CN1054924C - Base film for photographic film - Google Patents

Abstract

A base film for photographic films, characterized by (a) having a refractive index (nz) in the thicknesswise direction of at least 1.498, (b) having a haze value of 2.0 % or less, (c) having one direction wherein a tan delta value at 80 DEG C due to the tensile viscoelasticity at 0.05 Hz is 0.09 or less, (d) having a curling resistance ratio of 70 DEG C of 45 % or above, (e) having a thickness of 40-120 mu m, and (f) substantially comprising polyethylene 2,6-naphthalene-dicarboxylate. This base film has various performances suitable as photographic films, such as curling resistance, transparency and slipperiness.

Description

The method for preparing base film for photographic film

Technical field

The invention relates to base film for photographic film, more particularly, about have curling resistance, the transparency and sliding etc., with poly-2, the 6-(ethylene naphthalate) is the base film for photographic film of raw material.

Background technology

Biaxial stretch-formed gathers 2, and 6-(ethylene naphthalate) film has favorable mechanical performance, thermal behavior and electrical property, thereby people constantly study, develop its application in every field.At present, it obtains practical application in magnetic recording media, art of electrical insulation.

One of purposes of this film is a sensitive photographic material.This technical field can roughly be divided into X ray film, reproduction film, sheet film etc. with the photosensitive material of plain film shape use and the photosensitive material that uses with the film form.Representational film be wide 35mm or 35mm following, be accommodated in the magazine, install to and be used to the colour or the black and white negative film of photographing in the typical CCD camera.

The sheet base of plain film shape film mainly is to adopt the Biaxially oriented polyester film that is made of polyethylene terephthalate, and the sheet base of film then uses by with the film of triacetyl cellulose (hereafter is TAC) for the cellulosic polymer formation of representative.

The characteristics of TAC film are that to have to eliminate crimpiness after optic anisotropy, transparency height, the development treatment not good, and particularly its good elimination performance of curling is that the film of other material was not found.But this TAC film needs in manufacture process with an organic solvent, therefore these solvents must be reclaimed fully, to prevent the pollution of the environment.Since particularly nearest, destroying problem of environment becomes the focus that people pay close attention to, and people require to avoid as far as possible using the organic solvent that may cause environmental pollution day by day consumingly.

In addition, a kind of pet film is arranged, can adopt to melt extrude the legal system film, do not need to use above-mentioned organic solvent, partly be used as the sheet base film of sensitive photographic material at present.

But polyethylene terephthalate also exists problem, promptly produces and curls (batching defective), and be not easy to eliminate.The sheet base film of sensitive photographic material normally coils into web-like and stores, and film is taken out later on again, is cut into suitable size, is used as tabular films such as X ray film, reproduction film, page film that looses.Under the situation of film, be rolled into web-like and be received in egative film in the magazine, after photography, development, photographic fixing, it is cut into certain length, be placed in the film holder and preserve with the plain film shape.But, to state in the use under the situation of polyethylene terephthalate, curling when coiling into web-like originally still remains, and still curling behind the sheet that looses even cut into.

People proposed the scheme of curling, improve crimpiness that many eliminations have produced and minimizing and even did not produce scheme curling, that improve crimpiness for this reason, and these schemes are summarized as follows.

The spy opens and has announced a kind of biaxial stretch-formed laminated polyester film among the clear 50-16783, is made of two kinds of polyester layers, and their limiting viscosities separately are in the 0.35-1.0 scope, and the limiting viscosity difference of the two is in the 0.02-0.5 scope.

The mylar of this lamination, the differential contraction stress difference of each layer in its table, thereby generation is curling, according to this opposite direction of curling film being batched, curls thereby eliminate.

The spy open announced among the clear 50-81325 a kind of with biaxial stretch-formed poly-2, the 6-(ethylene naphthalate) is the photographic film of plate substrate material, the ratio of the vertical and horizontal Young modulus of this plate substrate material is in the 0.9-1.1 scope, in 180 ℃ saturated shrinkage factors or saturated expansivity below 0.9%, below 0.4%, the haze degree is below 4.5% in the difference of the saturated shrinkage factor of the vertical and horizontal below 200 ℃ or saturated expansivity.

The spy opens and announced a kind of mylar manufacture method among the clear 50-95374, it is characterized in that, and is biaxial stretch-formed, and heat fixation adds thermal maturation then in 40 ℃ of-130 ℃ of temperature ranges.Announced in the embodiment and a kind ofly carried out biaxial stretch-formedly with vertical 4.3 times and horizontal 3.5 times that at 200 ℃ of heat fixations, 24 hours thickness of slaking is the poly-2 of 12 μ m in 40 ℃ of-130 ℃ of temperature ranges subsequently, 6-(ethylene naphthalate) film.

The spy opens and has announced a kind of photographic film among the clear 50-109715, it at least with film described below as the plate substrate material, this film is 0.40 at least by limiting viscosity (35 ℃, in orthomonochlorphenol) and constitutes all that at least 90% (mole) is 2 in the unit, the polyester of 6-(ethylene naphthalate) constitutes, the haze degree is no more than 5%, and through biaxial orienting, heat fixation.

Announced a kind of method in the U.S. Patent No. 4141735, the Tg that is 5-50mm and the firing rate of dividing with 20K/ by thickness, utilizes DSC to measure is higher than the independence film that 60 ℃ thermoplastic polymer forms to heat-treat, make film indeformable basically, do not shrink, thereby the fixing crimpiness of the volume core that reduces film.This method is achieved in that promptly 30 ℃ of maintenances about 0.1-1500 hour to the relative humidity the Tg temperature and 100% of above-mentioned polymkeric substance below, until the volume core of film fixedly crimpiness reduce till 15% at least.Above-mentioned volume core fixedly crimpiness reduce be with through heat treated film on the volume core of 3 inches of external diameters, the Board Lot that curls of the ANSI fixedly the time changed definite with not carrying out the number change of above-mentioned heat treated corresponding film in the curling unit of ANSI fixedly time the through same volume core to compare through 24 hours volume cores under 49 ℃ and 50%RH.

Listed Tg in the embodiment 10 of this patent specification, the table 7 and be 198 ℃ poly-(2, the 6-(ethylene naphthalate)) heat treatment temperature of film and the fixing clean ANSI crimp values of crimpiness of volume core, promptly under 60 ℃, 71 ℃, 100 ℃, 120 ℃, 149 ℃ and 180 ℃ of treatment temperatures, clean ANSI crimp values is respectively 18,16,13,16,20 and 25.

Announced a kind of photographic film among the special public clear 56-53745, it be with by separately limiting viscosity 0.35-1.0 scope and the limiting viscosity difference of the two two kinds of polyester layers of 0.02-1.0 scope constitute and stretched, heat fixation and curling laminated polyester film as the sheet base film, on that one deck that limiting viscosity is low on this sheet base film, be coated with photosensitive material layer, utilize the contraction of this photosensitive material layer to offset curling of sheet base film.

Announced a kind of sensitive photographic material among the Te Kaiping 1-244446, it includes haze is below 3% and polyester film base film and at least one deck photonasty coating of water percentage more than 0.5% (weight).The feature of this photosensitive material is that the sheet base film has the above water percentage of 0.5% (weight), in order to obtain above-mentioned water percentage, will contain the aromatic dicarboxylic acid composition copolymerization of metal sulfonate.

Disclosure of an invention

The purpose of this invention is to provide base film for photographic film.

Another object of the present invention provides and has good curling resistance the base film for photographic film of (i.e. opposing produces curling performance owing to batching), the transparency and sliding.

Another purpose of the present invention provides to gather 2, and the 6-(ethylene naphthalate) is the base film for photographic film of raw material.

Another object of the present invention provides has the good resistance crimpiness, and has the base film for photographic film of good curling elimination performance (promptly in case produce the easy performance with its elimination of curling).

Another purpose of the present invention provides has the base film for photographic film that good anti-layer is peeled off (delamination) property and mar resistance.

A further object of the present invention provides the good and less base film for photographic film of thickness offset (thick spot) of planarity.

A further object of the invention produces the photograph sheet base film of smear metal pettiness when providing cut-out or perforation.

Another object of the present invention provides a kind of photograph of the present invention that will possess above-mentioned performance and batches with the state that adhesion blocks with the sheet base film, thus the film that can easily film be drawn.

Another purpose of the present invention provides and a kind ofly contains inert particulate, has top layer as thin as a wafer and possess the base film for photographic film of above-mentioned various performances.

Other purpose of the present invention and advantage can clearly be seen that from following narration explanation.

According to the present invention, above-mentioned purpose and advantage at first are to realize by the base film for photographic film with following feature, that is:

(a) refractive index on the thickness direction (nz) is 1.498 at least;

(b) the haze value is below 2.0%;

(c) have one under 0.05Hz, depend on stretch viscoelastic, 80 ℃

Tan δ value is in the direction below 0.09;

(d) the anti-roll curvature under 70 ℃ is more than 45%;

(e) thickness is in the 40-120 mu m range;

(f) to gather 2, the 6-(ethylene naphthalate) is that substantial raw material constitutes.

The simple declaration of accompanying drawing

Fig. 1 is used for the oblique view that illustrative sheet volume is gone up the sheet volume of the strumae that produces;

Fig. 2 is the local amplification oblique drawing of the scratch state on the illustrative film surface, wherein (a) and (b) and the different abrasive state of (c) expression.

Preferred forms of the present invention

Base film for photographic film of the present invention is by above-mentioned necessary condition (a)-(f) be particularly limited.

At first be its raw material, condition (f) defined is such if necessary, is in fact to be made of poly-NDA glycol ester. Described poly-NDA glycol ester is preferentially selected the homopolymers take the NDA glycol ester as whole repetitives, and perhaps at least 97% (mole) is the copolymer of NDA glycol ester in whole repetitives.

The third composition that consists of copolymer is that two compounds that can form the functional group of ester are arranged in the molecule, for example: oxalic acid, adipic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), 2, the dicarboxylic acids such as 7-naphthalenedicarboxylic acid, diphenyl ether dicarboxylic acids, P-hydroxybenzoic acid, to hydroxy acids such as '-hydroxyethoxy yl benzoic acids, perhaps propane diols, 1, ammediol, BDO, 1, the di-alcohols such as 6-hexylene glycol, neopentyl glycol, diethylene glycol (DEG).

In addition, poly-2, the 6-(ethylene naphthalate) also can be with simple function compounds such as benzoic acid, methoxyl group PAG with the hydroxyl of end and/or part or all end-blocking of carboxyl, or in the scope of acquisition linear polymer, carry out modification with above become ester compounds of trifunctional such as the glycerine of minute quantity, pentaerythrites.

The homopolymers that the preferential selection of poly-NDA glycol ester consists of as whole repetitives with the NDA glycol ester in fact.

Poly-NDA glycol ester like this can contain additive, such as stabilizing agent, ultra-violet absorber, colouring agent, fire retardant etc.

Base film for photographic film of the present invention has sliding in order to make it, can contain the inert particulate of less ratio.

These inert particulates, it can be included in poly-2, in the 6-(ethylene naphthalate) raw material, its concrete example can be enumerated the inorganic particles such as spherical, calcium carbonate, aluminium oxide, zeolite, perhaps the organic granulars such as silicone resin particle, crosslinked polystyrene particle. Being in the situation of inorganic particle at inert particulate, preferentially selecting the synthesizing inorganic particle, is anyly all to be fine as for its crystal habit.

Wherein, spherical is one of preferred inert particulate. This spherical, the shape of each particle are close to real sphere, and size ratio (maximum gauge/minimum diameter) is advisable with 1.0-1.2, and preferred 1.0-1.1 is preferably in the 1.0-1.05 scope. In addition, this spherical exists with monodisperse status, and for example it is not the spheric granules that forms the primary particle of flocculated particle. Spherical such as the fruit increase, produce easily the space around the particle, in addition, the space that has produced relatively becomes greatly, haze is increased, thereby be worthless.

In addition, silicone resin particle and crosslinked polystyrene particle also are preferred inert particulates.

The silicone resin particle, 80% (weight) of preferred structure unit is above by with CH₃·SiO _3/2The organo-polysilane granules that the construction unit of expression consists of. Its construction unit CH₃·SiO _3/2Represent with following formula:

In addition, also can to show as more than 80% (weight) of its construction unit be with (CH to above-mentioned silicone resin particle₃·SiO _3/2) polysiloxane of the three-dimensional bond structure that represents of n, the n in the formula represents the degree of polymerization, preferably more than 100. Other composition can be enumerated the organic siloxane derivative of dual functional polysiloxane or other trifunctional.

The characteristics of above-mentioned silicone resin particle are, have good lubricity, and proportion is less than inorganic inert particulate, and heat resistance is better than other organic fine particles, in addition, it is insoluble to organic solvent, and are non-meltings. The silicone resin particle demonstrates good compatibility for poly-NDA glycol ester. The volume shape factor of above-mentioned silicone resin particle is 0.20-π/6 preferably. If have this characteristic, the sliding of biaxially oriented film can be better, and cause the silicone resin particle for the good compatibility of poly-NDA glycol ester, greatly improves the transparency of film.

In addition, the crosslinked polystyrene particle best shape is spherical, and size distribution is narrow. With regard to shape, the size ratio of the ratio definition of usefulness maximum gauge/minimum diameter is comparatively suitable in the 1.0-1.2 scope, preferably 1.0-1.15 scope, particularly 1.0-1.12 scope.

Crosslinked polystyrene particle is not subjected to the restriction of its manufacture method; for example; spherical crosslinked polystyrene particle can make by the following stated: except styrene monomer; the methyl styrene monomer; α-methylstyrenemonomer; outside the styrene derivative monomers such as dichlorostyrene monomer; make the conjugate diene monomer from butadiene; the unsaturated nitrile monomer of acrylonitrile and so on; the monomers such as the methacrylate of methyl methacrylate and so on; the functional monomer of unsaturated carboxylic acid and so on; hydroxyethyl methacrylate and so on has the monomer of hydroxyl; GMA and so on has the monomer of epoxides base; the monomer of one or more that select in the unsaturated sulfonic acid etc. makes polymer beads form the polyfunctional vinyl compounds of the crosslinking agent of three-dimensional structure with conduct; divinylbenzene for example; GDMA; trimethylolpropane triacrylate; diallyl phthalate etc.; emulsion polymerization in the molten aqueous medium that has water soluble polymer (as a protecting colloid); adjust the emulsion of polymer beads; from this emulsion, reclaim polymer beads; it is removed then classification with jet mill after dry.

The average grain diameter of above-mentioned inert particulate is comparatively suitable in the 0.05-1.5 mu m range. If inert particulate is inorganic particle, average grain diameter is better in the 0.1-0.8 mu m range, preferably 0.2-0.5 μ m; If inert particulate is the silicone resin particle, then average grain diameter is better at 0.1-1.5 mu m ranges, preferably 0.2-1.3 μ m; In addition, if inert particulate is crosslinked polystyrene particle, then average grain diameter is better at the 0.1-1 mu m range.

If the average grain diameter of inert particulate is less than 0.05 μ m, the effect that then improves the sliding of film, anti-cutting property or batching property etc. is smaller, otherwise, if average grain diameter greater than 1.5 μ m, then the transparency of film descends, and all is worthless therefore.

As for the size distribution of inert particulate, the relative standard deviation that is expressed from the next is being advisable below 0.5, preferably below 0.3, preferably below 0.12.

Relative standard deviation= $\sqrt{\underset{i=1}{\overset{n}{\mathrm{\Σ}}}(\mathrm{Di}-\mathrm{Da}{)}^2/n}/\mathrm{Da}$ In the formula: Di is the projected area equivalent diameter (μ m) of each particle

Da is the mean value of projected area equivalent diameter $\mathrm{Da}=\left(\underset{i=1}{\overset{n}{\mathrm{\Σ}}}\mathrm{Di}\right)/n----\left(\mathrm{\μm}\right)$

N is the number of the particle of mensuration.

If use relative standard deviation at the inert particulate below 0.5, this particle be spherical and size-grade distribution extremely steep, so the height of film surface projection is very even.In addition, the shape of the projection one by one that forms on film surface is very sharp-pointed, and the sliding of film is good especially.

The content of inert particulate is comparatively suitable at 0.001-0.2% (weight).If inert particulate is an inorganic particle, its content suits at 0.001-0.1% (weight), and preferred content is 0.002-0.007% (weight), particularly 0.003-0.005% (weight); If inert particulate is the silicone resin particle, its content is advisable at 0.001-0.1% (weight), preferably 0.002-0.02% (weight), particularly 0.003-0.01% (weight); If inert particulate is a crosslinked polystyrene particle, its content is better at 0.002-0.1% (weight), preferably 0.003-0.05% (weight).The addition of inert particulate causes film sliding deficiency during less than 0.001% (weight) easily, otherwise if surpass 0.2% (weight), then the haze of film increases, and the transparency is not enough, thereby is worthless.

Add the time of inert particulate so long as gathering 2, the stage before the 6-(ethylene naphthalate) film forming gets final product, and does not have other restriction of spy, for example can carry out at polymerization stage, and perhaps the stage before film forming carries out.

Refractive index n z on the thickness direction of base film for photographic film of the present invention is 1.498 (necessary condition (a)) at least.If this refractive index is less than 1.498, and then the scuffing of easy leafing of film and generation zigzag (concavo-convex) is turned white significantly in leafing or scuffing place, thereby is worthless.

Refractive index on the thickness direction of above-mentioned film (nz) is the value of the Na-D line under 25 ℃ being obtained with Abbe refractometer, and the tow sides of film are measured, and gets its mean value.

In order to reach the purpose that improves refractive index (nz), as long as reduce stretching ratio, the raising heat fixation temperature of film.But, if too reduce stretching ratio or improve the heat fixation temperature, can cause the thick spot of film to increase, produce wrinkle (groove) on the film surface.

Refractive index (nz) is preferably below 1.510.

In addition, the haze value of base film for photographic film of the present invention is at (necessary condition (b)) below 2.0%.The haze value is better below 1.5%, preferably below 1.0%.If haze is too high, the transparency of film will reduce, and is worthless.

Have again, base film for photographic film of the present invention has one under 0.05Hz, the preferred tan δ value of direction (necessary condition (c)) that depends on the tan δ viscoelastic, 80 ℃ that stretches and be 0.09 below is less than 0.085, below 0.08 better, 0.06-0.07 preferably.

If tan δ surpasses 0.09, then film curls easily, and as base film for photographic film, performance can not meet the demands.

One of maximum characteristics of base film for photographic film of the present invention are to have curling resistance, as the index of direct these characteristics of sign, and must be 70 ℃ anti-roll curvature at (necessary condition (d)) more than 45%.Better anti-roll curvature is more than 50%.In daily life, usually the photographic film maximum temperature that may run into is about 70 ℃.The film that demonstrates so high anti-roll curvature under 70 ℃ had not been seen report so far.

In the past, to the evaluation of batching defective of photographic film, only relate to photographic film through development or drying process after its degree of curling and being eliminated.

Photographic film of the present invention has the character that good difficult formation is curled, and promptly curling resistance in addition, curls also easily with its elimination even produce, and the so-called property eliminated of curling is also very good.

Of the present invention base film is even still demonstrate good curling resistance under low 21 ℃ than 70 ℃ 49 ℃.That is, on the volume core of 3 inches of external diameters, 49 ℃ and 50%RH condition last volume core fix under (thermal treatment) situation of 24 hours, its clean ANSI crimp values is below 10.

The thickness of base film for photographic film of the present invention is (necessary condition (e)) in the 40-120 mu m range.Preferred one-tenth-value thickness 1/10 is 50-100 μ m.

Of the present invention base film can be biaxial stretch-formed by carrying out with the non-stretched film that conventional method obtains, heat fixation, annealing in process is made then.Biaxial stretch-formed can be successively vertically, transversely biaxial stretch-formed, also can carry out biaxial stretch-formed simultaneously.In addition, vertical, horizontal biaxial stretch-formed after, can also on the either direction of vertical and horizontal or both direction, stretch once more.Stretching condition can adopt known in the past condition, and for example the multiplying power of 2.0-5.0 suits.The biaxially oriented film of system film under usual conditions like this, its vertically go up under 0.05Hz, depend on that the tan δ value viscoelastic, under 80 ℃ that stretches is about 0.10.This tan δ value is reduced to below 0.09.The method that can reduce tan δ value effectively is, is in the temperature of being heated under the rolled state and is lower than 150 ℃ being higher than film, preferably higher 10 ℃ and be lower than under 130 ℃ the temperature than this heating temperature, carries out annealing in process.If annealing in process is carried out below the temperature that film is heated with the state that curls, then can not fully prevent to curl, otherwise, if carry out annealing in process in the temperature that is higher than 150 ℃, cause that easily oligomer separates out and core transfer printing etc. on pellicular front at film surface, be unfavorable for the use of film, thereby be worthless.

The annealing method of biaxially oriented film has following several for instance: the film of biaxial stretch-formed, heat fixation, do not batch, and make it method with the heating of warm-up mill surface of contact; Method with noncontact heating in the process of hot-air conveying; In the process of the film uncoiling of will batch, adopt the method for method heating same as described above; And film heat-treating methods etc. in baking oven that will be rolled into volume.

In addition, when biaxial stretch-formed heat fixation, heat fixation after biaxial stretch-formed is divided into plurality of sections, the heat fixation temperature is reduced gradually, do not produce rapid temperature variation, so just can not cause that thick spot increases and the generation of wrinkle, and easily the refractive index (nz) of thickness direction be brought up to more than 1.498.Have, by dwindling the width of stenter track, film is shunk in the heat fixation district of maximum temperature on Width, then above-mentioned effect is more remarkable.

For example, the heat fixation after biaxial stretch-formed is distinguished into 3 more than the district, preferably is divided into 4 more than the district, the temperature in last district in this heat fixation district is arranged on below 140 ℃, preferably below 120 ℃.

To the last district, temperature is low reduced from the district of the highest heat fixation temperature, do not produce rapid temperature variation.Thermograde between each district is below 70 ℃, preferably below 60 ℃.

Of the present invention base film can also possess the character of following excellence as base film for photographic film.

Sticky limit between the film/film of of the present invention base film is comparatively ideal to be below 3 grades, and better is below 2.5 grades, it would be desirable below 2 grades.The grade of sticky limit is big, and the expression film is difficult to slide, otherwise the little expression film of grade slides to each other easily.Sticky limit is greater than 3 o'clock, film slip variation to each other, and adhesion mutually is transferred the roller scratch when film moves, be easy to generate strumae on the volume when being rolled onto on the spool, and it is unfavorable being used as photographic film.

The flatness of of the present invention base film is advisable below 250cm/m is wide.If it is wide that the flatness of film surpasses 250cm/m, the photosensitive emulsion coating is difficult for evenly.Flatness is preferably below 200cm/m is wide.

Of the present invention base film when carrying out the heat analysis, 120-160 ℃ of temperature range, preferably observed endothermic peak in 130-150 ℃ of temperature range.By the big or small represented heat absorption energy of this endothermic peak, more than the preferred 0.3mJ/mg, more preferably more than the 0.5mJ/mg.Endothermic peak is in the said temperature scope and when having above-mentioned energy, and of the present invention base film demonstrates very good curling resistance.

Of the present invention base film, in one direction, through the shown percent thermal shrinkage that goes out after 150 ℃, 30 minutes hot air treatment, preferably below 3%, more preferably below 2%, most preferably below 1.5%.Of the present invention base film preferably allowed the thickness offset (thick spot) that 5 μ m are following, preferably allows the thick spot that 4 μ m are following.If thick spot surpasses 5 μ m, on film surface, be coated with photosensitive emulsion and be difficult for evenly, the quality of photographic film is descended.

Want to reduce thick spot, effectively way is to improve stretching ratio, reduces heat fixation temperature, vertical draft temperature, horizontal draft temperature.

In addition, the Young modulus of of the present invention base film on mutually perpendicular both direction is at 750kg/mm ²Below be advisable, even more ideal is at 700kg/mm ²Below.If above-mentioned Young modulus surpasses 750kg/mm ², film is cut off or is easy to generate during perforation procedure a lot of smear metals.The lower limit of the Young modulus of vertical and horizontal all is 400kg/mm ², preferred 450kg/mm ²

Difference to the Young modulus of both direction has no particular limits, preferably at 150kg/mm ²Below.

As mentioned above, of the present invention base film has curling resistance, the transparency and sliding basically, in addition, according to the inventor's research, can provide and not damage crimpiness is only further improved sliding with the transparency sheet base film.

Promptly, according to the present invention, second, a kind of base film for photographic film is provided, it is made of the lamilated body of the ground floor and the second layer, and ground floor is inert particulate poly-2 of 0.01-1.5 μ m by can randomly containing less than 0.003% (weight) mean grain size, and the 6-(ethylene naphthalate) constitutes, the second layer is by containing inert particulate poly-2 that 0.003-0.5% (weight) mean grain size is 0.01-1.5 μ m, the 6-(ethylene naphthalate) constitute and thickness below 10 μ m.

This base film for photographic film (hereinafter being called second kind of sheet base film of the present invention), the same with above-mentioned base film of the present invention, all satisfy above-mentioned necessary condition (a) and (b), (c), (d) and (e).

As mentioned above, second kind of sheet base film of the present invention is to be made of the different ground floor of inert particulate content and the laminate film of the second layer.Many and second layer very thin thickness of inert particulate content is laminated in a side or the both sides of ground floor.

Ground floor can randomly contain the inert particulate that mean grain size is 0.01-1.5 μ m, is containing under the situation of inert particulate, and its content is less than 0.003% (weight), below preferred 0.001% (weight).

About mean grain size is the inert particulate of 0.01-1.5 μ m, and the place that here is not illustrated especially can be thought, being described in of relevant inert particulate also is to be suitable for fully here in the initial of the present invention base film of recording and narrating of this paper is that part of.

The content of the inert particulate of ground floor is less than 0.003% (weight).The thickness of second kind of sheet base film of the present invention is 50-120 μ m (necessary condition (e)), and in addition as mentioned above, the thickness of the second layer is at most 10 μ m, so the thickness of ground floor is more much bigger than the second layer.By increasing the thickness that does not contain inert particulate or contain the considerably less ground floor of inert particulate, increase thickness shared ratio in sheet base film gross thickness of ground floor, thereby guarantee the transparency of sheet base film.

It is the inert particulate of 0.01-1.5 μ m that the second layer contains 0.003-0.5% (weight) mean grain size.

To the inert particulate of the second layer, should go equally according to inert particulate to understand with ground floor.

The content of the inert particulate in the second layer is advisable with 0.003-0.5% (weight), preferred 0.01-0.1% (weight).If inert particulate content is less than 0.003% (weight), the film sliding is poor, and film is adhesion easily each other, otherwise if surpass 0.5% (weight), then therefore the mar resistance of film, transparent bad is worthless.

The thickness t of the second layer ₂The mean grain size d of contained inert particulate in (μ m) and this layer ₂Ratio (the t of (μ m) ₂/ d ₂) be advisable preferred 0.2-5, more preferably 0.3-3 with 0.1-10.This ratio (t ₂/ d ₂) if less than 0.1, the inert particulate of its top layer part came off from film surface easily when film moved, and the sliding variation of film, otherwise if greater than 10, then mar resistance is bad, and is also inadvisable.

The main effect of the second layer is to give second kind of sheet base film of the present invention with sliding.

The thickness of the second layer (second layer is meant the thickness of each layer when two surveys of ground floor are total two-layer) is below 10 μ m, below the preferred 5 μ m.The lower limit of thickness is advisable with 0.1 μ m.

The biaxial orientation laminated film that is used for second kind of sheet base film of the present invention can be made as follows, be about to constitute the ground floor and the second layer separately poly-2,6-(ethylene naphthalate) or the composition that contains it melt respectively, by the mould coextrusion, before solidifying, make it the lamination fusion, become the film that does not stretch, biaxial stretch-formed then, heat fixation, perhaps each polymkeric substance or composition are melted, extrude, form film respectively, make both lamination fusions in unstretched state or after stretching.Then, the biaxial orientation laminated film of gained by carrying out annealing in process with the same method of above-mentioned annealing in process, can be obtained second kind of sheet base film of the present invention.

For second kind of part that the sheet base film is not addressed of the present invention, being interpreted as foregoing corresponding description to of the present invention base film is to be suitable for fully.

According to the present invention, equally also provide the sheet volume of the base film for photographic film that of the present invention base film (comprise second kind of sheet base film, below identical) batched, keeps and form with the state that does not have adhesion.

That is, the feature of the sheet of base film for photographic film of the present invention volume is that film is an of the present invention base film, and the space of 7-20% (volume) air layer is arranged at the interlayer of film.

Of the present invention volume should make the interlayer of film that 7-20% (volume), preferred 8-19% (volume), the more preferably air layer of 10-18% (volume) are arranged when take-up.If this air layer less than 7% (volume), then the sheet volume will be because of the annealing in process crimping, thereby generation adhesion or the foregoing small wound of tearing, otherwise, if air layer surpasses 20% (volume), the problems referred to above do not take place, but replace the rolled state instability, the end face of sheet volume is uneven when batching, and produces volume distortion etc. when volume send, and all is worthless therefore.

With regard to the sheet volume, the method that air capacity between thin layer is adjusted to above-mentioned scope can be exemplified below, when being become web-like, film rolling near two edges of sheet volume, is involved in the method for film in a narrow margin simultaneously, perhaps form the method for concavo-convex (for example embossing processing) in advance at length direction, specifically adopt which kind of method without limits near near the film the edge of sheet volume.

On the surface of of the present invention base film, can form various thin layers based on sensitive emulsion layer, make photographic film.The formation of these thin layers can be adopted known method.

Embodiment

Illustrate in greater detail the present invention by the following examples, but the present invention is not subjected to the restriction of these embodiment.

The refractive index (nz) of the tan δ described in embodiment and the comparative example, thickness direction, anti-roll curvature and bending leafing albefaction rate are measured as described below.

(1) refractive index of thickness direction (nz)

Use Abbe refractometer (manufacturing of the ア of Co., Ltd. go), under 25 ℃, utilize the Na-D line to obtain the refractive index of film thickness direction.Positive and negative two sides to film sample is measured, with their mean value as refractive index (nz).

(2) haze

Press JIS K-6714 method, each opens the full haze value of film with commercially available nephelometer is measured.

(3)tanδ

The thermal stress strain determinator TMA/SS120C that uses Seiko electronics industry (strain) to make measures under following condition.

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

The load median of unit cross-sectional area: 120g/mm ²

Unit cross-sectional area load change amplitude: 90g/mm ²

Programming rate: 5 ℃/minute

Sample width: 4mm

Sample length (chuck spacing): 10mm

Measure direction: vertically

(4) anti-roll curvature

The film sample of 120mm * 35mm size is wound on the volume core of diameter 10mm, it is temporarily fixed making it not uncoiling, heating is 72 hours under 70 ℃, 30%R H condition, discharges from the volume core then, and dipping is 15 minutes in 40 ℃ distilled water.Add 50g load then, sample vertically hung, be determined at residual have under the curling state " specimen length " (mm), with its ratio (%) with respect to primary sample length (120mm) as anti-roll curvature.

" specimen length " in this case when sample is curling very big, when formation is round or semicircle, is its diameter, and be less when curling, and when not forming semicircle, is its chord length.

This anti-roll curvature is high more, and expression is difficult to produce more curls.

(5) clean ANSI crimp values

Test method A (21 ℃ 50%RH) are carried out that ANSI/ASC PH1.29-1971 is pressed in the evaluation of curling.Winding film on the volume core of 3 inches of external diameters, was handled 24 hours under 49 ℃, 50%RH, made it to produce and curl, the film size of use is 4 inches * 6 inches.

Clean ANSI crimp values=on the volume core, batch the ANSI crimp values that forms after curling

ANSI crimp values before-volume core batches

(6) sticky limit

Rubber slab is layered on the estrade on a plane, stacks 2 films in the above, do not have dust, pollutant etc. between the film.With the cylindrical counterweight of external diameter 70mm, heavy 10kg from directly over be placed on lightly on the film, take counterweight after 10 minutes more lightly away.Place after 30 seconds, the contact vestige film recording in circular is got off, measure the area ratio of adhesion part, be divided into the 0-5 level by the regulation in the table 1.

Table 1

Level	The ratio (%) of adhesion part
		0 1 2 3 4 5	Below 10% more than 10%, below 30% more than 30%, below 50% more than 50%, below 70% more than 70%, below 90% more than 90%

(7) flatness

Roll up the film sample that cuts long 2 m from sheet, be positioned at be rolled in the surperficial side of sheet volume when sheet is rolled up up, expansion flatly is placed on the platform.After leaving standstill 10 minutes, the length (cm) of wrinkle residual on this surface (groove) is measured on the whole surface of viewing film sample, with the width (m) of its sum divided by film, calculates flatness.

(8) endothermic peak temperature T _k(℃)

The 10mg film is contained on the thermal analysis system SSC580DS (DSC) of Seiko electronics industry (strain) system, at N ₂With the heating of 20 ℃/minute programming rate, resolve the heat absorption situation of this film in the air-flow, determine the peak value display temperature with a subdifferential, second differential, with it as the endothermic peak temperature.

(9) heat absorption energy Δ H _k(mJ/mg)

Same with (8), the 10mg film is contained on thermal analysis system SSC580, the SDC20 of Seiko electronics industry (strain) manufacturing, at N ₂In the air-flow with the heating of 20 ℃/minute programming rate, by with the corresponding DSC figure of the heat absorption energy of film on the heat absorbing side area try to achieve.

This area is to shift to heat absorbing side owing to heat up from baseline, continues to heat up through turning back to the area of the heat absorbing side till the baseline position after the endothermic peak again, connects straight line in the temperature position to the end by heat absorption beginning temperature position, obtains area (A).Measure In (indium) under same DSC condition determination, establishing this area (B) is 28.5mJ/mg, obtains Δ H by following formula _k

(A/B)×28.5＝ΔH _k(mJ/mg)

(10) percent thermal shrinkage

In 150 ℃ hot blast, kept 30 minutes, connect the change in size that following formula is obtained its front and back.

In the formula, L ₀It is the gauge length before the thermal shrinkage

L is the gauge length after the thermal shrinkage

(11) thickness offset of film

Use ア Application リ Star, the K-312A type electronic ga(u)ge that Co., Ltd. makes, with 30g pin pressure, 25mm/ translational speed second, vertical and horizontal at film are measured 2m length respectively, obtain the continuous thickness map of precision ± 4 μ m, obtain the maximal value and the minimum value of thickness in the 2m scope by this figure, with their poor R (μ m) as thickness offset.

(12) Young modulus

By the sample that cuts wide 10mm, long 15cm on the film, spacing jig 100mm with the draw speed of 10mm/ branch, the speed of paper that 500mm/ divides, stretches on the Instron universal tensile testing machine.Tangent line by the rising part of resulting load elongation chart calculates Young modulus.

(13) Juan form

With the film rolling rolling of wide 500mm, long 500m, with the naked eye scrutiny is somebody's turn to do the outward appearance of volume, and number goes out the number of as shown in Figure 1 the wart like structure of maximum gauge more than 1mm, is divided into the 1-5 level by table 2, and 4 grades and 5 grades is defective.

Table 2

Level	The number of projection (individual)
		1 2 3 4 5	0 1～2 3～5 6～10 more than 11

(14) bending leafing albefaction rate

Cut the film sample of 80mm * 80mm size, with the light doubling of have gentle hands, after clamping with a pair of flat sheet metal, again with the pressure P of pressing machine with regulation ₁(kg/cm ²G) pressurization is 20 seconds.After pressing, revert to original state, clamp with above-mentioned sheet metal, in pressure P with the film of handgrip doubling ₁(kg/cm ²G) pressurizeed 20 seconds down, take out film sample then, measure, add up to the length (mm) of the albefaction part of folding line place appearance.

Use new film sample respectively, with pressure P ₁=1,2,3,4,5,6 (kg/cm ²G) repeat above-mentioned test respectively.

To represent the index of the film complexity that delamination occurs with its conduct as bending leafing albefaction rate in the mean value of the total of the length (mm) of the albefaction under each pressure part shared ratio in folding line length overall (80mm).

(15) situation of generation smear metal

Adhesive tape (day eastern diaphragm SPV-363 on the perforated portion of the film of use tapping machine perforation and the metallic roll that bonding plane is contained in diameter 10cm outwardly; eastern electrician of day (strain) makes) contact; the speed of dividing with 10m/ moves 100m; visualization is attached to the scrap rate on the adhesive tape, by following standard grading.

◎: do not observe smear metal and adhere to

Zero: do not observe smear metal basically and adhere to

△: observe some smear metals and adhere to

*: observe a large amount of smear metals and adhere to

(16) adhesion after the annealing in process

The film of wide 500mm, long 500m is rolled the rolling shape, 110 ℃ of annealing in process 24 hours.About 400m is cut on volume after annealing surface, and visualization volume core segment has or not adhesion, passes judgment on by following standard.

Zero: a bit do not produce adhesion, the volume surface is smooth.

△: have 3-5 to sentence down the adhesion of grain of rice shape, other parts are smooth.

*: the adhesion of the above grain of rice shape in 6 places is arranged, perhaps have 1 place above greater than 10mm ²

Adhesion

(17) mar resistance

Use ヘ イ De Application-14 type scratch tester (new eastern science Co., Ltd. make), the diamond needle that with tip radius is 50 μ m is as the cut pin, under pin loading 200g, the translational speed 2mm/ condition of second on film surface the about 100mm of cut along its length.

Observe the cut part with 100 times transmission microscopies, press standard grading in the table 3 according to the cut state.

Table 3

Grade	Use fractographic state	Shape
			A	Observe the ditch shape and scratch, but not obvious	Fig. 2 (a)
B	The squamous apperance is arranged in the ditch, scratch obvious a little	Fig. 2 (b)
			C	Because moving of pin, the film surface part cracks (concavo-convex), scratches and obviously turns white	Fig. 2 (c)

A level and B level can allow in practicality.

(18) ratio of air layer

The diameter D of the sheet volume that mensuration is batched with certain-length in addition, is calculated the diameter D of sheet volume when not having air layer by film thickness and length gauge ₀, obtain the ratio of air layer in following formula according to calculated value and measured value.

(19) mean grain size of particle

Measure with the centrifugal particle-size analyzer of CP-50 type (Centrifugal Particle Size Analyzer) that Shimadzu Seisakusho Ltd. makes.Calculate the summation curve of each size particles and amount according to resulting centrifugal settling curve, go out to be equivalent to the particle diameter of 50 mass percents (mass percent) by this curve calculating, (issue as above-mentioned mean grain size with this value referring to " granulometry technology " Nikkan Kogyo Shimbun, 1975, P242-247).

(20) volume shape factor (f)

Take 10 visual fields of lubricant particle with 5000 times of enlargement factors with scanning electron microscope, utilize image analysis processing device Le-ゼ Star Network ス 500 (Japanese レ ギ ニ レ--manufacturing) to calculate the mean value of maximum gauge in each visual field, obtain the mean value of 10 visual fields again, as D.

By the particle mean grain size d that obtains in above-mentioned (19), press V=(π/6) d ³Obtain the volume of particle, calculate shape coefficient f by following formula again.

F=V/D ³V is volume (the μ m of particle in the formula ³), D is the maximum gauge (μ m) of particle.

(21) particle diameter ratio

With the fixing shaping of film small pieces, make the ultra-thin section (with the parallel cut-out of film flow direction) of thick about 600 with epoxy resin with the shave machine.Utilize transmission electron microscope (Hitachi makes: the section configuration of the lubricant particle in the viewing film sample H-800 type), represent particle diameter ratio with the particle maximum gauge and the ratio of minimum diameter.

(22) mean grain size of particle, particle diameter ratio etc.

With powder spraying on the sample bench of Electronic Speculum, each and every one particle is not overlapping as far as possible, utilize golden sputter equipment to form the gold thin film evaporation layer of thick 200-300 in its surface, doubly observe down at 10000-30000 with scanning electron microscope, obtain maximum gauge (Dli), minimum diameter (Dsi) and the projected area equivalent diameter (Di) of at least 100 particles with the Le-ゼ Star Network ス 500 of Japanese レ ギ ニ レ--(strain) manufacturing.With their maximum gauge (D1), minimum diameter (Ds), the mean grain size (Da) of the number average value representation particle that is expressed from the next, obtain particle diameter ratio by them again. $D1=\left(\underset{i=1}{\overset{n}{\mathrm{\Σ}}}D1i\right)/\mathrm{nDs}=\left(\underset{i=1}{\overset{n}{\mathrm{\Σ}}}\mathrm{Dsi}\right)/n$ $\mathrm{Da}=\left(\underset{i=1}{\overset{n}{\mathrm{\Σ}}}\mathrm{Di}\right)/n$

In addition, the particle in the film is asked calculation as described below.

The film sample small pieces are fixed on the sample bench of scanning electron microscope, the sputter equipment (JFC-1100 type ion etching device) with NEC (strain) is made imposes the ion etch to film surface under the following conditions and handles.Sample is placed in the glass bell jar, and gas clean-up is to about 10 ^-3The straight dummy status of holder, the ion etch is about 10 minutes under voltage 0.25KV, electric current 125mA.Use same device sputter gold on film surface again, amplify 10000-30000 with scanning electron microscope and doubly observe, obtain maximum gauge (Dli), minimum diameter (Dsi) and the projected area equivalent diameter (Di) of at least 100 particles with the Le-ゼ Star Network ス 500 of Japanese レ ギ ニ レ--(strain) manufacturing.Below carry out equally with above-mentioned.

Embodiment 1-4 and comparative example 1-3

To contain inert particulate shown in the table 4 and limiting viscosity and be 0.60 poly-2, the 6-(ethylene naphthalate) is by melt extruding in the die slot, cooling curing on the curtain coating drum, make non-stretched film, then, under 130 ℃ with 3.0 times of its longitudinal stretchings, then use the two ends of the Width of stenter pressing plate clamping film, at 135 ℃ of following cross directional stretchs 3,3 times, again under tension at 230 ℃ of heat fixations, unclamp clamping subsequently, at tensioning state contact chilling roller and quench cooled, the film of biaxial orienting is batched rolling.

By the film sample that cuts wide 500mm, long 500m on the gained biaxially oriented film, batch and on the volume core of diameter 165mm, make the sample volume, under this state, carry out annealing in process by condition shown in the table 4.

The rerum natura of the biaxially oriented film after the annealing in process is shown in Table 4.

The biaxially oriented film of embodiment 1-4 is that annealed processing makes tan δ value reach the film of setting, satisfies the desired performance of photographic film material.

Comparative example 1 is the example that does not carry out annealing in process, and it is restorative not obtain to curl fully.In addition, comparative example 2 be too high because of annealing temperature, do not obtain desired tan δ value, thereby do not have to obtain to curl fully restorative example.

Comparative example 3 is that the lubricant addition too much and not obtains the example of the transparency fully.

Table 4

Table 4 (continuing)

Embodiment 5,6 and comparative example 4,5

Except use contain particulate shown in the table 5, limiting viscosity be 0.60 poly-2, beyond the 6-(ethylene naphthalate),, obtain the biaxially oriented film that annealing in process is crossed with the identical operation of embodiment 1-4.

The character of the biaxially oriented film of the annealed processing of gained is shown in Table 5.

Table 5

Table 5 (continuing)

Embodiment 7-10 and comparative example 6,7

With conventional method with limiting viscosity be 0.60 poly-2, the 6-(ethylene naphthalate) makes it cooling curing on the curtain coating drum by melt extruding in the die slot, makes the film that does not stretch.

It is biaxial stretch-formed, heat fixation under condition shown in the table 6 are pressed the annealing in process of condition shown in the table 6 again, obtain the biaxially oriented film of thick 75 μ m.

Heat fixation is to adopt heat fixation is divided into X ₁, X ₂, X ₃And X ₄The device in district carries out, and the district that the heat fixation temperature is the highest is X ₁The district by reducing the width of stenter track, can make film shrink at Width.

Annealing in process is undertaken by the following stated, film behind soon biaxial stretch-formed, the heat fixation contacts with chill roll under tensioning state, make it cooling, by the film that takes out wide 500mm, long 500m on the film parent roll that batches, batching on the volume core of the about 165mm of diameter becomes web-like, puts into baking oven then and heats.

Table 6

*: annealing conditions

A condition: be warming up to 100 ℃ with 24 hours, keep after 24 hours, with 24

Hour reduce to room temperature.

B condition: be warming up to 90 ℃ with 24 hours, keep after 24 hours, with 24

Hour reduce to room temperature.

Each biaxially oriented film of resulting annealed processing is measured refractive index (nz), anti-roll curvature, the bending leafing albefaction rate of its tan δ, thickness direction etc., the result is as shown in table 7.

Table 7

Embodiment 11-14 and comparative example 8

With conventional method with limiting viscosity be 0.60 poly-2, the 6-(ethylene naphthalate) makes it cooling curing on the curtain coating drum by melt extruding in the die slot, forms non-stretched film.

Press that condition shown in the table 8 is biaxial stretch-formed with it, the tensioning heat fixation, press the annealing in process of condition shown in the table 8 again, obtain the biaxially oriented film of thick 75 μ m.

Annealing in process is undertaken by the following stated, film behind soon biaxial stretch-formed, the heat fixation contacts with the chilling roller under tensioning state and makes it cooling, by the film that takes off wide 500mm, long 500m on the film parent roll that batches, batching on the volume core of the about 165mm of diameter becomes web-like, puts into baking oven and heats.

Table 8

The implication of the annealing conditions in the table 8 is identical with table 6.

Measure the stretch viscoelastic δ of tan longitudinally (80 ℃), flatness, the anti-roll curvature etc. of depending at 0.05Hz of the biaxially oriented film of resulting annealed processing, the result is as shown in table 9.

Table 9

Embodiment 15-18 and comparative example 9

With conventional method with limiting viscosity be 0.60 poly-2, the 6-(ethylene naphthalate) is by melt extruding in the die slot, cooling curing on the curtain coating drum forms non-stretched film.

Press that condition shown in the table 10 is biaxial stretch-formed with it, the tensioning heat fixation, press the annealing in process of condition shown in the table 10 again, obtain the biaxially oriented film of thick 75 μ m.

Annealing in process is undertaken by the following stated, film behind soon biaxial stretch-formed, the heat fixation contacts with the chilling roller under tensioning state, makes it cooling, by the film that takes off wide 500mm, long 500m on the film parent roll that batches, on the volume core of the about 165mm of diameter, batch rolling, put into baking oven and heat.

Table 10

The implication of the annealing conditions in the table 10 is identical with table 6.

To resulting biaxially oriented film, measure its Young modulus that depends on stretching viscoelastic vertical tan δ (80 ℃), vertical and horizontal, draw crimp percentage, produce the situation of smear metal etc. at 0.05Hz, the results are shown in the table 11.

Table 11

Embodiment 19 and comparative example 10

With conventional method with limiting viscosity be 0.60 poly-2, the 6-(ethylene naphthalate) is by melt extruding in the die slot, cooling curing on the curtain coating drum forms non-stretched film.

Press that condition shown in the table 12 is biaxial stretch-formed with it, the tensioning heat fixation, press the annealing in process of condition shown in the table 12 again, obtain the biaxially oriented film of thick 75 μ m.

Annealing in process and embodiment 15-18 are identical, and the characteristic of resulting film is shown in Table 12.

Table 12

Table 12 (continuing)

Embodiment 20-23 and comparative example 11-14

Except use contain inert particulate shown in the table 13 and limiting viscosity be 0.60 poly-2, outside the 6-(ethylene naphthalate),, obtain the biaxially oriented film that annealing in process is crossed with the identical operation of embodiment 1-4.

The character of the biaxially oriented film that resulting annealing in process is crossed is shown in Table 13.

Table 13

Table 13 (continuing)

Embodiment 24-27 and comparative example 15-17

Repeat embodiment 1-4, but use contain the inert particulate shown in the table 14 and limiting viscosity be 0.60 poly-2, the 6-(ethylene naphthalate), other and embodiment 1-4 are identical, obtain the biaxially oriented film that annealing in process is crossed.

The character of the biaxially oriented film that the gained annealing in process is crossed is shown in Table 14.

Table 14

Table 14 (continuing)

Embodiment 24-27 and comparative example 15 have reproduced embodiment 1-4 and comparative example 1 respectively well.The film that the annealing in process of these embodiment is crossed has desirable T _k(℃) and Δ H _k(mJ/mg) value.

Embodiment 28-31 and comparative example 18

To add the poly-2 of particle diameter ratio is 1.07, mean grain size is 0.3 μ m preparing spherical SiO 2 particulate by content shown in the table 15 with conventional method, 6-(ethylene naphthalate) (limiting viscosity is 0.60) melt extrudes, make non-stretched film.

Press that condition shown in the table 15 is biaxial stretch-formed with it, heat fixation, obtain the biaxially oriented film of thick 75 μ m.Heat fixation is to adopt heat fixation is divided into X ₁, X ₂And X ₃Next three districts are that the device of cooling zone (cz) carries out, at the district of the highest heat fixation temperature (X ₁The district) in, shrinks by dwindling the width of stenter track, can making on the thin-film width direction.

Table 15

The refractive index of the thickness direction of each biaxially oriented film of mensuration gained and mar resistance etc., test result is as shown in table 16.

Table 16

Embodiment 32-35 and comparative example 19,20

With conventional method melt extrude limiting viscosity be 0.60 poly-2, the 6-(ethylene naphthalate) is made non-stretched film.

Press that condition shown in the table 17 is biaxial stretch-formed with it, thermal treatment, obtain the biaxially oriented film of thick 75 μ m.Above-mentioned thermal treatment is to adopt to be divided into X ₁, X ₂, X ₃And X ₄The annealing device in four districts carries out, at the X of the highest heat fixation temperature ₁In the district, can make on the thin-film width direction by the width that dwindles the stenter track and to shrink.

Table 17

To each biaxially oriented film of gained, measure the refractive index (nz) of its thickness direction, thick spot, flatness and the bending leafing albefaction rate of vertical and horizontal.The result is as shown in Table 18.

Table 18

Embodiment 36 and comparative example 21

To contain 0.008% (weight) mean grain size and be 0.3 μ m preparing spherical SiO 2 (major diameter/minor axis=1.07), limiting viscosity be 0.60 poly-2, the 6-(ethylene naphthalate) is by melt extruding in the die slot, cooling curing on the curtain coating drum is made the film that does not stretch.Then 3.0 times of 130 ℃ of following longitudinal stretchings, then clamp the two ends of thin-film width direction with the stenter pressing plate, 3.3 times of 135 ℃ of following cross directional stretchs, again under tensioning state at 230 ℃ of heat fixations, unclamp clamping subsequently, under tensioning state, contact cooling, the biaxially oriented film of thick 75 μ m is batched rolling, obtain parent roll with the chilling roller.

By on the volume core of on the gained parent roll film rolling of wide 500mm, long 500m being got a diameter 165mm time, be involved in the poly-2 of thick 10 μ m, wide 10mm, 6-(ethylene naphthalate) film simultaneously in the both sides of the edge part of this film rolling (wide 500mm).By condition shown in the table 19 this film rolling is carried out annealing in process.

The rerum natura of the biaxially oriented film after the annealing and be shown in Table 19 as the evaluation result of used for photo sensitive material.

Table 19

Table 19 (continuing)

The biaxially oriented film of embodiment 36 is rolled into volume with suitable air layer ratio, has the haze value and the tan δ value of regulation, satisfies the desired performance of photosensitive photographic film material.

Embodiment 37-41 and comparative example 22-24

Will with content shown in the table 20 contain mean grain size be 0.3 μ m, particle diameter ratio (maximum gauge/minimum diameter) be 1.05 preparing spherical SiO 2 and limiting viscosity be 0.60 poly-2, the 6-(ethylene naphthalate) melts with conventional method, then by coextrusion in the die head adjacent to each other, formation (A) layer and (B) layer respectively, the two sides that will (B) is stacked be placed on (A) layer, make their fusions, chilling solidifies then, makes non-stretched film.

Then, with this non-stretched film 3.0 times of 130 ℃ of following longitudinal stretchings, then clamp the two ends of thin-film width direction with the stenter pressing plate, 3.3 times of 135 ℃ of following cross directional stretchs, again under tensioning state in 230 ℃ of heat fixations, unclamp clamping subsequently, under the state of tensioning, contact chilling, obtain biaxial orientation laminated film with the chilling roller.

Press the annealing in process of condition shown in the table 20 subsequently, obtain the film that gross thickness is 75 μ m.In addition, (A) layer and (B) thickness of layer press shown in the table 20 change respectively.

Annealing in process promptly by biaxial orientation laminated film being batched the film that takes out wide 500mm, long 500m on the film parent roll that forms, is batched rolling by following described carrying out, and puts into baking oven and heats.The character one of the film after the gained annealing in process is listed in the table 20.

Table 20

Table 20 (continuing)

The implication of the annealing conditions in the table 20 is identical with table 6.

Embodiment 42-44 and comparative example 25-27

Use conventional method, will with content shown in the table 21 contain mean grain size shown in the table 21, particle diameter ratio (maximum gauge/minimum diameter) be 1.05 preparing spherical SiO 2 and limiting viscosity be 0.60 poly-2, the fusing of 6-(ethylene naphthalate), by coextrusion in the die head adjacent to each other, form A layer and B layer respectively,, make their fusions the stacked two sides that is put in the A layer of B, chilling solidifies then, makes the laminated film that does not stretch.In this process, adjust the extrusion capacity of each extruder, regulate the thickness of A layer and B layer.

Subsequently, under 130 ℃ with 3.0 times of this non-stretched film longitudinal stretchings, then use the two ends of the Width of stenter clamping plate clamping film, press the cross directional stretch of multiplying power shown in the table 21 down at 135 ℃, under tensioning state, press the heat fixation of temperature shown in the table 21 again, unclamp clamping subsequently, under tensioning state, contact and cool off with the chilling roller, obtaining gross thickness is the biaxial orienting laminated film of 75 μ m, carries out annealing in process by the A condition of embodiment 7-10 then.The thickness of A layer and B layer is pressed respectively shown in the table 21 and is changed.

The haze of the film that mensuration obtains, the refractive index of thickness direction, mar resistance etc., its result is shown in table 21.

Table 21

Table 21 (continuing)

Claims (19)

1. the method for preparing base film for photographic film, comprise and make poly-2, the non-stretched film biaxial orienting of 6-(ethylene naphthalate), the film of heat fixation biaxial orienting also carry out annealing in process to resulting film with rolled state, the temperature of annealing in process is between the temperature of being heated under the rolled state and the 150 ℃ of following temperature being higher than film, so that film is reduced to below 0.09 in the viscoelastic 80 ℃ tan δ value of stretching that depends on of 0.05Hz, to form base film for photographic film, it is characterized in that:

(a) the refractive index n z of thickness direction is 1.498 at least;

(b) the haze value is below 2.0%;

(c) having on the direction in depending on of the 0.05Hz viscoelastic 80 ℃ tan δ value that stretches is below 0.09;

(d) be more than 45% 70 ℃ anti-roll curvature;

(e) thickness is in the 40-120 mu m range; With

(f) to gather 2, the 6-(ethylene naphthalate) constitutes for substantive raw material.

2. according to the method for claim 1, it is characterized in that the refractive index n z of sheet base film thickness direction is below 1.510.

3. according to the method for claim 1, it is characterized in that sheet base film haze value is below 1.5%.

4. according to the method for claim 1, it is characterized in that the sheet base film stretches viscoelastic 80 ℃ tan δ value less than 0.085 depending on of 0.05Hz.

5. according to the method for claim 1, it is characterized in that the sheet base film stretches viscoelastic 80 ℃ tan δ value below 0.08 depending on of 0.05Hz.

6. according to the method for claim 1, it is characterized in that, the sheet base film 70 ℃ anti-roll curvature more than 50%.

7. according to the method for claim 1, it is characterized in that the clean ANSI crimp values of the thermal treatment film of fixing 24 hours on the volume core of 3 inches of external diameters, at 49 ℃ and 50%RH condition last volume core is below 10.

8. according to the method for claim 1, it is characterized in that described poly-2, the 6-(ethylene naphthalate) contains 97 moles of %2 at least, 6-(ethylene naphthalate) unit.

9. according to the method for claim 1, it is characterized in that the sticky limit between the sheet base film is below 3 grades.

10. according to the method for claim 1, it is characterized in that, sheet base film flatness be 250cm/m wide below.

11. the method according to claim 1 is characterized in that, the sheet base film has endothermic peak in 120-160 ℃ of temperature range and it absorbs heat energy more than 0.3mJ/mg.

12. the method according to claim 1 is characterized in that, the sheet base film has the percent thermal shrinkage of a direction after 150 ℃, 30 minutes dry heat treatment below 3%.

13. the method according to claim 1 is characterized in that, the sheet base film has a direction thickness offset below 5 μ m.

14. the method according to claim 1 is characterized in that, it is 750kg/mm that the sheet base film has two orthogonal direction Young moduluss ²Below.

15. the method according to claim 1 is characterized in that, it is the inert particulate of 0.05-1.5 μ m that the sheet base film contains 0.001-0.2 weight % mean grain size.

16. the method according to claim 1 is characterized in that, has the space of the air layer of 7-20 volume % in the film rolling between thin layer.

17. prepare the method for base film for photographic film, comprise and make the laminate film biaxial orienting that do not stretch, the laminate film of heat fixation biaxial orienting also carries out annealing in process to resulting laminate film with rolled state, the temperature of annealing in process is between the temperature and the temperature below 150 ℃ of being heated under the rolled state being higher than film, so that laminate film is reduced to below 0.09 in the viscoelastic 80 ℃ tan δ value of stretching that depends on of 0.05Hz, to form base film for photographic film, described laminate film is by first strata 2, the 6-(ethylene naphthalate) layer and second strata 2,6-(ethylene naphthalate) layer is formed, wherein can to contain the following mean grain size of 0.003 weight % be the inert particulate of 0.01-1.5 μ m to ground floor, it is the inert particulate of 0.01-1.5 μ m that the second layer contains 0.003-0.5 weight % mean grain size, the sheet base film is characterised in that

(a) the refractive index n z of thickness direction is 1.498 at least,

(b) the haze value is below 2.0%,

(c) there is a direction to stretch viscoelastic 80 ℃ tan δ value below 0.09 depending on of 0.05Hz,

(d) 70 ℃ anti-roll curvature more than 45%,

(e) thickness is at the 40-120 mu m range, and

(f) its laminate film for constituting by the ground floor and the second layer, ground floor is by poly-2, the 6-(ethylene naphthalate) constitutes, the mean grain size that can contain less than 0.003 weight % is the inert particulate of 0.01-1.5 μ m, the second layer is by poly-2, the 6-(ethylene naphthalate) constitutes, and containing 0.003-0.5 weight % mean grain size is the inert particulate of 0.01-1.5 μ m, and second layer thickness is below 10 μ m.

18. the method according to claim 17 is characterized in that, the thickness t of the sheet base film second layer ₂The particle diameter d of the inert particulate that (μ m) and the second layer are contained ₂The ratio of (μ m) is in the 0.1-10 scope.

19. the method according to claim 17 is characterized in that, the thickness of the sheet base film second layer is below 5 μ m.

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