JPH0858011A - Plastic film hard to get into winding habit and silver halide photosensitive material having the same as support - Google Patents

Abstract

PURPOSE: To provide a plastic film hard to get into a winding habit even if rolled. CONSTITUTION: A laminated film has a laminated structure of three or more layers of two or more kinds of resins different in winding habit tendency or shrinkage with the elapse of time and is characterized by that the layer highest in winding habit tendency or shrinkage with the elapse of time is positioned as the inner layer among three or more resin layers and adapted to a silver halide photosensitive material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic film which is hard to have a curl even when stored in a roll form, and a silver halide photographic light-sensitive material using them as a support.
In particular, the present invention relates to a laminated film having a laminated structure with less curl and a silver halide photographic light-sensitive material which uses them as a support and is hard to curl and is easy to handle.

[0002]

2. Description of the Related Art Generally, a sheet-like substance, for example, paper or a plastic film, is wound in a roll form, and over time, a tendency of curling develops, which becomes stronger with time, and depending on the conditions when the substance is wound. , And reaches a certain degree of winding habit depending on the diameter of the winding core. When a plastic film with a curl is released from the rolled state, a force to return to a flat state is exerted, but a film that has been rolled for a long time is difficult to return to the original flat state.

The silver halide photographic light-sensitive material includes a roll film and a sheet-like sheet film. Even a sheet-shaped film may easily have a problem in transporting the film due to a very slight curl that is attached during manufacturing. For example, in the field of medical films, automatic transportation such as an automatic transportation photographing machine and an automatic transportation developing machine is progressing, and even a slightly curled film has a high probability of causing trouble. In recent years, printing film materials have also changed from sheet films to roll films. In this case, curling at the time of printing makes it difficult to be sucked in the vacuum printer, uniform printing cannot be performed, and there is a high possibility that the film has poor reproducibility.

In applications other than photographic materials, for example, marking films, drafting films, printing films, OHP films, etc., if there is a winding tendency, some troubles and difficulty in handling tend to occur.

As a method of returning the film having the curl to a flat state, there is a method of reversing the film with the curled side facing outward or squeezing it. For example, there is a method in which a reverse curl is applied in a stepwise or continuous manner from a winding core portion to an outer peripheral portion when a film is wound into a roll.
No. 4-166929, and a method of seasoning in the form of a winding roll so that the emulsion layer side is wound outside during production, and rewinding so that the emulsion layer side is wound inside during shipment.
It is proposed in the specification of 4-273239, but this also requires new equipment and work, resulting in cost increase, and the state of curl after release is unstable and difficult to handle.

There is also a method of imparting a peculiarity by subjecting the film to a certain pretreatment and reducing the peculiar curl which is caused by the subsequent winding. For example, U.S. Pat.
No. 5, or JP-A No. 51-16358, the curl curl of the self-supporting film was reduced by at least 15% to 100%.
A relative humidity of less than% RH and a temperature in the range of from about 30 ° C. to the glass transition temperature (Tg) of the polymer for about 0.1 to 1500 hours, heat-humidifying the film in the form of a storage roll without shrinkage or distortion, As described in JP-B-60-16611, a polymer film wound into a roll is cut into a sheet, and the above sheet is placed in an atmosphere at a temperature of 10 to 40 ° C and a dew point temperature of 25 ° C or less. A method has been proposed in which the ingredients are stacked and hermetically sealed and heat-treated at 28 to 65 ° C. for 1 hour or more, but both of them require a long time for heat treatment and may damage the surface of the film. In addition, it is said that it is relatively hard to have a curl even if it is wound around a core with a larger diameter, or it is flattened and heat-treated to maintain its curl tendency to give a peculiarity, and then to a smaller core later. There are methods, but they are insufficient.

Further, there has been proposed a method of imparting a property of being hard to have a curl to the film itself during the production of the plastic film. For example, a method of making a stretching roll of a stretching machine have a temperature gradient ΔT of more than 10 ° C. from the surface of the film to another surface at the time of producing the film to make the longitudinal tension of the film during stretching less than 10 N / m ² is known. In Japanese Patent Application Laid-Open No. 64-70748, a film produced in the presence of such a temperature gradient ΔT is wound into a roll and the relative humidity is less than 100% and the temperature is in the range of about 30 ° C. to Tg. A method of heat and humidity control is disclosed in JP-A-2-54254. In addition, JP 62-
No. 31653 proposes a method of heating a silver halide photographic light-sensitive material and then cooling it, but none of them has sufficiently reduced the tendency to curl.

[0008]

Films generally used in sheet form, for example, OHP film, drafting film, printing film, marking film, silver halide X-ray photographic light-sensitive material, silver halide printing photograph. Photosensitive materials, silver halide color photographic photosensitive materials, etc. are sold in the form of a specified number of sheets in a sturdy flat packaging box of a specified size, but this requires manufacturing, cutting, and packaging costs. Therefore, in recent years, it has come to be sold in the form of a roll-shaped roll for the purpose of cost reduction. In this case, when using it, cut out the required amount from the roll roll into a sheet, but when using it immediately, it will be used in a curled state with curl, which is not only difficult to handle but also adversely affects the quality. Can affect To avoid this, it may take a long time until the curl curl disappears, which leads to a loss of time and, on the contrary, may increase the cost on the user side.

As described above, the film wound into a roll has a curl and is unlikely to be flat, but this is an unavoidable general property of plastic films. The current situation is that we try to remove the curl as much as possible. In particular, it is desirable to use a silver halide photographic light-sensitive material as flat as possible, and it is necessary to give the plastic film that is the support the property that it does not tend to curl. Development of such a plastic film Is an urgent task.

The first object of the present invention is to provide a plastic film which is hard to have a curling tendency even when it is wound. The second object is to provide a plastic film having a multi-layered structure that is hard to curl. A third object of the present invention is to provide a silver halide photographic light-sensitive material having a peculiar curl-like plastic film support.

[0011]

As a result of studies to solve this problem, the present invention could be achieved by developing a plastic film having less curl as described below.

That is, (1) an inner layer in which two or more kinds of resin layers having different curl tendencies have a laminated structure of at least three layers, and the resin layer having the strongest curl tendency among the resin layers is laminated. (2) Two or more kinds of resin layers having different shrinkage rates with time have a laminated structure of at least three layers, and the resin layer having the highest shrinkage rate among the resin layers is (3) To be a laminated film which is located in the inner layer of the laminate; (3) When the thickness of the laminated film is equally divided into two, the laminated structure is asymmetrical on both sides of the divided layers; (4) A laminated film in which the resin layer having the strongest tendency to curl or the resin layer having the largest shrinkage ratio with time is a modified polyester layer having a metal sulfonate group; (5) Polyethylene terephthalate resin layer and / or poly A laminated film in which the thylene naphthalate resin layer is located on both sides of the outermost surface layer of the laminated structure and at least one of the inner layers is a modified polyester resin layer having a metal sulfonate group; (6) Different curl tendency Two or more resin layers have a laminated structure of at least three layers, and the resin layer having the strongest curl tendency among the resin layers has a laminated film as an inner layer of the laminated layer as a support, and A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on at least one side of a laminated film support; (7) at least three layers of two or more resin layers having different shrinkage rates over time. Which has a laminated structure in which the resin layer having the largest shrinkage rate with time among the resin layers is located in the inner layer of the laminate as a support, and at least one side of the laminated film support To provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer; (8) When the laminated film support divides the thickness of the laminated film into two equal parts, the layer constitution on both sides of the division. (9) A modified polyester resin layer having a sulfonate group as the resin layer having the strongest tendency to curl or the resin layer having the largest shrinkage ratio with time as the laminated film support. (10) The laminated film support has a polyethylene terephthalate resin layer and / or a polyethylene naphthalate resin layer on both sides of the outermost surface layer of the laminated structure, and at least one of the inner layers is provided. The layer is a silver halide photographic light-sensitive material in which the layer is a modified polyester resin layer having a metal sulfonate group.

First, the terms used in the present invention will be defined and explained.

What is a curl? When a sheet-like substance such as a plastic film is wound around a cylindrical core having a certain diameter, it gradually becomes fixed in a rolled state with time. Okay, that tendency is called curl tendency.

The fact that the curl tendency is strong means that the curl tends to be formed when the core is wound.

The term "time-dependent shrinkage" means that a film left to stand for a long time under a certain condition undergoes a dimensional change with time. In the present invention, a dimensional change rate after 12 months in an environment of 23 ° C. and 55% RH is used. It is the shrinkage rate over time.

The degree of curl is determined by removing the sheet-like material wound around the winding core from the rolled state and releasing it, and measuring the curl degree after a certain period of time from the moment of release. The curled degree of the sheet-like material released from the wound core changes from moment to moment, and the curled degree changes greatly at first, and gradually approaches a constant degree of curl.

Curl means a state in which a sheet-like substance is curved. Regarding the direction of curl, one of the front and back surfaces of the sheet-like material is defined, and the state in which that surface is concavely curled is called plus curl (abbreviated as + curl), and the opposite convex surface side is Minus curl (-curl is abbreviated).

The curl degree is represented by a curvature, and is represented by 1 / radius of the curvature. The unit is 1 / m (or represented by m ^-1 ).

The degree of curl depends on the atmosphere in which the sheet material is placed. That is, if the temperature is high, the curl tends to stick, and if the time is long, it tends to stick again.
Regarding humidity, when the sheet-shaped substance is a water-absorbing substance, the substance moves in a complicated manner due to the elasticity of the substance being added. Further, in the case of a composite material such as a laminated structure, it is easy to depend on the change of the material which is easily affected by humidity.

The tendency of curl can be explained by applying the creep phenomenon in the field of polymer chemistry. In other words, the curl of a plastic film or the like is due to the fluidity of the polymer and has temperature and time dependence. Therefore, in evaluating the degree of curl, the time can be shortened by increasing the temperature, and the tendency of curl can be emphasized, instead of the tendency of curl caused by winding for a long time. The conditions can be set by changing the conditions.

The present invention will be described in detail below.

The basic feature of the present invention is that at least two resin layers having different curl tendencies or different shrinkage rates have a laminated structure of at least three layers, and the most curl among the resin layers. A laminated film in which a resin layer having a strong tendency or a resin layer having the largest shrinkage rate with time is positioned as an inner layer of the laminate. The most characteristic point of the present invention is to use a resin layer having a strong tendency to curl or a resin layer having a large shrinkage rate with time as the inner layer of the laminated structure.

As described above, almost no plastic film has a curling tendency or is extremely hard to have a curling tendency in the world, and any plastic film has a curling tendency. Then, as a result of diligent examination of the present invention, it was found that the above-mentioned idea is fundamental, as to whether the tendency to curl is small, what kind of plastic film does not exist, and what exists in this world. .

[0025] As a concrete example, a basic three-layer laminated structure is shown as an example. A polyethylene terephthalate resin layer and / or a polyethylene naphthalate resin layer are formed on the innermost two outermost layers. A layer is a laminated film in which a modified polyester resin layer containing a metal sulfonate group is arranged, and when the thickness of the laminated film is divided into two equal parts, the divided layer structure on both sides is asymmetric. . The inventors have found that a modified polyester single film containing a metal sulfonate group has a property of shrinking over time, and the present inventors wondered if this property of the product could be utilized. In other words, the contracting force may be a force that counteracts the curl. This could be proved to some extent by the two-layer structure of the polyethylene terephthalate resin layer and the modified polyester resin layer having a metal sulfonate group. However, in this structure, shrinkage of the modified polyester resin layer containing a metal sulfonate group progresses over time, and depending on the thickness, it may reverse curl, and the degree of curl may change due to aqueous treatment such as development. It was difficult to get things.

Therefore, a method that does not change due to an aqueous treatment such as development was considered. In order to sandwich the modified polyester resin layer having a metal sulfonate group that is time-shrinkable between the inner layers of the laminated structure and to appropriately develop the force to return to the curl, the thickness direction of the laminated film is divided into two equal parts. It was found that it is important that the laminated structures on both sides of the dividing position are asymmetrical to each other.

In the present invention, the laminated structure on both sides of the laminated film is asymmetric with respect to the position where the laminated film is divided into two parts in the thickness direction. It is designed by changing the composition, film forming conditions, etc., and selecting and combining them appropriately. Asymmetrical here means that they are physically, mechanically, or chemically different, and are composed of layers of different materials (layers of completely different nature), the order in which the layers are formed, the thickness, and the constituents (copolymerization composition). The types of units), the amounts of constituent components (amount ratio of constituent units of copolymerization), and the physical properties such as intrinsic viscosity are different.

A method for measuring the asymmetry of these laminated films can be carried out by using various analytical instruments, and is not particularly limited, but regarding the layer constitution, the cross section of the film is observed under a microscope and a micrograph is taken. You can Further, while observing the film under a microscope, each layer is scraped off, or the film is divided into halves, each of which is scraped from above and below to obtain an analyte of each of the upper and lower layers, and hydrolysis is performed to perform liquid chromatography and NMR.
It may be measured by various measuring devices such as, etc., or the analyte may be dissolved in a solvent and then NMR, GPC (gel permeation chromatography), intrinsic viscosity, etc. may be measured, or the analyte may be directly powdered. Can be mixed with X-ray spectroscope or KBr to measure IR (infrared spectrophotometer), etc., and as a result, absolute amount, or equivalent peak position of measurement result, asymmetry in intensity difference, etc. Sex can be measured.

As described above, the laminated film of the present invention has at least 2 different curling tendency or different shrinkage rate with time.
It has a structure in which at least three kinds of resin layers are laminated.

The resin layers having different curl tendencies used in the present invention need only have different curl tendencies between the two laminated resin layers, and an absolute value is not necessary separately.
One measure for different curl tendencies is the shrinkage property of the film when the resin layer is a single film. That is, the tendency can be grasped by measuring the shrinkage property over time using each resin layer as a single film instead of the laminated state. However, although it was recognized that the strength of the curl tendency of a single film is almost parallel to the magnitude of the shrinkage rate with time of the film, it does not necessarily have an absolute relationship. Therefore, in the present invention, the tendency to curl and the shrinkage with time are used as independent measures.

The degree of time-dependent shrinkage is exhibited even with a single film of the same resin if the film forming conditions such as stretching conditions and heat setting conditions are different, and if the resin composition of the single film is different, the time-dependent shrinkage is shown. However, two or more resin layers can be arbitrarily selected. However, a silver halide photographic light-sensitive material is required to have a plastic film support which is hardly influenced by the external environment or has a dimensional change with time, which is one of the criteria for selecting the support. Therefore, the outermost surface layer of the three-layer laminated structure must be a plastic film with little expansion and contraction and good dimensional stability. Examples of the component of the resin layer used as the outermost surface layer of the laminated film of the present invention include polyethylene terephthalate, polyethylene naphthalate, polysulfone, polyamide, polyaramid, polyimide and the like, among which polyethylene terephthalate and polyethylene naphthalate are preferable. Among the polyethylene naphthalates, polyethylene-2,6-naphthalate, polyethylene-1,5-naphthalate and polyethylene-2,7-naphthalate are preferable. Polyethylene terephthalate and poly-ethylene-2,6-naphthalate polyester resins are particularly preferred. The two outermost layers may be the same polyester resin or different resins.

The polyester resin used in the resin layer used as the outermost surface layer of the laminated film of the present invention is not particularly limited, but when used in a silver halide photographic light-sensitive material, a photographic grade one is preferable. Further, the intrinsic viscosity of the polyester resin is preferably 0.50 to 0.85, and particularly 0.55 to 0.85.
0.70 is preferred.

A resin layer having a greater shrinkage over time than that used for the inner layer of the laminated film of the present invention is used. The following modified polyester resin is useful in the present invention as the resin layer having a greater shrinkage with time.

The modified polyester resin used in the present invention preferably has polyethylene terephthalate or polyethylene naphthalate as a main constituent component of the modified polyester. That is, it is a polymer having many repeating units containing terephthalic acid and ethylene glycol as main constituents, and a polymer having many repeating units containing naphthalenedicarboxylic acid and ethylene glycol as main constituents. The naphthalene dicarboxylic acid is preferably naphthalene-2,6-dicarboxylic acid. Here, having many repeating units means that the repeating units are 70 mol% or more, preferably 85 mol% or more, and particularly preferably 90 mol% or more.

The remaining modified portion is terephthalic acid, 2,6-naphthalenedicarboxylic acid, other naphthalenedicarboxylic acid,
Aromatic dicarboxylic acids containing a metal sulfonate group, aromatic dicarboxylic acids such as isophthalic acid, or these aromatic dicarboxylic acids and C ₁ -C ₄ alcohols or C ₂
A glycol dihalf ester with C ₁₀ ; adipic acid,
Aliphatic dicarboxylic acids such as sebacic acid or these aliphatic dicarboxylic acids and C _{1 to} C ₄ alcohols or C ₂ to
Di half ester with C ₁₀ ; polyether dicarboxylic acid such as polyethylene oxide dicarboxylic acid and polypropylene oxide dicarboxylic acid; or acid component such as C _{1 to} C ₈ alcohol or C _{2 to} C ₁₀ diester; and ethylene glycol, propylene Glycols such as glycol, butanediol, neopentyl glycol, p-xylidene glycol, 1,4-cyclohexanedimethanol; diethylene glycol, triethylene glycol,
Polyethylene glycol, polypropylene glycol,
It comprises an ester or polyester component with a glycol component such as polyolefin oxide glycols such as polyethylene oxide-polypropylene oxide copolymer glycol.

The aromatic dicarboxylic acids as the modifying component useful in the present invention are preferably isophthalic acid containing a metal sulfonate group, the metal ion is an alkali metal such as sodium, potassium, lithium or cesium, and sodium is preferable. Specifically, 5-sodium sulfoisophthalic acid, 2-sodium sulfoisophthalic acid, 4-sodium sulfoisophthalic acid, 4-sodium sulfo-2,6-naphthalenedicarboxylic acid or their methyl esters, ethylene glycol half esters, other Examples thereof include glycol half esters represented by 1.
Preferably, 5-sodium sulfoisophthalic acid or its methyl ester or ethylene glycol ester is also used. 2 for all ester bonds of modified polyester of aromatic dicarboxylic acid having metal sulfonate group
It is preferable to be contained in a proportion of up to 10 mol%. Preferably 2
It is 7 mol%, and particularly preferably 3 to 6 mol%.

[0037]

Embedded image

The polyalkylene glycols as the modifying component useful in the present invention are preferably polyethylene glycols, and the molecular weight thereof is not particularly limited, but is preferably 300 to 100,000, more preferably 600 to 10,000, and particularly preferably 1,000 to It is 5,000. The content of the modified polyester of polyalkylene glycol is preferably 3 to 10% by weight, preferably 4 to 8% by weight, based on the total weight of the polyester.

Examples of the aliphatic dicarboxylic acid as the modifying component useful in the present invention include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and the like, and adipic acid, suberic acid, azelaic acid are preferable, Particularly, adipic acid is preferably used. It is preferably 3 to 10% by weight, and preferably 4 to 8% by weight, based on the total weight of the polyester of the aliphatic dicarboxylic acid, but when the polyalkylene glycol and this aliphatic dicarboxylic acid are used together, the total amount is 3 -10 wt% is preferable, and 4-8 wt% is particularly preferable.

As the polyether dicarboxylic acid useful in the present invention, polyethyleneoxydicarboxylic acid, polypropyleneoxydicarboxylic acid, poly (ethylene / propylene) oxydicarboxylic acid, polytetramethyleneoxydicarboxylic acid and copolymers thereof are preferable. From the viewpoints of polymerization reactivity of polyester and plane stability of the film, it is more preferable to use polyethyleneoxydicarboxylic acid ester represented by the following formula.

R ¹ OOCCH ₂ — (OCH ₂ CH ₂ ) _n —OCH ₂ COOR ² Here, R ¹ and R ² are hydrogen or an alkyl group having 1 to 8 carbon atoms, and n is a positive integer.

The modification ratio of the polyether dicarboxylic acid component is 2 to 30% by weight of the total polyester weight,
Preferably 5 to 15% by weight, particularly preferably 7 to 12% by weight
Is.

The intrinsic viscosity of the modified polyester resin used in the inner layer of the laminated film of the present invention and having a greater shrinkage property with time is preferably 0.45 to 0.85, particularly preferably 0.50 to 0.70. If the intrinsic viscosity is less than 0.45, coloring will occur and it will become brittle, making it impractical. On the other hand, when it is 0.85 or more, the melt viscosity becomes too high and film formation becomes difficult.

The modification ratio of the modified polyester resin used in the present invention may be such that it is copolymerized with other components or blended with other resins as long as the effects of the present invention are not impaired. Absent. The resin to be blended is preferably a polyester resin.

The modified polyester resin useful in the present invention can be synthesized by a conventionally known polyester production method. For example, in the esterification reaction, both direct esterification of an acid component with a glycol component and esterification by a transesterification method with glycol using an acid component as a dimethyl ester can be used. In particular, the acid component as the modifying component is preliminarily prepared by ethylene glycol diester (more specifically, ethylene glycol dihalf ester).
It is preferably used in the form of. At this time, if necessary, a polyester can be polymerized and synthesized by using a transesterification reaction catalyst for the esterification and a polymerization reaction catalyst such as antimony trioxide in the polymerization reaction. Regarding the polyester components and the synthetic method described above, for example, Polymer Experimental Science Vol. 5, "Polycondensation and Polyaddition" (Kyoritsu Shuppan, 1980), No. 10
Pages 3-136, or "Synthetic Polymer V" (Asakura Shoten, 1971)
Year) You can refer to the description on pages 187-286.

Specific methods for synthesizing the modified polyester resin are described in US Pat. No. 4,217,441 and JP-A-5-210199, and the modified polyester resin useful in the present invention can be synthesized by these methods.

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

In order to obtain the modified polyester, the acid component and the glycol component may be transesterified, and then the above-mentioned modified component may be added to carry out the melt polymerization, or the modified component may be added before the transesterification. Then, melt polymerization may be carried out after transesterification, or a known synthesis method such as solid phase polymerization of a resin obtained by melt polymerization may be employed.

The catalyst used for the polymerization of polyester (after transesterification) includes antimony trioxide, zinc oxide, manganese dioxide, titanium dioxide, etc.
Of these, antimony trioxide is preferable.

Both the polyesters used in the present invention may contain phosphoric acid, phosphorous acid and their esters and inorganic particles (silica, kaolin, calcium carbonate, calcium phosphate, titanium dioxide, etc.) at the polymerization stage. After the polymerization, inorganic particles may be blended with the polymer. Further, at any stage after the polymerization and after the polymerization, pigments, ultraviolet absorbers, antioxidants, matting agents, slip agents, stabilizers, surfactants, dispersants, anti-tacking agents, softening agents, and imparting fluidity. You may add agents.

The above-mentioned antioxidant is not limited to its kind, and specific examples thereof include hindered phenol compounds, allylamino compounds, phosphite compounds, thioester compounds, and the like. Can be used. Among these, hindered type is preferable. In the production of the modified polyester, it is most preferable to add the antioxidant before extrusion. In order to obtain excellent photographic performance without increasing the turbidity of the laminated film, its content is usually 0.01 to 2 with respect to the modified polyester.
%, Preferably 0.1 to 0.5% by weight. The antioxidants may be used alone or in combination of two or more.

The polyester used in the present invention may contain various additives. For example, light piping phenomenon (flickering) that occurs when light enters from the cross section of a photographic support film coated with a photographic emulsion layer.
A dye may be added to the polyester for the purpose of preventing the above. The type of this dye is not particularly limited, but it is preferable that it has excellent heat resistance in the film forming process.
For example, anthraquinone chemical dyes and the like can be mentioned.

The laminated film of the present invention has a structure in which two or more kinds of resin layers are laminated in three or more layers. An example of a laminated film having a two-layer laminated structure by combining such resin layers is shown below. Explaining, it can be manufactured as follows. That is, for example, two kinds of resins are dried by two separate vacuum dryers, each of the resins is charged into the extruder in two separate extruders, melt-extruded, and then each melted resin is put in one conduit. Guide it up and down, 2 in the conduit
The molten resin of the layer forms a laminar flow and is extruded from the extrusion die with one slit onto the cooling drum to form one unstretched sheet, or another method is to use two kinds of molten polymer in one die. Introducing the molten polymer of, the two layers in a laminar flow form from an extrusion die with two slits or from an extrusion die with two slits combined into one slit in the die. Extruded on a cooling drum,
A single sheet was formed and cooled and solidified on a cooling drum to obtain an unstretched film, which was then stretched in a machine direction in a machine direction, then stretched in a cross machine in a transverse direction, and subsequently. It is a method of laminating in a molten state to obtain a biaxially stretched film by heat-setting in a heat-setting zone in the same machine, which is a method useful in the present invention. Another method is another position film forming method in which two types of molten polymers are separately extruded onto a cooling drum and cooled and solidified, which is also useful in the present invention. These are also called coextrusion methods.

In addition to this, there is a method of laminating and laminating separately formed films. That is, two kinds of resins are separately formed into an unstretched film or a uniaxially stretched film, and after coating them with an anchor agent, an adhesive, etc., these two kinds of films are laminated and laminated,
Then, this is a method of biaxially stretching and heat setting. However, this method is not practical in terms of quality because the process is complicated and the equipment cost is too high, and the coextrusion method is preferable because of its simplicity.

The temperature at which the modified polyester resin useful in the present invention is melted in an extruder is in the range of 260 to 320 ° C.
It is preferably 280 to 310 ° C. In the case of coextrusion, the modified polyester resin is preferably melted at the same temperature as the resin used for the outermost surface layer, for example, polyethylene terephthalate resin.

The stretching conditions of the laminated film of the present invention are not particularly limited, but in general, a plurality of resin layers having a high glass transition temperature (Tg) are biaxially stretched in the temperature range of Tg to Tg + 100 ° C. . At this time, the following methods A, B, and C can be adopted in the same manner as the stretching method of the polyethylene terephthalate layer. The stretching ratio is preferably in the range of 4 to 16 times in area ratio. The heat setting can be performed in the temperature range of 150 to 240 ° C.

(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 stretched in the transverse direction first and then in the longitudinal direction (C) Unstretched A method in which a sheet is stretched in the longitudinal direction in one or multiple stages, then stretched in the longitudinal direction again, and then stretched in the transverse direction.

The layers such as the resin layer, the outermost surface layer, and the inner layer are films having a certain thickness of the resin serving as a support, and include an undercoat layer, an antistatic layer and an emulsion layer. And so on.

The shrinkage rate with time of the single film of the resin used for each of the outermost surface layer and the internal layer of the laminated film of the present invention is preferably at least twice the shrinkage rate with time of the smallest resin layer.

The total thickness of the laminated structure film of the present invention is not particularly limited and can be arbitrarily determined according to the application, but is usually 40 to 250 μm, and particularly preferably 65 to 180 μm.

Further, like the heat shrinkage, the aging shrinkage is influenced by the stretching condition and the heat setting condition at the time of manufacturing, and therefore it is desirable to determine these film forming conditions.

The use of the laminated film of the present invention is not particularly limited, but it is useful as a photographic support in addition to an OHP film, a drawing film, a marking film, a printing sheet and the like.

<Undercoat layer> When the laminated film of the present invention is used as a photographic support, the emulsion layer of the silver halide photographic light-sensitive material is provided on the support to enhance the coating property of the emulsion layer. The undercoating treatment is performed for the purpose of maintaining strong adhesiveness.

Since the outermost surface layer of the laminated film of the present invention preferably has a polyethylene terephthalate (hereinafter abbreviated as PET) and / or polyethylene naphthalate (hereinafter abbreviated as PEN) layer, a subbing method for PET is used here. However, it goes without saying that it can be applied to PEN and modified polyester. .

The subbing on PET can be carried out in any of the processes before stretching during film formation, after uniaxial stretching, after biaxial stretching and before heat setting, or after biaxial stretching and heat setting. PET
Oriented crystallization is completed after heat setting after biaxial stretching,
It becomes relatively difficult for an upper object such as an emulsion layer to adhere. Therefore,
An undercoating agent is generally applied before the completion of oriented crystals. The following publicly known undercoating agents and subbing methods in which an undercoating agent is applied before heat setting can be used. For example, U.S. Pat.
378, 358,608, 3,630,741, 2,627,088
No. 2,698,235, JP-A-51-135991, JP-B-52-483
No. 12, Belgian Patent Nos. 721,469, 742,769, etc., and vinylhalogenoester-containing copolymers or vinylhalogenoester-containing copolymers and vinyl chloride and / or
Or vinylidene chloride containing copolymer, Japanese Patent Publication No. 58-5866
1, copolymers containing diolefins as a monomer described in JP-B-58-55497, JP-A-52-108114, etc., JP-A-61-204
242, an acrylic polymer described in JP-A-61-204241,
Examples thereof include polyester-based polymers described in JP-B-57-971, JP-A-61-204240, JP-A-60-248231, JP-A-3-265624 and the like.

The undercoating after the biaxial stretching heat setting is carried out by organic solvent-based undercoating or a so-called etching solvent (eg phenol, cresol, resorcin, hydrate) which etches PET to bond the undercoating material by the anchoring effect. There is also a method of applying an organic solvent-based or water-based undercoat liquid containing chloral, chlorophenol, etc.). This is because PET has a regular structure that makes it difficult to adhere,
This surface structure is loose or chemically changed. For this purpose, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment,
It is preferable to apply a surface activation treatment such as ozone treatment. Good adhesive strength can be obtained by directly coating the photographic emulsion after the above treatment, but in order to further strengthen the adhesive strength, a further subbing layer may be provided and a photographic emulsion layer may be formed on the undercoating layer. A good film is obtained. Even with a water-based undercoating agent, the adhesiveness can be easily improved by utilizing the above various treatments as a pretreatment. For example, a quaternary copolymer latex composed of n-butyl methacrylate: t-butyl methacrylate, styrene and 2-hydroxyethyl methacrylate according to the method described in JP-A-55-67745, JP-A-59-19941 and the like, an interface Activator,
An aqueous subbing solution consisting of a curing agent is applied and dried, followed by corona discharge treatment again, and then an aqueous gelatin solution such as an antihalation layer or emulsion layer is applied to the photographic emulsion layer side to improve the adhesiveness. A good photosensitive material can be obtained. Further, on the opposite side of the antistatic layer, after the same treatment or undercoat layer is applied, the antistatic composition is directly applied, and the antistatic layer binder such as cellulose diacetate is applied in advance and then the antistatic composition is applied. A desired photographic light-sensitive material can be finished by applying the product as an organic solvent system liquid.

When the laminated film of the present invention is applied to uses other than the photographic support of a silver halide photographic material, for example, an OHP film, a drafting film, a marking film, etc. It is also possible to use the subtraction method as it is.

<Back Layer or Antistatic Layer> A layer provided on the opposite side of a photosensitive material having a photosensitive layer on one side without the photosensitive layer is called a back layer. A back layer is provided depending on the type of silver halide light-sensitive material. The back layer is usually required to have antistatic properties. In general, PET or the like is subjected to the above-mentioned subbing and then a back layer such as an antistatic layer is applied.

In the antistatic layer useful in the present invention, most of the antistatic agents and antistatic compositions generally useful for silver halide photographic light-sensitive materials can be used. For example,
Styrene described in No. 47-28937 or Japanese Patent Publication No.
Anionic polymer antistatic agent such as sodium maleate copolymer, sodium vinylbenzyl sulfonate copolymer described in JP-A-53-82876, sodium styrene sulfonate copolymer described in JP-B-48-23451 Agent; JP-A-51-4
2535, JP-A-54-159222 and JP-A-55-7763, ionene polymers (for example, a polymer of triethylenediamine and xylidene dichloride), US Pat. No. 2,882,
No. 157, for example, polymethacryloylethyldiethylmethylammonium methylsulfonate, JP-B-60-516
No. 93, JP-A-61-223736 and JP-A-62-9346, a cross-linked copolymer particle having a quaternary ammonium group in its side chain (for example, copolymer [N, N, N-trimethyl-N -Vinylbenzylammonium chloride-co-divinylbenzene]), containing alumina sol as a main component described in JP-B-57-12979, ZnO, SnO ₂ , Ti described in JP-A-57-104931
_{O 2, Al 2 O 3,} In 2 O 3, SiO 2, MgO, BaO, MoO 3, ZiO particulate metal oxides such as _2, metal oxides such as V ₂ O ₅ described in JP-B-55-5982 charged Antistatic agent, higher fatty alcohol phosphate antistatic agent described in JP-B-52-32572, poly- (5-dodecylbenzothiophene), poly- (3 described in JP-A-2-255770 or JP-A-2-308246. -Dodecylthiophene),
Examples thereof include polythiophene-based polymers such as methacroylethyloxymethyl-3-polythiophene, and conjugated double bond conductive polymers such as poly (isothianaphthene) -based polymers described in JP-A-2-252726.

If desired, a back layer may be applied to the back surface. A hydrophilic binder layer may be used as the back layer. As the hydrophilic binder, gelatin, which is similar to the binder for the photosensitive layer, is most preferably used, and various gelatins are used. Other hydrophilic colloids, matting agents, slip agents, surfactants, hardeners, dyes, thickeners, polymer latices, antistatic agents and the like can be added as required.

<Photosensitive layer such as silver halide emulsion layer> As the silver halide photosensitive material according to the present invention, an ordinary black-and-white photographic light-sensitive material (for example, black-and-white light-sensitive material for photographing, black-and-white light-sensitive material for printing, black-and-white light-sensitive material for X-ray) is used. Materials, etc.), ordinary multilayer color light-sensitive materials (eg color negative film, color reversal film, color positive film, etc.)
Various light-sensitive materials can be mentioned.

Silver halide grains and other additives of the silver halide emulsion used in the silver halide light-sensitive material of the present invention, for example, chemical sensitizers, spectral sensitizing dyes, hardeners, surfactants, color couplers, There are no particular restrictions on
For example, Research Discl
osure) No. 308119 (hereinafter abbreviated as RD308119) can be used. The description location is shown below.

[Item] [Page of RD308119] Iodine composition 993 IA Item Manufacturing method 〃 and 994 E Item Crystal habit Normal crystal 〃 Twin crystal 〃 〃 Epitaxial 〃 〃 Halogen composition Uniform 993 IB Item uniform Not 〃 Halogen conversion 993 I-C item Halogen substitution 〃 Metal-containing 993 I-D item Monodisperse 995 I-F item Solvent addition 〃 Latent image forming surface 995 I-G inner surface 〃 Applied photosensitive material Negative 995 Item IH Positive (including internal fog grains) 〃 〃 Mixed emulsion 995 IJ Item Desalting 995 II-A Item The silver halide emulsion was subjected to physical ripening, chemical ripening and spectral sensitization. Use one. Additives used in such processes, Research Disclosure No. 17643,
Same No. l8716 and same No. 308119 (hereinafter referred to as RDl7643,
(Abbreviated as RDl 8716 and RD308119). The description location is shown below.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A 23 648 Spectral sensitizer 996 IV-A, B, C, D, 23 to 24 648 to 9 E ~ J Item Supersensitizer 996 IV-A ~ E, J item 23 ~ 24 648 ~ 9 Antifoggant 998 VI 24 ~ 25 649 Stabilizer 998 VI 24 ~ 25 649 The photographic additives that can be used are also in the above RD. Has been described.
Descriptions are shown below [Item] [Page of RD308119] [RD17643] [RD18716] Color turbidity inhibitor 1002 VII-I 25 650 Dye image stabilizer 1001 VII-J 25 Whitening agent 998 V 24 UV absorber 1003 VIII-C 25-26 XIII-C Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Antistatic agent 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27
650 Lubricants 1006 XII 27 650 Activators and coating aids 1005 XI 26 to 27 650 Matte agents 1007 XVI Developers 1011 XX-B (included in the photosensitive material) Various couplers can be used. Specific examples are also described in the above RD. The relevant description is shown below.

[Item] [Page of RD308119] [RD17643] Yellow coupler 1001 VII-D item 25 VII-C to G item Magenta coupler 1001 VII-D item 25 VII-C to G item Cyan coupler 1001 VII-D item 25 VII-C to G Colored coupler 1002 VII-G 25 VII-G DIR coupler 1001 VII-F 25 VII-F BAR coupler 1002 VII-F Other 1001 VII-F useful residue releasing coupler Alkali Soluble 1001 VII-E coupler The additives used can be added by the dispersion method described in RD308119XIV.

For the color light-sensitive material, the above-mentioned RD308119 VII-
An auxiliary layer such as a filter layer or an intermediate layer described in the section K can be provided. In addition, the above-mentioned RD308,119 VII-K
Various layer configurations such as the forward layer, the reverse layer, and the unit configuration described in the section can be adopted.

To develop the silver halide photographic light-sensitive material of the present invention, for example, T.W. H. James, Theory of the Photographic Process 4th Edition (Th
e Theory of The Photographic Process Forth Editio
n) Pages 291 to 334, and Journal of the
American Chemical Society (JournaI of the A
American Chemical Society) Vol. 73, p. 3,100 (195
The known developer described in 1) can be used. In addition, the color photographic light-sensitive material is 28 of RD17,643 described above.
˜29, RDl8,716, page 615 and RD308,119, XIX, by conventional methods.

<Magnetic Recording Layer> If necessary, the silver halide photographic light-sensitive material may be coated with a magnetic recording material on the upper surface of the photosensitive layer or on the upper surface of the back layer for the following purposes.

For example, a stripe-shaped magnetic recording layer in which fine ferromagnetic particles are dispersed is provided on the emulsion surface or the back surface next to the image area to record information such as voice and shooting conditions. KAISHO 50-62627 publication, JP 49-4503 publication,
U.S. Pat. Nos. 3,243,376 and 3,220,843, etc., and a transparent magnetic recording on the back surface of a photographic light-sensitive material with the required transparency by selecting the amount and size of magnetic particles. Providing layers is US license No. 3,782,947
No. 4,279,945, No. 4,302,523, and the like. Also, US Pat. No. 4,947,196 and WO90 / 04254 describe a photographing camera having a magnetic head together with a roll-shaped film having a magnetic recording layer containing a magnetic material that enables magnetic recording on the back surface of the photographic film. Has been done.

As described above, the silver halide photographic light-sensitive material contains various kinds of information on the photographic light-sensitive material such as the kind / manufacturing number of the photographic light-sensitive material, the manufacturer name, and the emulsion No. , Exposure time, lighting conditions, filter used, weather, size of shooting frame, camera model, use of anamorphic lens, and other various information at the time of camera shooting, for example, number of prints, selection of filter, customer Various information necessary for printing, such as the color preference and trimming frame size, for example, the number of prints,
Entering various information obtained at the time of printing such as filter selection, customer's color preference, trimming frame size, and other customer information is important for management and print quality improvement. It is convenient if the above-mentioned matters are recorded in order to improve the efficiency of printing work.

In the conventional photographic light-sensitive material, it is impossible to input all of these pieces of information.
At the time of shooting, I was only optically entering information such as the shooting date / time, aperture, and exposure time. Moreover, at the time of printing, it was completely impossible to input the above information into the photographic light-sensitive material because there was no means for that.

Since the magnetic recording method is easy to record / reproduce, the use of the magnetic recording method for inputting the above various information to the photographic light-sensitive material has been studied, and various techniques have been proposed as described above. There is.

By providing these magnetic recording layers, it becomes possible to record the above-mentioned various kinds of information in the photographic light-sensitive material, which has been difficult in the past, and further, it is possible to record voice and image signals. are doing.

As the magnetic fine powder used in the magnetic recording layer, metal magnetic powder, iron oxide magnetic powder, Co-deposited iron oxide magnetic powder, chromium dioxide magnetic powder, barium ferrite magnetic powder, etc. are used. it can.

When the transparent magnetic recording layer is provided on the photosensitive layer side, a hydrophilic binder such as gelatin is used as the binder of the magnetic recording material. In the case of a hydrophilic binder, gelatin is preferably used. When the magnetic recording layer is provided on the back side without the photosensitive layer, a hydrophobic solvent-soluble binder such as cellulose nitrate is used.

[0086]

EXAMPLES The present invention will be described in detail below with reference to Examples, but it goes without saying that the present invention is not limited thereto.

(Example 1) <Preparation of Laminated Film Nos. 1 to 13> 0.1 part by weight of calcium acetate hydrate was added to 100 parts by weight of terephthalic acid and 64 parts by weight of ethylene glycol, and esterification reaction was carried out by a conventional method. went. 28 parts by weight of an ethylene glycol solution of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid (concentration 35% by weight) (5 mol% / total acid component),
8.1 parts by weight of polyethylene glycol (number average molecular weight 3000) (7% by weight / polymer), 0.05 parts by weight of antimony trioxide and 0.13 parts by weight of trimethyl phosphate were added.
Then, 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 modified polyester resin having an intrinsic viscosity of 0.55.

Each of the modified polyester resin (abbreviated as M in the table) and a commercially available PET resin having an intrinsic viscosity of 0.65 (also abbreviated as P) was vacuum dried at 150 ° C., and then three extruders were used. The mixture was melt extruded at 0 ° C., three layers were joined in layers in a T-die so as to be composed of the materials shown in Table 1, and rapidly solidified while being brought into close contact with a cooling drum by an electrostatic contact method to obtain a laminated unstretched film. At this time, the extrusion amount of each material was adjusted so that the thickness ratio of each layer was as shown in Table 1. Then, draw it 3.5 times in the machine direction at 85 ℃, and then in the transverse direction at 95 ℃.
After stretching 3.5 times, it was heat set at 210 ° C. to obtain a biaxially stretched film. Each of them was cut into a size of 120 mm in length × 35 mm in width, and sample Nos. 1 to 13 were shown in Table 1. In addition, Table 1
Regarding the layered structure and the layered ratio (upper / outer / lower / outer) in the section of the layered structure of (1), the left side of the data of the layered ratio in Table 1 is the upper outer side, and the right side is the lower outer side. That is, when the laminated film is divided into two in the thickness direction, the thicker inner layer is the upper outer layer and the thinner inner layer is the lower outer layer. Further, a curl concave to the upper outer side is a + (plus) curl, and a curl concave downward to the outer side (curl convex to the upper outer side) is a − (minus) curl.

<Measurement of Intrinsic Viscosity> The measurement was carried out using an Ubbelohde viscometer. The weight ratio of phenol and 1,1,2,2-tetrachloroethane as a mixed solvent is about 55:45 (flow time 42.0 ± 0.
Adjust the sample resin concentration to 0.2, 0.
A 6,1.0 (g / dl) solution (temperature: 20 ° C) was prepared. The specific viscosity (η _sp ) at each concentration (C) was calculated with an Ubbelohde viscometer and Was extrapolated to zero concentration to obtain the intrinsic viscosity [η].

<Single modified polyester film No. 14 to 1
Preparation of 8> Only the modified polyester resin constituting the laminated film is used, the three extruders in the section of the laminated film preparation are changed to only one extruder, and the other steps are the same as the film forming method. A modified polyester single film was prepared in the same manner and cut into a size of 120 mm × 35 mm in the same manner as above, and samples Nos. 14 to 18 were shown in Table 1.

<Preparation of individual PET films No. 19 to 23>
A single film of PET resin was prepared in the same manner as the single modified polyester film, cut into a size of 120 mm × 35 mm, and sample Nos. 19 to 23 were shown in Table 1.

<Measurement Method of Curling Degree with Time> Measurement of curling value with time standing on a flat plate (curvature 0 m ⁻¹ ): all the samples 1 to 23 above have almost no curl immediately after film formation. The initial uncurled sample was cut into a size of 120 mm in the longitudinal stretching direction and 35 mm in the transverse stretching direction, and in Table 1, the upper and outer sides were placed on the surface of the flat plate and allowed to stand flat at 23 ° C and 55% RH. 12 as it is in a conditioned atmosphere
The curl degree after standing for a month was measured using a curl scale, and the results are shown in Table 1.

However, in this case, standing means that no external force acts on the film other than its own weight.

The curl scale has a curvature (m ^-1 ) of 0.5.
A curve with an arc of 0 to 200 at intervals of ~ 1 (in the range of small curvature) or 5 to 10 intervals (in the range of large curvature) (0
Is a line drawn on a transparent film or is photographically printed. The curl scale is applied to the film edge in the length direction of the curled sample film, and the curl degree (curvature) corresponding to each arc is read.

<Measuring Method of Curling Conditions and Curling Degree of Curling> A winding core having a curvature of 185.2 m ^-1 (a spool of a 135 format photographic cartridge with a diameter of 10.8 mm) is curled concavely over time. (Reverse winding) Wrap the film sample, fix the outermost end of the film with adhesive tape, leave it in the environment adjusted to 23 ° C, 55% RH, and release the winding after 12 months Then, with the surface curled concavely on the flat plate facing up, or if the curl is large, stand the curled film upright so that the arc can be seen from the top, and leave the film after 20 minutes. Was measured and the results are shown in Table 1.

A film sample was wound around the above core in the same manner as described above to fix the end, and heat-treated for 15 days in an environment of 40 ° C. and 55% RH, and cooled in an environment of 23 ° C. and 55% RH. Then, the roll was released, and the curl degree was measured after 20 minutes. The results are shown in Table 1.

Curvature 26.2 m ^-1 (Diameter 3 inches = 76.2 mm)
Wrap the film sample around the resin core with the side that curls concavely over time (reverse winding) and fix the outermost end of the film with adhesive tape, 23 ° C, 55% RH
After leaving it for 12 months, release the roll, and in the same way as above, make the surface that is curled concave on the flat plate the upper side, or if the degree of curl is large. The curled film was erected so that the arc was seen from above, the film was allowed to stand, the curl degree was measured after 20 minutes, and the results are shown in Table 1.

A film sample was wound around the above core in the same manner as above to fix the end, and heat-treated for 15 days in an environment of 40 ° C. and 55% RH and cooled in an environment of 23 ° C. and 55% RH. Then, the roll was released, and the curl degree was measured after 20 minutes.
The results are shown in Table 1.

<Measurement of Amount of Time-dependent Shrinkage> With respect to a single film, the percentage of time-dependent shrinkage was measured as shown in Table 1. The sample size was 120 mm in the vertical direction and 35 mm in the horizontal direction, and two fine dot marks were attached to the film in the vertical direction at exactly 100 mm intervals, and the film was left for 12 months in an environment where the humidity was adjusted to 23 ° C. and 55% RH. Then, the dimension between the marks was read on a flat plate using a loupe, the dimension after shrinkage was measured, and the shrinkage rate was calculated according to the following formula. The results are shown in Table 1.

Shrinkage with time (%) = (Dimension after shrinkage /
Original dimensions before shrinkage) x 100

[0101]

[Table 1]

<Results and Evaluation> As can be seen from Table 1, the single film No. 14 to 23 and comparative sample films Nos. 1 to 4 having a symmetrical laminated structure did not cause curling with time. Although the modified polyester single film shrinks more than 10 times as much as the PET single film with time, the modified polyester as the inner layer and PET as the outermost layer are non-uniform in the thickness direction of the present invention. No. 13 has a curl degree extremely smaller than that of Comparative Laminated Film Nos. 5 to 7 in which PET is the inner layer and modified polyester is the outermost layer, and it is found that the curl is not easily attached.

Example 2 Three kinds of resins, a PET resin having an intrinsic viscosity of 0.65, a PEN resin having an intrinsic viscosity of 0.68 and a modified polyester resin having an intrinsic viscosity of 0.57 polymerized in the same manner as in Example 1, were used in the same manner as in Example 1. Sample Nos. 24 to 36 were prepared from the single film and the three-layer laminated film with the composition, thickness, laminated constitution and laminated ratio as shown in Table 2. In Table 2, N is an abbreviation for PEN. Further, as in the first embodiment, M,
A single film of P and N was prepared and used as sample Nos. 37 to 45.

Samples Nos. 24-45 were cut into A2 size sheets (with the longitudinal stretching direction oriented in the longitudinal direction),
The end of the film was left free in a round cylinder for storing drawings with a diameter of 90 mm (curvature 22 m ^-1 ) with the surface that curls concavely over time, and the end was free (the film is supported by spring force). It is in the state of pressing the inner wall of the round cylinder).

[0105] A round cylinder containing these films was stored for 12 months in an environment of 23 ° C and 55% humidity with the lid open.
After storing for 15 days in an environment of 55 ° C and 55% RH, take out the film from the round tube, cut out a piece of 120 mm in the longitudinal direction and 35 mm in the width direction from the center of the A2 size film, and curl it. The degree was measured, and the results are shown in Table 2.

[0106]

[Table 2]

<Results and Evaluation> As can be seen from Table 2, the single film Nos. 37 to 45 and the comparative sample films Nos. 24 to 27 having symmetrical laminated structures did not cause curling over time. The modified polyester single film has 10 times or more larger shrinkage over time than the PET single film, but the modified polyester is the inner layer and PET is the outermost layer, and the laminated film No. 31-is not uniform in the thickness direction of the present invention. No. 36, which has PET as an inner layer and modified polyester as the outermost surface layer, has a significantly smaller curl curl and is more difficult to curl than Comparative Laminated Film Nos. 28 to 30.

Example 3 A silver halide color photographic light-sensitive material was prepared as follows using the laminated film.

<Preparation of Photosensitive Material><Preparation of Photographic Support and Subsequent Pretreatment before Heat Fixing> 100 parts by weight of terephthalic acid and 64 parts by weight of ethylene glycol were added with 0.1 part by weight of calcium acetate hydrate, followed by a conventional method. To carry out the esterification reaction. The obtained product was 28 parts by weight of ethylene glycol solution of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid (concentration 35% by weight) (5 mol% / total acidic content), polyethylene glycol (number average molecular weight 300
0) 8.1 parts by weight (7% by weight / polymer), antimony trioxide 0.05 parts by weight, phosphoric acid trimethyl ester 0.13 parts by weight were added. Then gradually raise the temperature and reduce the pressure, 280 ℃, 0.5mmHg
Polymerization was carried out to obtain a modified polyester resin having an intrinsic viscosity of 0.57.

Each of the modified polyester resin (abbreviated as M in the table) and a commercially available PET resin having an intrinsic viscosity of 0.65 (also abbreviated as P) was vacuum dried at 150 ° C., and then three extruders were used. Melt extrusion was carried out at 0 ° C., three layers were joined in a T-die so that the three layers were made of the materials shown in Table 3, and rapidly solidified while being brought into close contact with a cooling drum by an electrostatic contact method to obtain a laminated unstretched film. At this time, the extrusion rate of each molten resin was adjusted so that the thickness ratio of each layer was as shown in Table 3. Then
It was stretched 3.5 times in the machine direction at 85 ° C.

On both sides of the longitudinally uniaxially stretched film, dimethyl terephthalate 37 parts by weight, dimethyl isophthalate 30 parts by weight, 5-sulfoisophthalic acid dimethyl sodium salt 10 parts by weight, ethylene glycol 52 parts by weight, 1,4-cyclohexanedicarboxylic acid An 8% aqueous solution of a modified polyester resin (intrinsic viscosity 0.52) obtained by polymerizing 16 parts by weight of acid and 5 parts by weight of polyethylene glycol (number average molecular weight 1,000) was used as the undercoat layer coating solution, and the dry weight was applied to both sides of the film after the vertical stretching. At 0.3
g / m ² was coated so as to have an undercoat layer, and subsequently stretched 3.5 times in the transverse direction at 95 ° C. and then heat-set at 210 ° C. to give a biaxially stretched film having a thickness as shown in Table 3 below. Obtained.

<Preparation of silver halide color negative photographic light-sensitive material> As described below, multilayer coating was repeated three times with a slide hopper coater for a light-sensitive layer such as an emulsion layer on the side of the above-mentioned undercoated laminated film having a convex curl with time. , 12 layers were provided, and a gelatin backing layer was similarly coated and dried on the opposite side to prepare a silver halide color photographic light-sensitive material (hereinafter abbreviated as color negative film). The dry film thickness of the backing layer and the photosensitive layer is 5 μm and 24 μm, respectively.
And

<< Backing Layer >> First Layer; Gelatin 4.5 mg Sodium-di-(-2-ethylhexyl) -sulfosuccinate 1.0 mg Sodium tripolyphosphate 76 mg Citric acid 16 mg Carboxyalkyl dextran sulfate 49 mg Vinyl sulfone type hardener 30 mg Second layer (outermost layer); gelatin 1.5 g Polymer beads (average particle size: 3 μm, polymethyl methacrylate) 24 mg Vinyl sulfone type hardener 45 mg Mixture of compound SB-1 and compound SB-2 30 mg Compound SB-1 100 mg << Photosensitive layer >> First layer; antihalation layer [HC] Black colloidal silver 0.15 g UV absorber (UV-1) 0.20 g Compound (CC-1) 0.02 g High boiling point solvent (Oil-1) 0.20 g High boiling point solvent ( Oil-2) 0.20 g Gelatin 1.6 g Second layer; Intermediate layer [IL-1] Gelatin 1.3 g Third layer; Low-sensitivity red-sensitive emulsion layer [RL] Silver iodobromide emulsion (average grain size 0.3 μm, average Udo content 2.0 mol%) 0.4 g Silver iodobromide emulsion (average particle size 0.4 .mu.m, the average iodide content of 8.0 mol%) 0.3 g Sensitizing dye (S-1) 3.2 × 10 -4 ( mol / 1 mol of silver ) Sensitizing dye (S-2) 3.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-3) 0.2 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C-1) 0.50 g Cyan coupler (C-2) 0.13 g Colored cyan coupler (CC-1) 0.07 g DIR compound (D-1) 0.006 g DIR compound (D-2) 0.01 g High boiling point solvent (Oil-1) 0.55 g Gelatin 1.0 g 4th layer: High-sensitivity red-sensitive emulsion layer [RH] Silver iodobromide emulsion (average grain size 0.7 μm, average iodine content 7.5 mol%) 0.9 g Sensitizing dye (S-1) 1.7 × 10 ⁻⁴ (mol / Silver 1 mol) Sensitizing dye (S-2) 1.6 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-3) 0.1 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C- 2) 0.23g empty Dosian coupler (CC-1) 0.03 g DIR compound (D-2) 0.02 g High boiling point solvent (Oil-1) 0.25 g Gelatin 1.0 g Fifth layer; Intermediate layer [IL-2] Gelatin 0.8 g Sixth layer; Low-sensitivity green-sensitive emulsion layer [GL] Silver iodobromide emulsion (average grain size 0.4 μm, average iodine content 8.0 mol%) 0.6 g Silver iodobromide emulsion (average grain size 0.3 μm, average iodine content 2.0 mol%) ) 0.2 g Sensitizing dye (S-4) 6.7 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-5) 0.8 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (M-1) 0.17g Magenta coupler (M-2) 0.43g Colored magenta coupler (CM-1) 0.10g DIR compound (D-3) 0.02g High boiling solvent (Oil-2) 0.7g Gelatin 1.0g 7th layer; high sensitivity green Sensitive emulsion layer [GH] Silver iodobromide emulsion (average grain size 0.7 μm, average iodine content 7.5 mol%) 0.9 g Sensitizing dye (S-6) 1.1 × 10 ⁻⁴ (mol / Silver 1 mol) Sensitizing dye (S-7) 2.0 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-8) 0.3 × 10 ⁻⁴ (mol / silver 1 mol) Magenta coupler (M-1) ) 0.30 g Magenta coupler (M-2) 0.13 g Colored magenta coupler (CM-1) 0.04 g DIR compound (D-3) 0.004 g High boiling point solvent (Oil-2) 0.35 g Gelatin 1.0 g Eighth layer; Yellow filter Layer [YC] Yellow colloidal silver 0.1 g Additive (HS-1) 0.07 g Additive (HS-2) 0.07 g Additive (SC-1) 0.12 g High boiling point solvent (Oil-2) 0.15 g Gelatin 1.0 g 9 layers; low-sensitivity blue-sensitive emulsion layer [BL] Silver iodobromide emulsion (average grain size 0.3 μm, average iodine content 2.0 mol%) 0.25 g Silver iodobromide emulsion (average grain size 0.4 μm, average iodine content) 8.0 mol%) 0.25 g sensitizing dye (S-9) 5.8 × 10 -4 ( mol / mole of silver) yellow coupler (Y-1) 0.6 g yellow coupler -(Y-2) 0.32 g DIR compound (D-1) 0.003 g DIR compound (D-2) 0.006 g High boiling point solvent (Oil-2) 0.18 g Gelatin 1.3 g 10th layer; high-sensitivity blue-sensitive emulsion layer [ BH] Silver iodobromide emulsion (average grain size 0.8 μm, average iodine content 8.5 mol%) 0.5 g Sensitizing dye (S-10) 3 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S- 11) 1.2 × 10 ⁻⁴ (mol / silver 1 mol) Yellow coupler (Y-1) 0.18 g Yellow coupler (Y-2) 0.10 g High boiling point solvent (Oil-2) 0.05 g Gelatin 2.0 g 11th layer; 1 Protective layer [PRO-1] Silver iodobromide (average particle size 0.08 μm) 0.3 g UV absorber (UV-1) 0.07 g UV absorber (UV-2) 0.08 g Additive (HS-1) 0.2 g Additive (HS-2) 0.1g High boiling solvent (Oil-1) 0.07g High boiling solvent (Oil-3) 0.07g Gelatin 0.8g 12th layer; 2nd protective layer [PRO-2] Compound (Compound A) 0.04g compound (Compound B) 0.004 g Polymethylmethacrylate (average particle size: 3 μm) 0.02 g Copolymer of methylmethacrylate: ethylmethacrylate: methacrylic acid = 3: 3: 4 (weight ratio) (average particle size: 3 μm) ) 0.13 g Gelatin 0.7 g << Preparation of silver iodobromide emulsion >> The silver iodobromide emulsion used in the 10th layer was prepared by the following method.

A silver iodobromide emulsion was prepared by a double jet method using monodispersed silver iodobromide grains having an average grain size of 0.33 μm (silver iodide content 2 mol%) as seed crystals.

A solution [G-1] having the following composition was treated at a temperature of 70 ° C. and pA.
The seed emulsion in charge of 0.34 mol was added with good stirring while maintaining g 7.8 and pH 7.0.

(Formation of Internal High Iodity Phase-Core Phase) Then, a solution [H-1] having the following composition and a solution [S-
1] and were added at an accelerated flow rate (the flow rate at the end was 3.6 times the initial flow rate) over 86 minutes while maintaining the flow rate ratio of 1: 1.

(Formation of External Low Iodity Phase-Shell Phase) Subsequently, [H-2] and [S] were maintained while maintaining pAg10.1 and pH6.0.
-2] was added at a flow rate accelerated by a flow rate ratio of 1: 1 (the flow rate at the end was 5.2 times the initial flow rate) over 65 minutes.

The pAg and pH during grain formation were controlled using an aqueous potassium bromide solution and a 56% aqueous acetic acid solution. After the particles are formed, they are washed with water by a conventional flocculation method, and then gelatin is added to redisperse them, and the pH is adjusted to 40 ° C.
And pAg were prepared at 5.8 and 8.06, respectively.

The obtained emulsion was a monodisperse emulsion containing octahedral silver iodobromide grains having an average grain size of 0.80 μm, a distribution width of 12.4% and a silver iodide content of 8.5 mol%.

[G-1] Solution Ocein gelatin 100.0 g 10% by weight solution of the following compound-I in methanol 25.0 ml 28% aqueous ammonia solution 440.0 ml 56% acetic acid aqueous solution 660.0 ml Finish with water 5000.0 ml * Compound-I: polypropyleneoxy -Polyethyleneoxy, di-succinic acid, sodium.

[H-1] Solution Ocein gelatin 82.4 g Potassium bromide 151.6 g Potassium iodide 90.6 g Finish with water 1030.5 ml [S-1] solution Silver nitrate 309.2 g 28% Aqueous ammonia solution Equivalent with water 1030.5 ml 28% Aqueous ammonia solution Equivalent to finish with water 1030.5 ml [H-2] solution Ocein gelatin 302.1 g Potassium bromide 770.0 g Potassium iodide 33.2 g Finish with water 3776.8 ml [S-2] solution Silver nitrate 1133.0 g 28% aqueous ammonia solution Equivalent to water Finishing 3776.8 ml For silver iodobromide emulsions used in emulsion layers other than the 10th layer, the average grain size, temperature, pAg, p
The above emulsions having different average grain sizes and silver iodide contents were prepared by changing H, flow rate, addition time, and halide composition.

All were core / shell type monodisperse emulsions having a distribution of 20% or less. Each emulsion was subjected to optimum chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate, and a sensitizing dye, 4-hydroxy-6
-Methyl-1,3,3a, 7-tetrazaindene, 1-phenyl-5-mercaptotetrazole was added.

The above light-sensitive material further comprises a compound
Su-1, Su-2, viscosity modifier, hardener H-1, H-2,
Stabilizer ST-1, antifoggant AF-1, AF-2 (weight average molecular weight 10,000 and 1,100,000), dye AI-
1, AI-2 and compound DI-1 (9.4 mg / m ² ).

The structures of the compounds are shown below.

[0125]

Embedded image

[0126]

[Chemical 3]

[0127]

[Chemical 4]

[0128]

[Chemical 5]

[0129]

[Chemical 6]

[0130]

[Chemical 7]

[0131]

Embedded image

[0132]

[Chemical 9]

[0133]

[Chemical 10]

[0134]

[Chemical 11]

[0135]

[Chemical 12]

The sample size, the production of PET single film, the production of modified polyester single film, the measurement of intrinsic viscosity, the method of measuring the degree of curl over time, and the method of measuring the curling degree of winding conditions and curl were the same as in Example 1. However, the color film was wound with the photosensitive layer side facing inward. Sample No.4
The contents of 6 to 62 are shown in Table 3, and the results are also shown in Table 3.
It was shown to.

[0137]

[Table 3]

As can be seen from Table 3, the color films Nos. 46 to 49 from the single film and the comparative color films Nos. 50 to 52 having a symmetrical laminated structure have a slight curl due to the light-sensitive layer. Observed as minute curls. Color films No. 53 to 58 made of the laminated film of the present invention, which is non-uniform in the thickness direction with the modified polyester as the inner layer and PET as the outermost surface layer, has PET as the inner layer,
From the comparative laminated film color films Nos. 59 to 62 in which the modified polyester was used as the outermost layer, it was found that the curl curl was extremely small and the curl was very hard to attach.

(Example 4) A silver halide emulsion for printing was coated on the emulsion layer side of an undercoated photographic support (see Table 4 for thickness ratio) prepared in the same manner as in Example 3. A photographic film for silver halide printing (hereinafter abbreviated as photographic film for printing) was prepared.

<Preparation of Silver Halide Emulsion A> A silver chloride emulsion consisting of 70 mol% of silver chloride, 0.2 mol% of silver iodide and the balance of silver bromide was prepared by the simultaneous mixing method. K ₃ during simultaneous mixing
8.1 × 10 ⁻⁸ mol of RhBr ₆ was added per mol of silver. The obtained emulsion was a cubic emulsion having an average grain size of 0.20 μm and monodisperse grains (variation coefficient: 9%). Next, the emulsion was desalted with phenylcarbamyl group-substituted modified gelatin. EAg after desalting
Was 190 mv at 50 ° C.

The obtained emulsion was adjusted to pH 5.58 and EAg123mv, and then the temperature was adjusted to 60 ° C., and chloroauric acid was added per mol of silver.
Add 2.2 × 10 ^-5 mol and stir for 2 minutes, then add inorganic sulfur to silver 1
2.9 × 10 ⁻⁶ mol was added per mol and chemical ripening was performed for 78 minutes. At the end of ripening, the following was added per mol of silver.

4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 7.5 × 10 ^-3 mol, 1-phenyl-5-mercaptotetrazole 3.5 × 10 ^-4 mol and gelatin 28.4 g An emulsion liquid was added.

(Preparation of silver halide photographic light-sensitive material) Formulation 1 (silver halide emulsion layer composition) Silver halide emulsion Silver amount 3.2 mg / m ² Gelatin 2.0 g / m ²

[0144]

[Chemical 13]

S-1 (sodium-iso-amyl-n-decylsulfosuccinate) 0.6 mg / m ² 2-mercapto-hydroxypurine 1.7 g / m ² EDTA 50 mg / m ² Formulation 2 (emulsion protective layer-1 composition) ) Gelatin 0.5 g / m ² S-1 12 mg / m ² Matting agent: Monodispersed silica 40 mg / m ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ^{2 with an} average particle size of 3.5 μm

[0146]

Embedded image

Formulation 3 (Emulsion protective layer-2 composition) Gelatin 0.8 g / m ² S-1 4 mg / m ² Latex polymer (L-1) 0.2 g / m ² Formulation 4 (backing layer composition) Saponin 133 mg / m ² S-1 0.1g / m ² Colloidal silica 100mg / m ² Latex polymer (L-1) 0.2g / m ²

[0148]

[Chemical 15]

Formulation 5 (Composition of backing protective layer) Matting agent: Monodispersed polymethylmethacrylate having an average particle size of 5.0 μm 50 mg / m ² Sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ² <Preparation of sample A backing layer coating solution and a backing layer protective film after corona discharge on the surface of the undercoated laminated photographic support used in Example 3 on the side where the curl with time becomes convex at an energy of 15 W / m ² · min The two layers were simultaneously coated with the layer coating solution using a slide hopper to give a dry film thickness of 4 μm. Also, 15 W is applied to the surface on the side where the curling with time of the support curls concavely.
After corona discharge at an energy of / m ² · min, the emulsion layer, the second layer of the emulsion protective film layer (formulation 3) and the protective layer upper layer (formulation 2) were coated with the photosensitive layers in the same manner as above. A photographic film for printing was prepared by coating and drying so that the dry film thickness of the photosensitive layer was 5 μm. 580m width of these films
It was cut into m and 1 m in length and used for the winding test. Table 4 shows the constitution and film thickness of each printing film sample.

A core having a curvature of 39.37 m ^-1 (diameter: 50.8 mm = 2 inches) and a length of 590 mm was prepared. The surface of the paper core coated with resin was coated on the photosensitive layer surface (curved concavely with time). (The surface to be sewn) is wound to form a roll film, and the outermost end of the film is fixed with adhesive tape.
Leave it in a room adjusted to% RH, release the roll after 12 months, cut out a small sample for curl measurement of 120 mm in length × 35 mm in width from the center of the sample, and place it on a flat plate with its concave surface facing up The sample was left to stand and the curl degree was measured after 20 minutes. The results are shown in Table 4.

A photographic film sample for printing was wound around the above core in the same manner as above to fix the end, and the temperature was kept at 40 ° C. for 55
Heat treatment was performed for 15 days in an environment of% RH, cooling was performed in an environment of 23 ° C. and 55% RH, the winding was released, the sample was left to stand in the same manner as above, and the curl degree was measured after 20 minutes. The results are shown in Table 4.

In addition, the measurement of the method for measuring the degree of curl over time was performed according to Example 1.

[0153]

[Table 4]

As can be seen from Table 4, the photographic films for printing No. 63 to 66 made from a single film and the photographic films for comparative printing No. 67 to 69 having a symmetrical laminated structure have a slight curling with time in the photosensitive layer. It was observed as the curl of the curl generated by. Photographic films for printing No. 70 to 73 made of the laminated film of the present invention having a modified polyester as the inner layer and PET as the outermost layer and not being uniform in the thickness direction, have PET as the inner layer and the modified polyester as the outermost surface. From the comparative laminated film printing photographic films No. 74 to 78 as layers, the curl curl degree is extremely small, and the curl curl degree is almost zero, and the curl is not easily attached.

[0155]

Since the present invention is configured as described above, it has the following effects.

Two or more resin layers having different curl tendency or different time-dependent shrinkage have a laminated structure of at least three layers, and the layer having the strongest curl tendency or the time-dependent shrinkage among the resin layers. By arranging the largest layer in the inner layer of the laminate, it is possible to obtain a plastic film having less curl.

Further, by providing a silver halide emulsion layer or the like on this laminated film, a silver halide light-sensitive material which is hard to be rolled and easy to handle can be obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location G03C 1/81

Claims (10)

[Claims] 1. Two or more resin layers having different curl tendencies,
A laminated film having a laminated structure of at least three layers, wherein the resin layer having the strongest curl tendency among the resin layers is located in the inner layer of the laminated layer. 2. Two or more kinds of resin layers having different temporal shrinkages have a laminated structure of at least three layers, and the resin layer having the largest temporal shrinkage among the resin layers is located in the inner layer of the laminate. A laminated film characterized in that. 3. The laminated film according to claim 1, wherein when the thickness of the laminated film is divided into two equal parts, the layer structure on both sides of the divided film is asymmetric. 4. The resin layer having the strongest tendency to curl or the resin layer having the largest shrinkage with time is a modified polyester resin layer containing a metal sulfonate group. The laminated film according to item 1. 5. A polyethylene terephthalate resin layer and / or a polyethylene naphthalate resin layer are located on both sides of an outermost surface layer of a laminated structure, and at least one of the inner layers is a modified polyester resin layer containing a sulfonate group. The laminated film according to any one of claims 1 to 4, which is characterized by the above-mentioned. 6. Two or more resin layers having different curl tendencies,
It has a laminated structure of at least three layers, and has as a support a laminated film in which the resin layer having the strongest curl tendency among the resin layers is located in the inner layer of the laminate, and at least one of the laminated film supports A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on its side. 7. Two or more types of resin layers having different shrinkage rates have a laminated structure of at least three layers, and the resin layer having the largest shrinkage rate among the resin layers is located in the inner layer of the laminate. A silver halide photographic light-sensitive material comprising a laminated film as a support and at least one silver halide emulsion layer on at least one side of the laminated film support. 8. The silver halide according to claim 6, wherein when the laminated film support divides the thickness of the laminated film into two equal parts, the layer structure on both sides of the divided film is asymmetric. Photographic material. 9. The laminated film support has a modified polyester resin layer containing a metal sulfonate group as the resin layer having a strong tendency to curl or the resin layer having the largest shrinkage ratio with time. Any one of 8
A silver halide photographic light-sensitive material as described in the above item. 10. A modified polyester in which the laminated film support has a polyethylene terephthalate resin layer and / or a polyethylene naphthalate resin layer on both sides of the outermost surface layer of the laminated structure, and at least one of the inner layers contains a metal sulfonate group. The silver halide photographic light-sensitive material according to any one of claims 6 to 9, which is a resin layer.