessary.

In addition to the above, in order to impart various properties such as slipperiness, adhesion, and antistatic performance, surface coating (giving easy slippage and easy adhesion by in-line coating, etc.) is performed on at least one side of the laminated polyester film. May be.

The photographic light-sensitive material having at least one silver halide emulsion layer on the laminated polyester support of the present invention is excellent in curling repellency, but can be easily cut in the development processing step by a cine type automatic development processor. From the viewpoint of improving working efficiency and productivity, the average intrinsic viscosity of the laminated support is preferably 0.55 (dl / g) or less, and preferably 0.52 (dl / g) or less. It is good to be. Therefore, the intrinsic viscosity of each layer constituting each layer of the laminated support is preferably 0.55 (dl / g) or less, and preferably 0.52 (dl / g) or less. good. The lower limit of the average intrinsic viscosity of the laminated support is not particularly limited, but is about 0.40 (dl / g). If the intrinsic viscosity of each layer constituting the laminated support is low, the laminated support cannot be formed. Therefore, the intrinsic viscosity of each layer is preferably 0.40 (dl / g) or more. Satisfying the above-mentioned film forming conditions, the tear strength in the width direction of the support is preferably 0.75 kg / mm or less, and most preferably 0.50 kg / mm or less. The tear strength is highly dependent on the thickness of the support, and increases as the thickness increases. Therefore, the laminated support thickness that satisfies the tear strength of 0.75 kg / mm or less in the above-mentioned average intrinsic viscosity range is 60 to 125 μm. A photographic light-sensitive material having at least one silver halide emulsion layer on a laminated polyester support satisfying such a tearing strength is excellent in curling repellency and can be easily developed in a cine type automatic development processor. It can be cut and has excellent work efficiency and productivity.

The film described in detail above can be applied to photographic photosensitive material applications, and is particularly useful as a support for a photographic photosensitive material used for a roll film.

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 To 100 parts by weight of dimethyl terephthalate and 64 parts by weight of ethylene glycol, 0.1 part by weight of calcium acetate hydrate was added as a transesterification catalyst, and a transesterification reaction was carried out by a conventional method. To the obtained product, 28 parts by weight (5 mol% / total ester bond) of ethylene glycol solution (concentration 35% by weight) of 5-sodium sulfo-di (β-hydroxyethyl) isophthalic acid (abbreviation: SIP), polyethylene glycol (Abbreviation: PEG) (number average molecular weight: 4,000) 11 parts by weight (8.5% by weight / total weight of reaction product), antimony trioxide 0.05 parts by weight, trimethyl phosphate 0.13 parts by weight Irganox 1010 (manufactured by CIBA-GEIGY) was added as an antioxidant so as to be 1% by weight based on the product polymer. Next, the temperature was gradually raised and the pressure was reduced, and polymerization was carried out at 280 ° C. and 0.5 mmHg to obtain a copolyester having an intrinsic viscosity of 0.57.

The copolymerized polyester and polyethylene terephthalate (inherent viscosity 0.56) were each vacuum dried at 150 ° C. and then melt extruded at 285 ° C. using three extrusions so that each of the three layers consisted of the materials shown in Table 1. The layers were joined in a T-die and rapidly 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 set as shown in Table 1. Next, at a longitudinal stretching temperature of 83 ° C., it is 3.2 times in the longitudinal direction, at a transverse stretching temperature of 95 ° C., 3.4 times in the transverse direction, successively biaxially stretched, heat fixed at 220 ° C. for 30 seconds, and a film thickness of 120 μm. A biaxially stretched film was obtained. In addition, the above-mentioned copolymer polyester (copolymerized polyethylene terephthalate) and polyethylene terephthalate are melt-extruded, and each layer is sampled separately immediately before joining each layer in a T-die, and the intrinsic viscosity (dl / g) of each layer Was measured.

(Example 2)
(1) Polymerization of copolymer polyester polymer In the same manner as in Example 1, a necessary amount of copolymer polyester polymer having an intrinsic viscosity of 0.55 (dl / g) was secured.

(2) Film formation of laminated polyester support In the same manner as in Example 1, a combination of a copolyester polymer having an intrinsic viscosity of 0.55 (dl / g) and a polyethylene terephthalate polymer having an intrinsic viscosity of 0.51 prepared separately, The molten polymer laminated at the ratio shown in Table 1 was rapidly cooled and solidified on a casting drum, and a laminated polyester unstretched support having a thickness of about 1270 μm was produced in the same manner as in Example 1. This unstretched support was formed into a film under the same conditions as in Example 1 to obtain a biaxially oriented laminated polyester support having a thickness of 120 μm. In the same manner as in Example 1, copolymer polyester (copolymerized polyethylene terephthalate) and polyethylene terephthalate were sampled separately, and the intrinsic viscosity (dl / g) of each layer was measured.

(Example 3)
(1) Polymerization of copolymer polyester polymer In the same manner as in Example 1, a necessary amount of copolymer polyester polymer having an intrinsic viscosity of 0.51 (dl / g) was secured.

(2) Film formation of laminated polyester support In the same manner as in Example 1, a copolymer polyester polymer having an intrinsic viscosity of 0.51 (dl / g) and a polyethylene terephthalate polymer having an intrinsic viscosity of 0.51 prepared in Example 2 were used. In combination, the molten polymer laminated at the ratio shown in Table 1 was rapidly cooled and solidified on a casting drum, and a laminated polyester unstretched support having a thickness of about 1270 μm was produced in the same manner as in Example 1. This unstretched support was formed into a film under the same conditions as in Example 1 to obtain a biaxially oriented laminated polyester support having a thickness of 120 μm. In the same manner as in Example 1, copolymer polyester (copolymerized polyethylene terephthalate) and polyethylene terephthalate were sampled separately, and the intrinsic viscosity (dl / g) of each layer was measured.

(Comparative Example 1)
For comparison, a commercially available cellulose triacetate film having a thickness of 120 μm (shown as CTA in Table 1 and Comparative Example 1) was obtained.

(Comparative Example 2)
(1) Polymerization of copolymerized polyester polymer In the same manner as in Example 1, a copolymerized polyester polymer having an intrinsic viscosity of 0.51 (dl / g) was melt polymerized, and then this polymer chip was solid-phase polymerized. A necessary amount of a copolyester polymer having an intrinsic viscosity of 0.60 (dl / g) was secured.

(2) Film formation of laminated polyester support In the same manner as in Example 1, a combination of a copolymer polyester polymer having an intrinsic viscosity of 0.60 (dl / g) and a polyethylene terephthalate polymer having an intrinsic viscosity of 0.65 is shown in Table 1. The molten polymer laminated at the stated ratio was rapidly cooled and solidified on a casting drum, and a laminated polyester unstretched support having a thickness of about 1270 μm was produced in the same manner as in Example 1. This unstretched support was formed into a film under the same conditions as in Example 1 to obtain a biaxially oriented laminated polyester support having a thickness of 120 μm. In the same manner as in Example 1, copolymer polyester (copolymerized polyethylene terephthalate) and polyethylene terephthalate were sampled separately, and the intrinsic viscosity (dl / g) of each layer was measured.

Intrinsic viscosity of each layer of laminated polyester film of Examples 1 to 3 and Comparative Example 2, layer structure, thickness ratio of each layer and intrinsic viscosity of film formed (indicated as film average intrinsic viscosity), transverse direction Elmendorf tear strength Is shown in Table 1.

(1) Surface treatment The contact angle with ion-exchanged water of the untreated surface of the copolymerized polyester film constituting both surface layers of the biaxially oriented laminated polyester support obtained as described above was 42 ° (degrees). . The surface of the laminated polyester film having a small thickness is subjected to corona treatment with a corona treatment discharge voltage of 12.0 (watt · min / m ² ) to obtain a laminated polyester film (support) having a contact angle of 16 ° (degrees). Got.

(2) Undercoat of laminated polyester film On the modified PET of the laminated polyester film subjected to the surface treatment described in (1) above, an undercoat layer having been subjected to antistatic treatment containing styrene-glycidyl acrylate and tin oxide fine particles was formed.

<< Preparation of Silver Halide Emulsion A >> Silver chlorobromide core grains having an average thickness of 0.05 μm and an average diameter of 0.15 μm made of silver chloride 70 mol% and the rest silver bromide were prepared using the simultaneous mixing method. At the time of mixing the core particles, 8 × 10 −8 mol of K 3 RuCl 6 was added per mol of silver. A shell was attached to the core particles using a simultaneous mixing method. At that time, K2lrCl6 was added at 3 × 10 −7 mol per mol of silver. The obtained emulsion was silver chloroiodobromide (90 mol% of silver chloride) having an average thickness of 0.10 μm and an average diameter of 0.25 μm of core / shell monodispersed (variation coefficient 10%) (100) plane as the main plane. Tabular grain emulsion comprising 0.2 mol% of silver iodobromide, the rest being silver bromide. Subsequently, desalting is performed using a modified gelatin described in JP-A-2-280139 (in which the amino group in gelatin is substituted with phenylcarbamyl, for example, Compound G-8 on page 287 (3) of JP-A-2-280139). did. The EAg after desalting was 190 mV at 50 ° C.

To the obtained emulsion, 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene was added in an amount of 1 × 10 −3 mol per mol of silver, and potassium bromide and citric acid were added to adjust the pH to 5.6. EAg was adjusted to 123 mv, 2 × 10 −5 mol of chloroauric acid was added, then 3 × 10 −6 mol of inorganic sulfur was added, and chemical aging was performed at a temperature of 60 ° C. until the maximum sensitivity was achieved. After ripening, 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene was 2 × 10.3 mol per mol of silver, 1 × phenyl-5-mercaptotetrazole 3 × 10 −4 mol and gelatin Added.

<< Preparation of Silver Halide Emulsion B >> Using the simultaneous mixing method, 60 mol% of silver chloride, 2.5 mol% of silver iodide, and the rest are silver bromide having an average thickness of 0.05 μm and an average diameter of 0.15 μm Silver iodobromide core grains were prepared. At the time of mixing the core particles, 2 × 10 −8 mol of K 3 Rh (H 2 O) Br 5 was added per mol of silver. A shell was attached to the core particles using a simultaneous mixing method. At that time, K2lrCl6 was added at 3 × 10 −7 mol per mol of silver. The obtained emulsion had an average thickness of 0.10 μm and an average diameter of 0.42 μm of core / shell monodisperse (variation coefficient 10%) silver chloroiodobromide (90 mol% of silver chloride, 0.5 mol of silver iodobromide) %, The rest consisting of silver bromide). Subsequently, desalting is performed using a modified gelatin described in JP-A-2-280139 (in which the amino group in gelatin is substituted with phenylcarbamyl, for example, Compound G-8 on page 287 (3) of JP-A-2-280139). did. The EAg after desalting was 180 mV at 50 ° C.

To the obtained emulsion, 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene was added in an amount of 1 × 10 −3 mol per mol of silver, and potassium bromide and citric acid were added to adjust the pH to 5.6. EAg was adjusted to 123 mv, 2 × 10 −5 mol of chloroauric acid was added, and then 3 × 10 −5 mol of N, N, N′-trimethyl-N′-heptafluoroselenourea was added and the temperature was the highest at 60 ° C. Chemical aging was performed until sensitivity was achieved. After completion of ripening, 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene was 2 × 10 −3 mol per mol of silver, 3 × 10 −4 mol of 1-phenyl-5-mercaptotetrazole and gelatin Added.

(3) Preparation of silver halide photographic light-sensitive material for printing plate making scanner for HeNe laser light source For each of the five types of supports obtained in the above (2), a gelatin undercoat of the following formulation 1 was formed on one undercoat layer. Further, the silver halide emulsion layer 1 of Formula 2 was further added so that the amount of gelatin was 0.5 g / m 2 and the amount of gelatin was 0.5 g / m 2. As an intermediate protective layer, a coating solution of the following formulation 3 is used as an intermediate protective layer so that the gelatin amount is 0.3 g / m 2, and a silver halide emulsion layer 2 of the formulation 4 is further formed thereon with a silver amount of 1.4 g / m 2 and gelatin. Further, a coating solution of the following formulation 5 was applied simultaneously so that the amount of gelatin was 0.6 g / m 2 so that the amount was 0.4 g / m 2. On the other side of the undercoat layer, a backing layer of the following formula 6 is coated with a hydrophobic polymer layer of the following formula 7 on it so that the amount of gelatin is 0.6 g / m 2, and further a formula 8 5 types of light-sensitive materials are produced by simultaneously coating the backing protective layer of the emulsion layer side with the emulsion layer side so that the amount of gelatin is 0.4 g / m 2.

Formula 1 (gelatin subbing layer composition)
Gelatin 0.5g / m2
Solid dispersion fine particles of dye AD-1 (average particle size 0.1 μm) 25 mg / m 2
Sodium polystyrene sulfonate 10mg / m2
S-1 (Sodium-iso-amyl-n-decylsulfo succinate) 0.4 mg / m 2
Formula 2 (composition of silver halide emulsion layer 1)
Silver Halide Emulsion A Solid dispersion fine particles of dye AD-8 (average particle size 0.1 μm) so that the silver amount is 1.5 g / m 2 20 mg / m 2
Cyclodextrin (hydrophilic polymer) 0.5g / m2
Sensitizing dye d-1 5 mg / m2
Sensitizing dye d-2 5mg / m2
Hydrazine derivative H-7 20 mg / m2
Redox compound: RE-1 20 mg / m 2
Compound e 100 mg / m2
Latex polymer f 0.5g / m2
Hardener g 5mg / m2
S-1 0.7 mg / m2
2-mercapto-6-hydroxypurine 5mg / m2
EDTA 30mg / m2
Colloidal silica (average particle size 0.05 μm) 10 mg / m 2
Formula 3 (interlayer composition)
Gelatin 0.3g / m2
S-1 2 mg / m2
Formula 4 (silver halide emulsion layer 2 composition)
Silver halide emulsion B Sensitizing dye d-1 3 mg / m2 so that the silver amount is 1.4 g / m2
Sensitizing dye d-2 3mg / m2
Hydrazine derivative H-20 20 mg / m2
Nucleation accelerator: Exemplified compound Nb-12 40 mg / m 2
Redox compound: RE-2 20 mg / m 2
2-mercapto-6-hydroxypurine 5mg / m2
EDTA 20mg / m2
Latex polymer f 0.5g / m2
S-1 1.7 mg / m2
Formula 5 (Emulsion protective layer composition)
Gelatin 0.6g / m2
Solid dispersion of dye AD-5 (average particle size 0.1 μm) 40 mg / m 2
S-1 12mg / m2
Matting agent: monodispersed silica having an average particle size of 3.5 μm 25 mg / m 2
Nucleation promoter: Exemplified compound Na-3 40 mg / m 2
1,3-vinylsulfonyl-2-propanol 40 mg / m 2
Surfactant h 1mg / m2
Colloidal silica (average particle size 0.05 μm) 10 mg / m 2
Hardener: K-1 30 mg / m2
Formula 6 (backing layer composition)
Gelatin 0.6g / m2
S-1 5mg / m2
Latex polymer f 0.3g / m2
Colloidal silica (average particle size 0.05 μm) 70 mg / m 2
Sodium polystyrene sulfonate 20mg / m2
Compound i 100 mg / m2
Formulation 7 (hydrophobic polymer layer composition)
Latex (methyl methacrylate: acrylic acid = 97: 3) 1.0 g / m 2
Hardener g 6mg / m2
Formula 8 (backing protective layer)
Gelatin 0.4g / m2
Matting agent: monodisperse polymethyl methacrylate having an average particle diameter of 5 μm 50 mg / m 2
Sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m 2
Surfactant h 1mg / m2
Dye k 20 mg / m2
H- (OCH2CH2) 68-OH 50 mg / m2
Hardener: K-1 20 mg / m2

The overall evaluation of the cutting ability of the photographic film coated with the emulsion was evaluated according to the following evaluation criteria.

(Photo film cutting)
While applying 5 (kg / mm 2) air pressure to the sandwich-type splicer, a 35 mm wide photographic film was cut in the width direction, and the cutting performance was evaluated in five stages.

(Cutability evaluation criteria)
1. Cutability is very poor, and when cutting, almost 100% cuts only about 1/2 of the photographic film width (35 mm width).

2. At the time of cutting, almost 100% cuts only about ¾ of the photographic film width (35 mm width).

3. At the time of cutting, almost 100% of the photographic film width (35 mm width) is left uncut.

4). Photo film can be cut without any problem, but it takes about 1.0 to 1.5 seconds for the set cutting time of 1.0 second.

5). The photo film can be cut without any problem, and the cutting can be completed within 1.0 seconds, compared to 1.0 seconds.

(Cutability)
1 to 3 are unusable levels; ×
4 is a level that can withstand practical use.
5 is a very good level;
Expressed in

The results are shown in Table 1.

As is clear from Table 1, from the comparison with Examples 1 to 3 and Comparative Examples 1 and 2, the photographic film that can be cut without problems in the process has an average intrinsic viscosity of the laminated polyester support of 0.55 (dl / g) or less, preferably 0.52 (dl / g) or less. It is understood that the Elmendorf tear strength in the lateral direction at this time is 0.75 (Kg / mm) or less, preferably 0.50 (Kg / mm) or less.

The invention's effect

According to the present invention, an easily cut silver halide photographic light-sensitive material having excellent thermal, mechanical, physical, chemical, and optical properties and excellent curl recovery can be provided.
# Add horizontal orientation to claims

Claims (5)

Any one of the polyester layers different from each other contains 2 to 7 mol% of an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component with respect to the total ester bond, and is a polyalkylene glycol and / or saturated. A photographic light-sensitive material having at least one silver halide emulsion layer on a laminated polyester support containing 3 to 10% by weight of an aliphatic dicarboxylic acid based on the total weight of the reaction product. A silver halide photographic light-sensitive material excellent in cutting property, characterized in that the average intrinsic viscosity of the light-sensitive material is 0.55 (dl / g) or less. The halogenated material having excellent cutting properties according to claim 1, wherein the support is formed by laminating three polyester layers, and the two copolyester layers located on both sides of the central layer have different thicknesses. Silver photographic material. 3. The silver halide photographic light-sensitive material having excellent cutting properties according to claim 1, wherein the average intrinsic viscosity of the support is 0.52 (dl / g) or less. The silver halide photographic light-sensitive material excellent in cutting property according to any one of claims 1 to 3, wherein the tear strength in the longitudinal direction of the support is 0.75 kg / mm or less. The silver halide photographic light-sensitive material having excellent cutting properties according to any one of claims 1 to 3, wherein the tear strength in the longitudinal direction of the support is 0.50 kg / mm or less.