KR100196055B1 - Base film for photographic film - Google Patents

Abstract

(a) the refractive index nz in the thickness direction is 1.498 or more, (b) the haze value is 2.0% or less, and (c) the tan δ value of 80 ° C due to tensile viscoelasticity at 0.05 Hz is 0.09 or less. (d) the anti-culling ratio at 70 ° C. is 45% or more, (e) the thickness is in the range of 40 to 120 μm, and (f) the polyethylene-2,6-naphthalenedicarboxylate is a substantial material. Base film for photographic film to assume. This base film has various suitable performances for photographic films, such as anti-colling property, transparency, and activity.

Description

[Name of invention]

Base film for photographic film

Detailed description of the invention

[Technical Field]

The present invention relates to a base film for photographic film. More specifically, the present invention relates to a base film for photographic films based on polyethylene 2,6-naphthalene dicarboxylate having anti-curling property, transparency, activity and the like.

Background Technology

Since the biaxially stretched polyethylene-2,6-naphthalenedicarboxylate film has the outstanding mechanical property, thermal property, electrical property, etc., use by various uses is examined. In the field of magnetic recording media and electrical insulation, it has been put to practical use.

It is used in the field of photographic photosensitive materials as one of film uses. The said photosensitive material can be classified roughly into what is used in sheet form, such as a film for X-rays, a film for making, a cut film, etc., and what is used as a roll film. Representative of roll films include color or black-and-white negative film that is housed in a Patrone in a width of 35 mm or less and loaded into a general camera and used for photographing.

As the base of the sheet-like film, a biaxially stretched polyester film formed of polyethylene terephthalate is mainly used, and the base of the roll film is a cellulose polymer represented by triacetyl cellulose (hereinafter sometimes abbreviated as TAC). The formed film is used.

The characteristic of a TAC film is that it is optically non-anisotropic, has high transparency, and is excellent in curl elimination property after image development processing. Especially, excellent curl elimination property is recognized as a characteristic not found in other material films. However, since this TAC film uses an organic solvent in the manufacturing process, care must be taken not to pollute the environment by performing solvent recovery completely. In particular, in recent years, the problem of environmental destruction has attracted attention, and the tendency to avoid the use of organic solvents that may cause environmental pollution is becoming stronger.

On the other hand, there is a polyethylene terephthalate film as a film which can form a film by the melt extrusion method without using such an organic solvent, and it is beginning to be used in part as a base film of a photosensitive material.

However, the polyethylene terephthalate film has a problem that curling (cold property) occurs and it is difficult to remove it. That is, the base film of a photosensitive material is stored in the form wound once on a roll, and the film is taken out from this, cut | disconnected to an appropriate size, and it is a flat sheet-like film, such as an X-ray film, a film for making, and a cut film. Used. Moreover, in the case of a roll film, the negative film accommodated in the partrone in roll shape is cut | disconnected to a fixed length after photography | photography, image development, and fixing, and put into a film album, and is preserve | saved in a sheet form. By the way, in the case of a polyethylene terephthalate film, the curl which generate | occur | produced when winding up in roll shape remains and there exists a problem of being curled even after cut | disconnecting to a sheet form.

Proposals are proposed to improve the curling properties by facilitating the elimination of curls generated or to improve the curling properties by reducing the curling properties so as not to curl.

Japanese Unexamined Patent Publication No. 50-16783 discloses a secondary stretched laminated polyester film formed of two polyester layers each having an intrinsic viscosity in a range of 0.35 to 1.0 and a difference in intrinsic viscosity of both in a range of 0.02 to 0.5. Is disclosed.

This laminated polyester film is intended to cause curl by a difference in shrinkage stress between the entire surface layer and the opposite surface layer, and to eliminate curl by winding the film in the opposite direction to the curl.

In Japanese Unexamined Patent Publication No. 50-81325, the ratio of the Young's modulus in the horizontal and horizontal ranges from 0.9 to 1.1, and the saturation shrinkage rate or the saturation expansion rate at 180 ° C is 0.9% or less, and the saturation shrinkage rate or the saturation expansion rate at 200 ° C or less. A photographic film is disclosed which describes a biaxially stretched polyethylene-2,6-naphthalenedicarboxylate film having a vertical and horizontal difference of 0.4% or less and a haze of 4.5% or less.

Japanese Patent Application Laid-Open No. 50-95374 discloses a method for producing a polyester film, which is biaxially stretched, heat fixed, and then heat aged at a temperature in the range of 40 ° C to 130 ° C. In the examples, polyethylene-2,6 having a thickness of 12 µm, which was biaxially stretched 4.3 times in the longitudinal direction and 3.5 times in the transverse direction, was thermally fixed at 200 ° C, and then aged at a temperature in the range of 40 to 130 ° C for 24 hours. -Naphthalenedicarboxylate films are disclosed.

Japanese Patent Application Laid-Open No. 50-109715 discloses that at least the base film has at least 0.40 intrinsic viscosity (35 ° C. in o-chlorophenol) and 90 mol% or more of ethylene-2,6-naphthalenedicarboxylate of all structural units. It is formed of a polyester containing and a photographic film is disclosed, wherein the film has a haze of not more than 5% and is biaxially oriented and heat fixed.

U.S. Patent No. 4,141,735 discloses a self-supporting film formed of a thermoplastic polymer having a thickness of about 5 to 50 mm and a Tg measured by DSC at a heating rate of 20 K / min. A method of reducing the core set curl property of a film without shrinking or shrinking is disclosed. This method is sealed by holding at about 0.1 ° C. to about 1,500 hours at 30 ° C. to a temperature of Tg of the polymer and a relative humidity of 100% or less until the core set curl property of the film is reduced by at least 15%.

This decrease in core-set curling properties is due to the change in the number of ANSI curl units when the heat-treated film passes through the core-set for 24 hours at 49 ° C. and 50% RH on a core having an outer diameter of 3. It is measured compared with the change in the number of ANSI curl units when a corresponding film is core-set in the same way.

In Table 7 of Example 10 of the specification, the heat treatment temperature of the poly (ethylene-2,6-naphthalenedicarboxylate) film having a Tg of 198 ° C and the ANSI curl value of the net in core set curl properties are shown. The ANSI curl values of the nets at the treatment temperatures of 60 ° C, 71 ° C, 100 ° C, 120 ° C, 149 ° C, and 180 ° C were 18, 16, 13, 16, 20, and 25, respectively.

Japanese Laid-Open Patent Publication No. 56-53745 discloses a laminate formed by two kinds of polyester layers in which each intrinsic viscosity is in the range of 0.35 to 1.0 and the intrinsic viscosity difference of both is in the range of 0.02 to 1.0, and is stretched, heat-set, and curled. The film which makes a polyester film a base film, apply | coates a photosensitive layer to the layer side with low intrinsic viscosity of this base film, and cancels the curl of a base film by shrinkage | contraction of this photosensitive layer is disclosed.

Japanese Patent Application Laid-Open No. 1-244446 discloses a photosensitive photosensitive material having a polyester base film having a haze of 3% or less and a water content of 0.5% by weight or more and at least one photosensitive layer. The characteristic of this photosensitive material is that the base film has a water content of 0.5% by weight or more, and in order to obtain this water content, an aromatic dicarboxylic acid component having a metal sulfonate is copolymerized.

[Initiation of invention]

An object of the present invention is to provide a base film for photographic film.

Another object of the present invention is to provide a base film for a photographic film which is excellent in anti-curling property, that is, winding property or resistance to formation of curls.

Still another object of the present invention is to provide a photo base film made of polyethylene-2,6-naphthalenedicarboxylate.

Still another object of the present invention is to provide a base film for photography that is excellent in curling property as well as anti-curling property, that is, the curling generated by the winding property is easily performed.

Still another object of the present invention is to provide a base film for photography excellent in peeling resistance and damage resistance.

Still another object of the present invention is to provide a photographic base film having excellent flatness and low thickness unevenness.

Still another object of the present invention is to provide a photographic base film with less dust generation during cutting or drilling.

Still another object of the present invention is to provide a roll film in which a photo base film of the present invention having all the above-described performances is wound in a state without blocking, and thus the film is easily taken out.

Another object of the present invention is to provide a base film for photographic film having an extremely thin surface layer containing inert fine particles and having all the above-described performances.

Still other objects and advantages of the present invention will become apparent from the following description. According to the present invention, the above objects and advantages of the present invention are as follows: (a) the refractive index (nz) in the thickness direction is 1.498 or more, (b) the haze value is 2.0% or less, and (c) the tensile point at 0.05 Hz. Tan δ at 80 ° C. due to elasticity has one direction of 0.09 or less, (d) anti-culling ratio at 70 ° C. is 45% or more, (e) thickness is in the range of 40 to 120 μm, and (f ) A base film for a photographic film, characterized in that it is produced using polyethylene-2,6-naphthalenedicarboxylate as a substantial material.

[Brief Description of Drawings]

FIG. 1: is a perspective view of the film winding roll for typically showing the roughening process which generate | occur | produced in the film winding roll.

2 is a partially enlarged perspective view schematically showing a state of a wound on the film surface. (a), (b) and (c) show the state of another wound.

Best Mode for Carrying Out the Invention

The base film for photographic films of this invention is specified by the structural requirements of (a)-(f) as mentioned above.

First, the base film is substantially produced from polyethylene-2,6-naphthalenedicarboxylate as specified in requirement (f). As polyethylene-2,6-naphthalenedicarboxylate, 97 mol% or more of a homopolymer or a totally overlapped unit using ethylene-2,6-naphthalenedicarboxylate as the total overlapping unit is ethylene-2,6-naphthalenedicar Copolymers which are carboxylates are suitably used.

Examples of the compound having two ester-forming functional groups in the molecule as the third component constituting the copolymer include oxalic acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, 2,7-naphthalenedicarboxylic acid, diphenyl ether dica Dicarboxylic acids such as carboxylic acid: hydroxycarboxylic acids such as p-hydroxybenzoic acid, p-hydroxyethoxybenzoic acid and the like: and propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol And dihydric alcohols such as diethylene glycol and the like.

The polyethylene-2,6-naphthalenedicarboxylate may be a polymer in which some or all of the terminal hydroxyl groups and / or carboxyl groups are blocked by a monofunctional compound such as benzoic acid or methoxypolyalkylene glycol. Or may be modified with an ester-forming compound having three or more functional groups such as, for example, extremely small amounts of glycerin, pentaerythritol, etc. within a range where a substantially linear polymer is obtained.

As polyethylene-2,6-naphthalenedicarboxylate, the homopolymer whose whole-lap unit is substantially ethylene-2,6-naphthalenedicarboxylate is preferable.

Such polyethylene-2,6-naphthalenedicarboxylate may contain additives such as stabilizers, ultraviolet absorbers, colorants, flame retardants and the like.

The base film for photographic films of this invention can contain a small amount of inert fine particles, in order to provide activity to a film.

Such inert fine particles can be contained in a polyethylene-2,6-naphthalenedicarboxylate material. Examples thereof include inorganic particles such as silica spherical particles, calcium carbonate, alumina and zeolite, and organic particles such as silicone resin particles and crosslinked polystyrene particles. When the inert fine particles are inorganic particles, synthetic inorganic particles are preferable, and the crystal form may be any.

Of these, silica spherical particles are one of the preferred inert fine particles. Each of these silica spherical particles has a particle shape close to a true sphere, and the particle size ratio (maximum diameter / minimum diameter) is preferably 1.0 to 1.2, more preferably 1.0 to 1.1, and more preferably 1.0 to 1.05. will be.

In addition, this silica spherical particle exists in a monodisperse state, and does not mean spherical particle as a primary particle which forms aggregate particle, for example. If this sphericity ratio is large, voids are likely to occur around the particles, and the generated voids are relatively large to increase the haze, which is not preferable.

Moreover, silicone resin particle and crosslinked polystyrene particle are another preferable inert particle.

As silicone resin particles, the organic polysiloxane particles formed is at least 80% by weight of the structural unit to the structural unit represented by SiO _3/2 and CH ₃ are preferred. This structural unit CH ₃ ㆍ SiO _3/2 is

It is expressed as

The silicone resin particles may also be expressed as organopolysiloxanes having a three-dimensional bonding structure in which at least 80% by weight of the total structural units are represented by (CH ₃ · SiO _3/2 ) n. Herein, n represents a degree of polymerization, and 100 or more are preferable. As another component, a bifunctional organopolysiloxane or another trifunctional organosiloxane derivative etc. are mentioned.

The silicone resin particles are excellent in lubricity, have a specific gravity smaller than other inert fine particles, have excellent heat resistance than other organic fine particles, are insoluble in organic solvents, and have inexpensive properties. In addition, the silicone resin particles exhibit excellent affinity for polyethylene-2,6-naphthalenedicarboxylate. It is preferable that the silicone resin particles further have a volume shape coefficient of 0.20 to pi / 6. If it has this characteristic, the biaxially stretched film which is more excellent in an activity will be obtained, and the transparency of a film will improve significantly because of the favorable affinity with respect to polystyrene-2, 6- naphthalenedi carboxylate of silicone resin particle.

In addition, as crosslinked polyethylene particles, those having a spherical shape and a narrow particle size distribution are preferable. About the shape, it is preferable that the particle size ratio defined by the ratio of the maximum diameter to the minimum diameter is in the range of 1.0 to 1.2, more preferably in the range of 1.0 to 1.15, particularly in the range of 1.0 to 1.12.

The crosslinked polystyrene particles are not limited by the preparation thereof. For example, the spherical cross-linked polystyrene particles are unsaturated nitrile monomers such as conjugated diene monomers of butadiene, and methylmethacryl, in addition to styrene derivative monomers such as styrene monomer, methistylene monomer, α-methistylene monomer, dichloro styrene monomer, and the like. Monomers such as methacrylate esters such as acrylates, functional monomers such as unsaturated carboxylic acids, monomers having hydroxyl groups such as hydroxyethyl methacrylate, monomers having epoxy groups such as glycidyl methacrylate and unsaturated sulfonic acids As a crosslinking agent for having one or two or more monomers selected from the like and the polymer particles having a three-dimensional structure, polyfunctional vinyl compounds such as divinylbenzene, ethylene glycol dimethacrylate, trimetholpropane tri Water-soluble polymer protects acrylate and diaryl phthalate By emulsion polymerization from among the dissolved aqueous medium as a Lloyd prepared an emulsion of polymer particles, from the emulsion and dried to recover the polymer particles and release them to the next jet mill, followed by classification can be obtained.

It is preferable that the average particle diameter of such inert microparticles | fine-particles exists in the range of 0.05-1.5 micrometers. In particular, when the inert fine particles are inorganic particles, the average particle size is more preferably in the range of 0.1 to 0.8 mu m, and particularly preferably in the range of 0.2 to 0.5 mu m. When the inert fine particles are silicone resin particles, the average particle size is preferably in the range of 0.1 to 1.5 µm, and particularly preferably in the range of 0.2 to 1.3 µm.

Moreover, when inert microparticles | fine-particles are crosslinked polystyrene particle, it is more preferable that average particle diameter exists in the range of 0.1-1 micrometer.

If the average particle diameter of the inert fine particles is smaller than 0.05 µm, the effect of improving the activity, abrasion resistance, or winding property of the film is less. On the other hand, if the average particle diameter is larger than 1.5 µm, the transparency of the film is lowered, which is not preferable.

The particle size distribution of the inert fine particles is preferably 0.5 or less, more preferably 0.3 or less, particularly 0.12 or less.

Here, Di is the area circle equivalent diameter (micrometer) of an individual particle, Da is the average value of the area circle equivalent diameter,

n is the number of particles measured.

When inert fine particles having a relative standard deviation of 0.5 or less are used, the particles are spherical and the particle size distribution is extremely steep, so that the height of the film surface projections is extremely uniform. Further, the individual projections formed on the surface of the film are extremely sharp in the shape of projections, and the activity of the film becomes extremely good.

The content of the inert fine particles is preferably 0.001 to 0.2% by weight. When the inert fine particles are inorganic particles, the content is preferably 0.001 to 0.1% by weight, more preferably 0.002 to 0.007% by weight, particularly 0.003 to 0.005% by weight.

In addition, when the inert fine particles are silicone resin particles, the content is preferably 0.001 to 0.1% by weight, more preferably 0.002 to 0.02% by weight, particularly 0.003 to 0.01% by weight. In addition, when the inert fine particles are crosslinked polystyrene particles, the content thereof is preferably 0.002 to 0.1% by weight, particularly preferably 0.003 to 0.05% by weight. When the content of the inert fine particles is less than 0.001% by weight, the activity of the film is likely to be insufficient. When the content of the inert fine particles exceeds 0.2% by weight, the film haze increases and the transparency is insufficient, which is not preferable.

The addition time of the inert fine particles is not particularly limited as long as it is a step up to film formation of polyethylene-2,6-naphthalenedicarboxylate, and may be, for example, a polymerization step or a step before film formation.

The refractive index nz of the thickness direction of the base film for photographic films of this invention is 1.498 or more (requirement (a)). If the refractive index nz is less than 1.498, the film is likely to be peeled off, the scratch due to scratching is likely to be a wound having irregularities, and the peeling part or the damaged part becomes visible in white, which is inappropriate.

Here, the refractive index nz of the thickness direction of a film is the value calculated | required with respect to the Na-D line | wire in 25 degreeC with the Upb refractometer, It is the value which measured about both surfaces of a film, and took the average.

In order to increase the refractive index nz, the operation ratio of the film may be lowered and the heat fixing temperature may be increased. However, if the draw ratio is too low or the heat setting temperature is too high, the thickness unevenness of the film becomes large, and wrinkles (pull roots) are generated on the film surface.

The refractive index nz is preferably 1.510 or less.

Moreover, haze value of the base film for photographic films of this invention is 2.0% or less (requirement (b)). The haze value is preferably 1.5% or less, particularly preferably 1.0% or less. If this haze is too high, transparency of a film will fall and it is unpreferable.

The base film for photographic films of the present invention further has one direction in which tan δ at 80 ° C. due to tensile viscoelasticity at 0.05 Hz is 0.09 or less (requirement (c)). The value of tan δ is less than 0.085, more preferably 0.08 or less, and still more preferably 0.06 to 0.07.

When tan δ exceeds 0.09, the film tends to have a winding property, and thus the performance is insufficient as a base film for photographic film.

Although the base film for photographic films of this invention has one of the largest characteristics which have anti-colling property, as an index which shows this directly, the anti-colling rate in 70 degreeC is 45% or more (requirement (d)). Preferred anti curling rates are at least 50%. In daily life, the maximum temperature that a photographic film can normally be exposed to is about 70 ° C. Films exhibiting such high anti-culling rates at 70 ° C. are not yet known.

Conventionally, evaluation of the winding property of a photographic film depends on how much the curling caused by the winding property is resolved through the development and drying process of a normal photographic film.

However, the base film for photographic films of the present invention is excellent in curling property that curling hardly occurs, that is, anti-culling property, and yet, curling once caused by winding property is easily eliminated.

The base film of this invention shows the outstanding anti-calculability also in 49 degreeC which is 21 degreeC lower than 70 degreeC. That is, when coreset (heat treatment) for 24 hours at 49 ° C. and 50% RH on a core having an outer diameter of 3 inches, the ANSI curl value of the net is preferably 10 or less.

The base film for photographic films of this invention exists in the range of 40-120 micrometers in thickness (requirement (e)). Preferably the thickness is 50-100 micrometers.

The base film of this invention can be advantageously manufactured by carrying out biaxial stretching of the unstretched film obtained by a conventional method, heat setting, and then annealing. The biaxial stretching treatment may be either longitudinally or laterally biaxial stretching or simultaneous biaxial stretching. In addition, the longitudinal and biaxial soft signals can be redrawn in either the vertical or horizontal direction or in both directions. As the stretching conditions, conventionally known conditions can be adopted. For example, the magnification is suitably 2.0 to 5.0 times. Thus, in the biaxially stretched film produced under normal conditions, the longitudinal tan δ value at 80 ° C. due to tensile viscoelasticity at 0.05 Hz is about 0.10. It is necessary to reduce this tan δ value to 0.09 or less. As a means of lowering the tan δ value, the film may be at a temperature higher than 150 ° C. below the heat history in the roll state and further below 10 ° C. and further below 130 ° C. below the temperature under this heat history. Ring processing is more effective and preferred. In order to prevent the winding property, it is insufficient to anneal at a temperature below the temperature at which the film is subjected to a heat history in a roll state. On the other hand, annealing at a temperature higher than 150 ° C. is not preferable because oligomers tend to precipitate on the film surface, core transfer and the like easily occur on the film surface, and are unsuitable for use of the film.

As an annealing treatment method for a biaxially stretched film, a method of heating a biaxially stretched and heat-fixed film without contacting a heating roll without being sensed once, a method of heating in a non-contact while conveying with heated air, and unwinding a film once wound The method of heating by the above method, or the method of heat-processing in a heating oven in a roll state, etc. are mentioned.

In the heat fixation after biaxial stretching, if the heat setting zone after biaxial stretching is divided into multiple stages, and the heat setting temperature is gradually lowered so as not to cause a sudden temperature change, increase in thickness uniformity or occurrence of wrinkles is observed. It is easy to raise the refractive index nz in the thickness direction to 1.498 or more without causing. Moreover, when the film is shrunk in the width direction by narrowing the width of the stenter rail in the heat setting zone at the highest temperature, this effect becomes more remarkable.

For example, the heat setting zone after biaxial stretching is divided into three or more zones, preferably four or more zones, and setting the temperature of the final zone of this heat setting zone to 140 degrees C or less, preferably 120 degrees C or less. desirable.

It is preferable that the temperature is gradually lowered so as not to give a sudden temperature change during the period from the highest heat setting temperature zone to the final zone.

The temperature gradient between each zone at this time is 70 degrees C or less, Preferably it is 60 degrees C or less.

The base film of this invention can be equipped with the following preferable property as a base film for photographic films.

The adhesion between the films / films of the base film of the present invention is preferably class 3 or less, more preferably class 2.5 or less, particularly preferably class 2 or less. The larger the grade of the adhesiveness, the worse the slipperiness of the film, while the smaller the grade, the tendency of slipping between films. When this adhesiveness is greater than 3 grades, the slipping between films is bad, the occurrence of blocking between films, the occurrence of scratches due to the conveyance roll during film running, and the like on the rolls at the time of roll hoisting, for the photo film, etc. It is not preferred for use as.

The flatness of the base film of the present invention is preferably 250 cm / m or less in width. If the flatness of the film exceeds 250 cm / m width, the uniform coating of the photosensitive emulsion becomes difficult and unsuitable. The flatness is particularly preferably not more than 200 cm / m wide.

As the base film of the present invention, when the thermal analysis is performed, an endothermic peak is preferably observed within a temperature range of 120 to 160 ° C, preferably within a temperature range of 130 to 150 ° C. The endothermic energy represented by the total area of the endothermic peak is preferably 0.3 mJ / mg or more, more preferably 0.5 mJ / mg or more. When the endothermic peak is in the temperature range and has the energy, the base film of the present invention exhibits sufficiently good anti-culling property.

In one direction, the base film of the present invention has a heat shrinkage in the range of 3% or less, more preferably 2% or less, and particularly preferably 1.5% or less by dry heat treatment at 150 ° C. for 30 minutes. Indicates.

The base film of the present invention preferably allows a thickness nonuniformity of 5 μm or less, more preferably 4 μm or less. When the thickness nonuniformity exceeds 5 micrometers, it becomes difficult to apply | coat a photosensitive emulsion uniformly to a film surface, and can also reduce the quality of a photographic film.

In order to reduce thickness nonuniformity, extending | stretching magnification is made high and heat setting temperature, longitudinal stretch temperature, and lateral stretch temperature are made low.

Moreover, it is preferable that the Young's modulus of the orthogonal | vertical 2 direction is 750 kg / mm <2> or less, and, as for the base film of this invention, it is more preferable that it is 700 kg / mm <2> or less.

If this Young's modulus exceeds 750 kg / mm <2>, a lot of dust will generate | occur | produce easily at the time of cutting of a film or perforation of perforation. The lower limit of the Young's modulus in the longitudinal direction and the transverse direction is preferably 400 kg / mm 2, more preferably 450 kg / mm 2.

The difference in Young's modulus in both directions is not particularly limited, but is preferably 150 kg / mm 2 or less.

As described above, the base film of the present invention basically has anti-culling property, transparency, and activity. According to a study before the present invention, a base film having only improved activity without impairing its curling property and transparency can be provided. It became obvious.

That is, according to the present invention, the first layer formed of polyethylene-2,6-naphthalenedicarboxylate may contain less than 0.003% by weight of inert fine particles having an average particle size of 0.01 ~ 1.5㎛, and the average particle size 0.01 Provided is a base film for a photographic film formed of a lamination agent with a second layer having a thickness of 10 μm or less and formed of polyethylene-2,6-naphthalenedicarboxylate containing 0.003 to 0.5% by weight of inert fine particles of ˜1.5 μm. do.

This base film for photographic film (hereinafter referred to as the second base film of the present invention) is similar to the electrical base film of the present invention in accordance with the electrical requirements (a), (b), (c), (d) and (e). Meets all.

As mentioned above, the 2nd base film of this invention is formed from the laminated | multilayer film of the 1st layer and 2nd layer from which content of inert fine particle differs. The second layer, which has a large amount of inert fine particles and is extremely thin, is laminated only on one side of the first layer or on both sides of the first layer.

The first layer may contain inert fine particles having an average particle diameter of 0.01 to 1.5 µm. However, the first layer is less than 0.003% by weight, preferably 0.001% by weight or less.

Regarding the inert fine particles having an average particle diameter of 0.01 to 1.5 μm, //// description of a portion not specifically described herein is understood that the technique relating to the inert fine particles for the base film of the present invention described first is applied as it is. do.

The content of the inert fine particles in the first layer is less than 0.003% by weight. Since the thickness of the 2nd base film of this invention is 50-120 micrometers (requirement (e)), and the thickness of a 2nd layer is up to 10 micrometers as mentioned above, the thickness of a 1st layer is compared with the thickness of a 2nd layer. You can see it's very big. That is, the thickness of the 1st layer which touches the thickness of the whole base film is enlarged by increasing the thickness of the 1st layer which is very small even if it does not contain or contains inert microparticles | fine-particles, and advantageously ensures transparency of a base film. .

The second layer contains 0.003-0.5% by weight of inert fine particles having an average particle diameter of 0.01-1.5 µm.

The inert fine particles of the second layer may also be understood like the inert fine particles of the first layer.

The content of the inert fine particles in the second layer is preferably 0.005 to 0.3% by weight, more preferably 0.01 to 0.1% by weight. If the content of the inert fine particles is less than 0.003% by weight, the activity of the film is deteriorated, and filming easily occurs. On the other hand, if the content of the inert fine particles is more than 0.5% by weight, the damage resistance and transparency of the film are poor, which is not preferable.

The ratio (t ₂ / d ₂ ) of the second layer thickness t ₂ (μm) and the average particle diameter d ₂ (μm) of the inert fine particles contained in the B layer is preferably 0.1 to 10, more preferably 0.2 to 5 More preferably, it exists in the range of 0.3-3.

If the ratio (t ₂ / d ₂ ) is less than 0.1, the inert fine particles of the film surface layer portion are easily desorbed from the film surface during film running, and the activity of the film is bad. I can't.

The second layer serves as an important function to impart activity to the second base film of the present invention.

The thickness of the second layer (the thickness of each of the second layers when the second layer is on both sides of the first layer) is 10 µm or less, preferably 5 µm or less. It is preferable that the minimum of thickness shall be 0.1 micrometer.

Biaxially oriented laminated film for the second base film of the present invention, the polyethylene-2,6-naphthalenedicarboxylate constituting each of the first layer and the second layer or a composition containing the same by separately melting die Coextruded from, and laminated and fused before solidification to produce an unstretched film, which is then biaxially stretched and heat set, or separately melted and extruded to form each polymer or composition, and in unstretched state or After extending | stretching, it can manufacture by the method of laminating and fusing both. Next, the second base film of the present invention can be obtained by annealing the obtained biaxially oriented laminated film in the same manner as in the annealing treatment described above.

And the part which does not have description about the 2nd base film of this invention is understood that the corresponding description about the base film of this invention mentioned above is applied as it is.

According to the present invention, the roll of the base film for photographic film, in which the base film (including the second base film of the present invention) of the present invention is wound and held without blocking, is similarly provided.

That is, as for the roll of the base film for photographic films of this invention, a roll film is a base film of this invention, and an air layer of 7-20 volume% exists between roll film layers.

The winding roll of this invention is wound up so that the film layer may be 7-20 volume%, Preferably it is 8-19 volume%, More preferably, the air layer of 10-18 volume% is interposed. If this air layer is less than 7 volume%, the winding roll is unpreferable because of the winding by an annealing process and the above-mentioned microscratches generate | occur | produce. On the other hand, when the air layer exceeds 20% by volume, these problems do not occur, but the shape of the roll roll becomes unstable, resulting in uneven roll cross section during roll winding, roll deformation during roll conveying, and the like, which is not preferable.

Wound roll WHEREIN: As a method of adjusting the air volume between film layers in the above-mentioned range, when winding up a film in roll shape, it winds up winding the narrow film in the vicinity of the both edges of a roll, or length to the film of the roll edge vicinity beforehand. Although the method of making an unevenness | corrugation (for example, embossing etc.) in a direction, etc. is mentioned, It does not limit about this method.

The photo film can be obtained by forming various thin layers, including a photosensitive emulsion layer, on the surface of the base film of this invention. Well-known means can be used for formation of these thin layers.

EXAMPLE

Next, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

In the Examples and Comparative Examples, tan δ, the refractive index nz in the thickness direction, the anti-colling rate, the fold peeling whitening rate, and the like were measured as follows.

(1) refractive index in the thickness direction (nz)

The refractive index of the film thickness direction is calculated | required using an UPBE refractometer (made by AGO AG Co., Ltd.), and using a Na-D line | wire at 25 degreeC. It measures about both front and back of a film sample, and makes the average value into refractive index (nz).

(2) haze

The total haze value per film measured by the commercially available haze meter by the method of JIS K-6714.

(3) tan δ

Seiko Electronic Industry Co., Ltd. product

Use the thermal stress distortion measuring device TMA / SS 120C and measure under the following conditions.

Load mode: sin wave (load change frequency: 0.05 Hz)

Median load per cross section: 120 g / ㎡

Load amplitude per cross section: 90 g / ㎡

Temperature rise rate: 5 ℃ / min

Sample Width: 4mm

Sample length (interline distance): 10 mm

Measuring direction: Longitudinal direction

(4) anti-culling rate

The sample film having a size of 120 mm x 35 mm is wound around a core of 10 mm in diameter and fixed so as not to be unwound, heated at 70 ° C. and 30% RH for 72 hours, then freed from the core, and soaked in distilled water at 40 ° C. for 15 minutes. .

Subsequently, 50 g of the load was applied, the sample was suspended vertically, and the "sample length" (mm) with the curl remaining was measured, and the ratio (%) of the sample length to the length of 120 mm of the initial sample was determined by the anti-culling ratio. do.

In this case, the "sample length" is taken as the diameter when the sample is largely curled to form a circle or semicircle, and when the curl of the sample is small and the mold is less than the semicircle, the length of the string is taken.

The higher the curling rate, the harder curling is provided.

(5) Net ANSI Curl Value

Curl | Karl evaluation was performed by test method A (21 degreeC, 50% RH) of ANSI / ASC PH 1.29-1971. Curing was performed by winding the film around a core having an outer diameter of 3 inches and treating the film at 40 ° C. and 50% RH for 24 hours. The film at the time of curling is 4 inches x 6 inches.

Net ANSI curl value = ANSI curl value after curling the film around the core-ANSI curl value before winding the film to the core

(6) adhesion

A rubber sheet is laid on a flat object, and two films which do not contain dust, dirt, or the like are layered thereon. A cylindrical weight having an outer diameter of 70 mm and a weight of 10 kg is slightly placed on the film from directly above the film, and after 10 minutes, the weight is removed. After standing for 30 seconds, the contact shape in the circle of the circumference is photographed, the ratio of the area of the adhesive part is measured, and it is divided into 0-5 grade according to Table 1.

(7) Flatness

From the film roll, a film sample of 2 m in length is taken out, and when it is wound on the roll, it is spread out on a horizontal and flat track with the side that was the surface side of the roll up. After stopping for 10 minutes, the entire surface of the film sample is observed, the length (cm) of wrinkles (flute) remaining on this surface is measured, and the sum is divided by the width m of the film to calculate flatness.

(8) endothermic peak temperature T _k (° C.)

10 mg of film was set in a thermal analysis system SSC 580 DS (DSC) manufactured by Seiko Electronics Co., Ltd., and heated at a temperature increase rate of 20 ° C./min in N ₂ streams. The second derivative is analyzed to determine the temperature at which the peak is indicated, which is taken as the endothermic peak temperature.

(9) endothermic energy ΔH _k (mJ / mg)

As in (8), 10 mg of film was set in Seiko Electronics Co., Ltd. thermal analysis system SSC 580, SDC 20, and heated at a temperature increase rate of 20 ° C./min in N ₂ air flow to the endothermic energy of the film. Obtain the endothermic energy from the area of the endothermic side on the corresponding DSC chart.

This area is an area on the heat absorbing side formed by a line from the base line to the heat absorbing side when the temperature is raised, and after passing through the heat absorbing peak and returning to the base line position when the temperature is continued. Calculate the area (A) by connecting up to a straight line. In (indium) is measured under the same DSC measurement conditions, and this area (B) is set to 28.5 mJ / mg, and the endothermic energy is obtained from the following equation.

(10) heat shrinkage

The sample is held for 30 minutes in a hot air of 150 ° C, and the order change before and after this is obtained by the following equation.

Here, L ₀ is the distance between the marks before heat shrink and L is the distance between the marks after heat shrink.

(11) film thickness non-uniform

Continuous thickness chart with a sensitivity of ± 4 µm using an electronic micrometer K-312A type manufactured by Allitz Co., Ltd., measured over a length of 2 m in the longitudinal and transverse directions of the film at a needle pressure of 30 g and a traveling speed of 25 mm / sec. Get From this chart, the maximum value and minimum value of the thickness over 2 m are obtained, and this difference R (µm) is made thickness nonuniform.

(12) Young's modulus

The film is cut into a sample width of 10 mm and a length of 15 cm, and is stretched by an Instron-type universal tensile test apparatus with a tensile strength of 10 mm / minute and a chart speed of 500 mm / minute with a distance of 100 m between chucks. The Young's modulus is calculated by the dotted line of the granular part of the obtained load-stretch curve.

(13) form of roll

A 500 mm wide and 500 m long film is wound on a roll. The appearance of this winding roll is visually inspected in detail, and the number of objects having a diameter of 1 mm or more is counted with a projection as schematically shown in FIG. 1, and classified into classes 1 to 5 as shown in Table 2. And grades 4 and 5 fail.

(14) fold peeling whitening rate

The film sample is cut into a size of 80 mm x 80 mm, and a pair of flat metal plates are sandwiched by light hand-folding in two, and then pressed at a predetermined pressure P (kg / cm 2 G) for 20 seconds by a press. After pressing, the double-folded film is returned to its original state by hand, pressed onto an electrometallic plate, and pressed for 20 seconds at a pressure P (kg / cm 2 G). Thereafter, the sample film is taken out, and the length (mm) of the whitening portion shown in the folded portion is measured and summed.

Each measurement is repeated for each press film P = 1,2,3,4,5,6 (kg / cm 2 G) using a new film sample.

The ratio of the average length band total length (80 mm) of the sum total of the length (mm) of the whitening part in each press pressure is made into the folding part peeling whitening rate, and this value is an index which shows the ease of layer peeling of a film. use.

(15) Dust generation state

The perforated part of the film which perforated the perforation by the perforator is contacted with the adhesive tape (Nitto protective film SPV-363, manufactured by Nitto Odenko Co., Ltd.) which attached the adhesive surface outside to the metal roll of diameter 10cm. After driving at 100 m / min at a speed of 10 m / min, the amount of dust adhering to the adhesive tape is visually observed and graded as follows.

◎: No adhesion of dust at all.

(Circle): The adhesion of dust hardly appears.

(Triangle | delta): Some dust adhesion appears.

X: A large amount of dust adhered.

(16) Blocking after annealing treatment

The film of 500 mm in width and 500 m in length is wound up on a roll, and this roll is annealed at 110 degreeC for 24 hours. The roll surface after annealing is cut about 400m and observed with or without blocking of the core part.

The determination is made based on the following criteria.

(Circle): There is no blocking and a roll surface is flat.

(Triangle | delta): Although the particulate-like blocking was 3-5 places or less, the other part is flat.

X: There are 6 or more places of fine particle blocking, or 1 or more places of blocking of 10 mm <2> or more.

(17) damage resistance

Using a Haydon-14 type scratch tester (manufactured by Shinto Chemical Co., Ltd.), a diamond needle having a tip radius of 50 µm was used as a scratch needle, and the film surface was lengthened at a needle load of 200 g and a traveling speed of 2 mm / sec. Scrape about 100 mm in the direction.

The part of the scratched wound is observed under a transmission microscope of 100 times, and the rank is given by the state as shown in Table 3 below.

Ranks A and B are acceptable in practical use.

(18) proportion of air layer

The film of a certain length is wound in a roll form, and the roll diameter D is measured. On the other hand, the roll diameter D (the air layer is not interposed) is calculated from the film thickness and the length, and the ratio of the air layer is obtained from the following equation using the calculated value and the measured value.

(19) Average particle diameter

It is measured using a Shimadzu Corporation CP-50 type centrifugal particle size analyzer. From the cumulative curves between the particles of each particle size calculated on the basis of the obtained settling curve and the amount of abundance, the particle size corresponding to 50 mass parcents is read out, and this value is referred to as the above average particle size. Measurement technology, published by Nippon Industrial Newspaper, 1975, pp. 242--247).

(20) Volumetric shape factor (f)

The photograph of the lubricant particles was magnified 5000 times by scanning electron microscope to capture 10 fields of view, and the average value of the maximum diameter was calculated for each field of view using the image analysis processing device Ruzex 500 (manufactured by Nippon Regulator). The average value is obtained and referred to as D.

The volume of the particles is calculated by V = (π / 6) d ³ using the average particle diameter d of the particles obtained in the above (19), and the shape coefficient f is calculated by the following equation.

In the formula, V represents the volume of the particles (µm ³ ), and D represents the maximum diameter of the particles (µm).

(21) Expenses

The film fragments are fixed-molded with epoxy resin, and ultra-thin sections (cut parallel to the flow direction of the film) of about 600 Angstroms in thickness are prepared.

The cross-sectional shape of the lubricant in the sample film was observed with a transmission electron microscope (Hitachi Co., Ltd. H-800 type), and is represented by the ratio of the maximum diameter of the particle to the maximum diameter.

(22) Average particle size, particle size ratio

The powder is scattered on the electron microscope sample table so that the individual particles do not overlap as much as possible. A gold thin film deposition layer is formed on the surface by a gold sputtering device to a thickness of 200 to 300 angstroms, and the scanning electron microscope is 10,000 to 30,000. Magnification and observation were carried out to find the maximum diameter (Dli), minimum diameter (Dsi) and area circle equivalent (Di) of at least 100 particles using Nippon Regulator Co., Ltd. Luxex 500. And as a number average value shown by following Formula, the largest diameter Dl, the minimum diameter Ds, and the average particle diameter Da are shown. Furthermore, the particle size ratio is calculated | required from these.

Moreover, about the particle | grains in a film, it calculates as follows.

The sample film piece was fixed to the sample stand for scanning electron microscope, and ion-etching process was performed to the film surface on the film surface using the sputtering apparatus (JFC-1100 type ion etching apparatus) by Nippon Electronics Co., Ltd. under the following conditions. A sample is placed in the bell jar, the vacuum degree is increased to a vacuum of about 10 ^-3 Torr, and ion etching is performed for about 10 minutes at a voltage of 0.25 KV and a current of 12.5 mA. In addition, a metal putter was applied to the surface of the film by the same apparatus, and observed with a scanning electron microscope at 10,000 to 30,000 times, and the maximum diameter (Dli) of at least 100 particles was determined by Nippon Regulator Co., Ltd. Find the minimum diameter (Dsi) and area circle equivalent diameter (Di). Hereinafter, it is performed as mentioned above.

[Examples 1-4 and Comparative Examples 1-3]

Polyethylene-2,6-naphthalenedicarboxylate having an intrinsic viscosity of 0.60 containing the inert fine particles shown in Table 4 was melt-extruded from the dieslet and cooled and solidified on a casting drum to prepare an unstretched film.

The unstretched film was stretched 3.0 times in the longitudinal direction at a temperature of 130 ° C., and subsequently stretched 3.3 times in the transverse direction at a temperature of 135 ° C. while holding both ends in the width direction of the film with a stenter clip, and further under tension. After heat-fixing at 230 degreeC, holding | gripping was continued, it quenched by contacting a quench roll in tension state, and the biaxially oriented film was wound up to the roll.

The film of 500 mm in width and 500 m in length was sampled from the obtained biaxially-oriented film, it was wound up to the core of 165 mm in diameter, the sample roll was produced, and the annealing process was performed on the conditions shown in Table 4 in this state.

Physical properties of the biaxially oriented film subjected to the annealing treatment are shown in Table 4.

The biaxially oriented films of Examples 1 to 4 were subjected to annealing treatment so as to have a predetermined tan δ value, and satisfied properties required as photographic film materials.

On the other hand, Comparative Example 1 is an example in which no annealing treatment is performed, and sufficient curl recovery property cannot be obtained. Moreover, the comparative example 2 is an example in which the annealing process temperature is too high and a desired tan-delta value is not obtained and sufficient curl recovery property is not obtained as a result.

Comparative Example 3 shows an example in which a sufficient amount of lubricant is not obtained to obtain sufficient transparency.

[Examples 5 and 6 and Comparative Examples 4 and 5]

In Examples 1-4, it carried out similarly to Examples 1-4 except having used the polyethylene-2,6-naphthalenedicarboxylate which contains microparticles | fine-particles shown in Table 5, and whose intrinsic viscosity is 0.60. The ring-treated biaxially stretched film is obtained.

Table 5 shows the properties of the obtained biaxially oriented film.

[Examples 7 to 10 and Comparative Examples 6 and 7]

Polyethylene-2,6-naphthalenedicarboxylate having an intrinsic viscosity of 0.60 was melt-extruded from the dieslet by a conventional method, and cooled and solidified on a casting drum to prepare an unstretched film.

This unoriented film is biaxially stretched and heat-fixed according to the conditions shown in Table 6, and further subjected to annealing under the conditions shown in Table 6 to obtain a biaxially oriented film having a thickness of 75 µm.

And heat setting is performed using the apparatus which divided the heat setting zone into the zone of X, X, X, X, and in the zone (X) which corresponds to the highest heat setting temperature, the width | variety of a film is narrowed by narrowing the width of a stent rail. The shrinkage can be given in the direction.

In addition, the annealing treatment cools the film after biaxial stretching and heat fixation in contact with a cooling roll in a tension state, takes out a film having a width of 500 mm and a length of 500 m from the wound film roll, and wound around a core of about 165 mm in diameter. It wound up on the roll and performed by heating the wound film in a heating oven.

A condition: It heated up to 100 degreeC over 24 hours, hold | maintained for 24 hours, and then cooled down to room temperature over 24 hours.

B condition: It heated up to 90 degreeC over 24 hours, hold | maintained for 24 hours, and then cooled down to room temperature over 24 hours.

About each obtained biaxially oriented film, tan (delta), the refractive index (nz) of a thickness direction, an anti-colling rate, a fold part peeling whitening rate, etc. were measured.

The results were as shown in Table 7.

[Examples 11 to 14 and Comparative Example 8]

Polyethylene-2,6-naphthalenedicarboxylate having an intrinsic viscosity of 0.60 was melt-extruded from the dieslet by a conventional method, and cooled and solidified on a casting drum to prepare an unstretched film.

The unstretched film is biaxially stretched and tension heat-set according to the conditions shown in Table 8, and further subjected to annealing under the conditions shown in Table 8 to obtain a biaxially oriented film having a thickness of 75 µm.

And the annealing process cools the film after biaxial stretching and heat fixation in contact with a quench roll in a tension state, takes out a film 500 mm in width and 500 m in length from the wound film roll, and has a diameter of about 165 mm. It wound up to the core in roll shape and performed by heating in the heating oven.

The meaning of the annealing conditions in Table 8 is as Table 6.

As a result of measuring tan δ (80 ° C.), flatness, anti-culling ratio and the like in the longitudinal direction due to tensile viscoelasticity at 0.05 Hz of the obtained annealing treated biaxially oriented film, it was as shown in Table 9.

[Examples 15-18 and Comparative Example 9]

Polyethylene-2,6-naphthalenedicarboxylate having an intrinsic viscosity of 0.60 was melt-extruded from the dieslet by a conventional method, and cooled and solidified on a casting drum to prepare an unstretched film.

The unstretched film is biaxially stretched and tension heat-set according to the conditions shown in Table 10, and annealing is performed under the conditions shown in Table 10 to obtain a biaxially oriented film having a thickness of 75 µm.

And the annealing process cools the film after biaxial stretching and heat fixation in contact with a quench roll in a tension state, takes out a film 500 mm in width and 500 m in length from the wound film roll, and winds about 165 mm in diameter. Winding was carried out on a shim roll, and heating was performed in a heating oven.

The meaning of the annealing conditions in Table 10 is as Table 6.

The results of measurement of tan δ (80 ° C.) in the longitudinal direction, Young's modulus in the longitudinal and transverse directions, anti-culling ratio, dust generation state and the like due to tensile viscoelasticity at 0.05 Hz of the obtained biaxially oriented film are shown in Table 11. It was like

Example 19 and Comparative Example 10

Polyethylene-2,6-naphthalenedicarboxylate having an intrinsic viscosity of 0.60 was melt-extruded from the dieslet by a conventional method, and cooled and solidified on a casting drum to prepare an unstretched film.

This unstretched film is biaxially stretched and tension heat-set according to the conditions shown in Table 12, and annealing is performed under the conditions shown in Table 12 to obtain a biaxially oriented film having a thickness of 75 µm.

And the annealing process is performed similarly to Examples 15-18.

The properties of the obtained film are shown in Table 12.

[Examples 20-23 and Comparative Examples 11-14]

In Examples 1-4, it carried out similarly to Examples 1-4 except having used the inert microparticles shown in Table 13, and using the polyethylene-2,6-naphthalenedicarboxylate of intrinsic viscosity 0.60. The ring-treated biaxially oriented film is obtained.

Table 13 shows the properties of the obtained biaxially oriented film.

Examples 24-27 and Comparative Examples 15-17

Examples 1-4 were repeated. The polyethylene-2,6-naphthalenedicarboxylate having an intrinsic viscosity of 0.60 containing inert fine particles shown in Table 14 was used and was carried out similarly to Examples 1 to 4 to obtain an annealing treated biaxially oriented film.

Table 14 shows the properties of the obtained biaxially oriented film.

It can be seen that Examples 24 to 26 and Comparative Example 15 reproduce Examples 1 to 4 and Comparative Example 1, respectively. Moreover, it turns out that the annealing film of these Examples has Tk (degreeC) and (DELTA) Hk (mJ / mg) of a preferable value.

[Examples 28-31 and Comparative Example 18]

Polyethylene-2,6-naphthalenedicarboxylate (high intrinsic viscosity 0.60) added with spherical silica fine particles having a particle size ratio of 1.07 and an average particle diameter of 0.3 μm to the contents shown in Table 15 was melt-extruded by a conventional method and not smoked. A new film was prepared.

The unstretched film is biaxially stretched and heat set under the conditions shown in Table 15 to obtain a biaxially oriented film having a thickness of 75 µm. The heat setting is performed by tn using a device in which the heat fixing zone is divided into three zones of X, X, and X, and the cooling zone CZ is set thereafter, and in the zone X having the highest heat setting temperature, By narrowing the width of the stent rail, shrinkage can be imparted to the width direction of the film.

About each biaxially oriented film obtained, refractive index (nz) of a thickness direction, damage resistance, etc. were measured. The result was as having shown in Table 16.

[Examples 32-35 and Comparative Examples 19, 20]

Polyethylene-2,6-naphthalenedicarboxylate having an intrinsic viscosity of 0.60 was melt-extruded by a conventional method to prepare an unstretched film.

The unstretched film is biaxially stretched and heat treated under the conditions shown in Table 17 to obtain a biaxially oriented film having a thickness of 75 µm. The heat treatment was performed by using a device in which the heat treatment zone was divided into four zones of X, X, X, and X. In the zone (X) having the highest heat fixed temperature, the width of the stent rail was narrowed, thereby shrinking in the width direction of the film. To be granted.

About each obtained biaxially-oriented film, the refractive index (nz) of the thickness direction, the thickness nonuniformity of the longitudinal direction and the horizontal direction, the flatness, and the fold part peeling whitening rate were measured.

The results were as shown in Table 18.

Example 36 and Comparative Example 21

Polyethylene-2,6-naphthalenedicarboxylate having an intrinsic viscosity of 0.60 containing 0.008% by weight of spherical silica (long diameter / short diameter = 1.07) having an average particle diameter of 0.3 µm was melt-extruded from a dielet and cooled and solidified on a casting drum. A new film was prepared. Subsequently, this unstretched film is stretched 3.0 times in the longitudinal direction at a temperature of 130 ° C., and subsequently stretched 3.3 times in the transverse direction at a temperature of 135 ° C., while holding the film in the width direction with a stenter clip. It heat-sets at 230 degreeC in tension state, it releases a grip, it contacts with a quench roll in tension state, it is quenched, and a 75-micrometer-thick biaxially oriented film is wound up on a roll, and a roll is obtained.

When winding the film roll of width 500mm and length 500m from the obtained one roll to the core of diameter 165mm, polyethylene-2,6- of thickness 10micrometer and width 10mm at the both edges of this film roll (500mm width). It wound up while inserting the naphthalenedicarboxylate film. This film roll was subjected to annealing under the conditions shown in Table 19.

The physical properties of the annealed biaxially oriented film and the evaluation for the photosensitive material were as shown in Table 19.

The biaxially oriented film of Example 36 was wound on a roll at a ratio of an appropriate air layer and had a predetermined haze value, a predetermined tan δ value, and the like, and as a result, the characteristics required as a photosensitive material were satisfied.

[Examples 34-41 and Comparative Examples 22-24]

Polyethylene-2,6-naphthalenedicarboxylate having an intrinsic viscosity of 0.60 containing spherical silica having an average particle diameter of 0.3 μm and a particle size ratio (maximum diameter / minimum diameter) of 1.05 in the amounts shown in Table 20, respectively, After melt | dissolving by the conventional method so that B) may be formed, it coextruded from the die | dye which adjoined mutually, laminated | stacked and fused the layer (B) on both surfaces of the layer (A), and hardened rapidly, and produced the unstretched laminated | multilayer film.

Subsequently, this unstretched film is stretched 3.0 times in the longitudinal direction at a temperature of 130 ° C., and subsequently stretched 3.3 times in the transverse direction at a temperature of 135 ° C. while holding both ends in the width direction of the film with a stenter clip. It heat-sets at 230 degreeC in tension state, and it hold | releases a grip | grip continuously, it is quenched by contacting a quench roll in tension state, and a biaxially-oriented film is obtained.

Thereafter, annealing treatment is performed under the conditions shown in Table 20 to obtain a film having a total thickness of 75 μm. And the thickness of layer (A) and layer (B) was changed as shown in Table 20, respectively.

Moreover, the annealing process was performed by taking out the film of width 500mm and the length of 500m from the film original roll which wound the biaxially oriented laminated film, winding up in roll shape, and heating in a heating oven. The properties of the obtained annealing film were listed in Table 20 together.

The meaning of the annealing conditions in Table 20 is as Table 6.

[Examples 42-44 and Comparative Examples 25-27]

A-layer and polyethylene-2,6-naphthalenedicarboxylate having an intrinsic viscosity of 0.60 each containing spherical silica having an average particle diameter shown in Table 21 and having a particle size ratio (maximum diameter / minimum diameter) of 1.05 in the amounts shown in Table 21, respectively. After melt | dissolution by the normal method so that B layer may be formed, it coextruded from the die | dye which adjoined mutually, laminated | stacked and fused the B layer on both surfaces of A layer, and solidified rapidly and produced unstretched composite film. At this time, by controlling the discharge amount of each extruder, the thickness of the A layer, B layer was adjusted.

Subsequently, the unstretched film was stretched 3.0 times in the longitudinal direction at a temperature of 130 ° C., and then laterally held at both ends in the width direction of the film with a stenter clip at a temperature of 135 ° C. in the transverse direction at the ratio shown in Table 21. It stretches and heat-sets at the temperature shown in Table 21 in a tension state, and it is continued to release | grip, and it contacts with a quench roll in tension state and quenchs, and obtains the biaxially-oriented film of 75 micrometers in total thickness. Next, the annealing treatment was performed according to the conditions A of Examples 7 to 10. And the thickness of A-layer and B-layer was changed as shown in Table 21, respectively.

The haze of the obtained film, refractive index (nz) of the thickness direction, damage resistance, etc. were measured. The results were as shown in Table 21.

Claims (19)

(a) one direction in which the refractive index nz in the thickness direction is 1.498 or more, (b) the haze value is 2.0% or less, and (c) the tan δ value at 80 ° C due to tensile viscoelasticity at 0.05 Hz is 0.09 or less. (D) anti-culling ratio in 70 degreeC is 45% or more, (e) thickness is 40-120 micrometers, (f) polyethylene-2,6-naphthalenedicarboxylate is a substantial raw material The base film for photographic films characterized by the above-mentioned. The base film of Claim 1 whose refractive index (nz) of a thickness direction is 1.510 or less. The base film of claim 1, wherein the haze value is 1.5% or less. The base film of Claim 1 whose tan delta value of 80 degreeC by tensile viscoelasticity in 0.05 Hz is less than 0.085. The base film of Claim 1 whose tan delta value of 80 degreeC by tensile viscoelasticity in 0.05 Hz is 0.08 or less. The base film of Claim 1 whose anti curling rate in 70 degreeC is 50% or more. The base film of claim 1, wherein the net ANSI curl value is 10 or less for a heat-treated film cored at 49 ° C. and 50% RH for 24 hours on a core having an outer diameter of 3 inches. The base film according to claim 1, wherein the polyethylene-2,6-naphthalenedicarboxylate contains 97 mol% or more of ethylene-2,6-naphthalenedicarboxylate units. The base film of Claim 1 whose adhesiveness between base films is 4 grade or less. The base film of claim 1, wherein the flatness is 250 cm / m wide or less. The base film according to claim 1, wherein the base film has an endothermic peak within a temperature range of 120 to 160 ° C and an endothermic energy is 0.3 m Joule / mg or more. The base film of Claim 1 which has a one-way direction whose thermal contraction rate is 3% or less when it dry-processes at 150 degreeC for 30 minutes. The base film of Claim 1 which has one direction whose thickness nonuniformity is 5 micrometers or less. The base film of Claim 1 which has the orthogonal 2 direction whose Young's modulus is 750 kg / mm <2> or less. The base film of Claim 1 containing 0.001-0.2 weight% of inert fine particles with an average particle diameter of 0.05-1.5 micrometers. The roll of the base film for photographic films whose space in which an air layer of 7-20 volume% exists exists between a roll film layer, and a roll film is a base film of Claim 1. (a) One direction in which the refractive index nz in the thickness direction is 1.498 or more, (b) the haze value is 2.0% or less, and (c) the tan δ value of 80 ° C due to tensile viscoelasticity at 0.05 Hz is 0.09 or less. (D) the anti-culling ratio at 70 ° C. is 45% or more, (e) the thickness is in the range of 40 to 120 μm, and (f) the inert fine particles having an average particle diameter of 0.01 to 1.5 μm is less than 0.003% by weight. Polyethylene-2,6-naphthalenedicarboxyl containing the first layer formed of polyethylene-2,6-naphthalenedicarboxylate which may be contained, and 0.003-0.5 weight% of inert fine particles of 0.01-1.5 micrometers of average particle diameters A base film for photographic film, which is formed at a rate and formed of a laminated film with a second layer having a thickness of 10 μm or less. The method of claim 17, wherein the base film is in a range of 0.1 to 10 ratio of the particle diameter d ₂ of the inert fine particles are contained thickness t for the second layer ₂ (㎛) of the second layer (㎛). The base film of Claim 17 whose thickness of a 2nd layer is 5 micrometers or less.