CN100339205C - Polyamide resin film roll, and production method therefor - Google Patents
Polyamide resin film roll, and production method therefor Download PDFInfo
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- CN100339205C CN100339205C CNB2005100742498A CN200510074249A CN100339205C CN 100339205 C CN100339205 C CN 100339205C CN B2005100742498 A CNB2005100742498 A CN B2005100742498A CN 200510074249 A CN200510074249 A CN 200510074249A CN 100339205 C CN100339205 C CN 100339205C
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Abstract
To provide a biaxially oriented polyamide based resin film roll capable of bag forming processing by lamination smoothly with high yield ratio and obtaining a package free from S-shaped curl efficiently. [SOLUTION] The polyamide based resin film roll of the present invention comprising: a first sample cutout portion within 2 m from the winding end of film; and a final cutout portion within 2 m from the winding start of film, wherein when a sample cutout portion is set up in approximately every 100 m from the first sample cutout portion, in all samples cut out from each of the cutout portions, mechanical properties such as boiling water shrinkage percentage and refraction index in the thickness direction are adjusted within a given range of variation width.
Description
Technical field
The present invention relates to a kind of manufacture method of making the even and high-quality film volume of rerum natura in the longitudinal direction with high production rate, this film batches polyamide-based resin film and forms, in more detail, relate to be used to make with polyolefin resin film lamination after the manufacture method of the good polyamide resin film roll of processability when being used for packing such as cooking food.
Background technology
Owing to the double-axle orientation polyamide based resin film that with nylon is main component is comparatively tough, aspects such as vapour lock, anti-pin hole, the transparency, printing are good, therefore be widely used in the packaging material of various food such as various food liquids, food containing water, frozen food, cooking food, paste food, poultry meat aquatic food, particularly in recent years, be widely used in the packing of cooking food.Laminations such as this polyamide-based resin film and for example polyolefin resin such as polyethylene and polypropylene film, be parallel to the direction doubling of scrolling, to cut out behind its 3 limit heat fusing joint, form 3 limit sealing bags of the open Kaifeng state in 1 limit, after sealing such as various food is filled in inside, pasteurization in boiling water is supplied to market.
But, when using the double-axle orientation polyamide based resin film, pasteurization is handled the back can produce bending in the corner portions located of packaging bag, and the curling phenomenon (hereinafter referred to as the curling phenomenon of S type) that becomes the S shape in its 4 limit takes place, and makes the remarkable variation of outward appearance of package goods sometimes.For this reason, as the method that this curling phenomenon is alleviated, shown in patent documentation 1, proposed a kind of with the double-axle orientation polyamide based resin film boiling water contraction distortion rate and the long-pending method that is adjusted to specific value of the rate of change of the thin-film width direction of angle of molecular orientation, but in this method, in order to improve the dimensional stability when the boiling water treating, temperature in the time of must be with heat fixation improves terrifically, and the lax heat treatment after exceedingly implementing to extend, thereby produce the obdurability of the film that obtains and the problem that anti-pin hole suffers damage.
Therefore, shown in patent documentation 2, propositions such as applicant are a kind of to be adjusted to specific number range by boiling water shrinkage and refractive index with film, can not reduced obdurability and anti-pin hole and not produce the method for the double-axle orientation polyamide based resin film that the S type curls.
Patent documentation 1: the spy opens flat 4-103335 communique
Patent documentation 2: the spy opens flat 8-174663 communique
By the method for above-mentioned patent documentation 2, it is good to obtain tough and anti-pin hole, does not produce the double-axle orientation polyamide based resin film that the S type curls.Yet, in the bag processing of adopting lamination, the condition of pressure when its heat fusing is engaged and time etc. will involve in the row fine setting according to the film of each use, therefore, even the mean value that is wound into physics values such as the boiling water shrinkage of film of film volume and refractive index is in the scope of patent documentation 2, when the variable quantity of a film volume is big, in bag processing, between film, produce fold when easily lamination taking place, make the problem of yield rate variation etc.
On the other hand, applicants etc. have also proposed a kind of winding film that twin shaft extends after will mixing various kinds of resin and melt extruding and have got up to make in the method for double shaft extensioning film volume, the method that the variation of the coefficient of kinetic friction is reduced, promptly making peace by the shape one that makes material web increases the angle of inclination of conduct to the funnel-form hopper of the raw material supply portion of extruder, can reduce the method (spy opens 2004-181777) of the segregation of raw material.Yet, as the variation of rerum naturas such as the boiling water shrinkage of the film that suppresses to be wound into the film volume and refractive index and the method for deviation, this method a kind of conclusive method of can't saying so.
Therefore, the applicant is after having carried out positive research and development to the production technology that is used to produce highly uniform double shaft extensioning film volume, the rerum natura height of having invented film thickness, boiling water shrinkage, refractive index is even, the polyamide resin film roll (the special 2004-262922 of hope) that can not produce fold during lamination between the film and can carry out the high bag processing of yield rate.
When making above-mentioned polyamide resin film roll,, do not extend thin slice and form from the extruder thin slice that melt extruded goes out by mould cooling curing on chill roll mobile cooling bodies such as (metallic roll).In addition, in aforesaid cooling curing process of being undertaken by chill roll, if the polyamide-based resin thin slice of molten condition directly is not close to by thin layer of air on the mobile cooling body, can the chilling molten resin, and can access the low not extension thin slice of crystal degree.Thus, in the cooling curing that is undertaken by chill roll, adopt following method: promptly forcibly be close on the cooling body surface at short notice for the fusion thin slice that will be extruded, and the electrode of wire-shaped is set between mould and mobile cooling body, and should be uncured after on the surface of uncured thin slice, separating out electrostatic charge thin slice force to be close on the cooling body surface (below, force the manufacturing process of the uncured thin slice be close to be referred to as to add the static forming process this electrostatic charge of utilizing).
Summary of the invention
But, when the draw speed of thin slice is slow, can be close to by the electrostatic charge of separating out at sheet surface, but the words that exceed draw speed just can not be close to by electrostatic force, and thin layer of air can enter between the thin slice and mobile cooling body surface of molten condition, cause the thickness of thin slice to change and delay the cooling of fusion thin slice, produce inhomogeneous cooling, promote crystalization also to obtain having uneven and the thin slice that the transparency is bad of crystalization.In addition, the oligomer that also can separate out polyamide polymers on the mobile cooling body surface.For this reason, in order to be increased in the amount of electrostatic charge of separating out on the sheet-like article surface, and when improving the voltage be applied on the electrode that disposes between mould and the mobile cooling body surface, produce discontinuous arc discharge between electrode and the cooling body surface, thereby destroy the sheet-like article on cooling body surface, when serious even can to destroy cooling body surface-coated.Therefore, the voltage that is applied to electrode is surpassed to a certain degree, add in the static forming process, can not improve film speed fully and produce the uniform polyamide resin film roll of height described in the above-mentioned special 2004-262922 of hope existing.
After the improvement of the prior art that inventors' active research of the present invention is relevant, obtain following opinion: the polyamide-based resin that will have film formation property is when mobile cooling body melt surface is squeezed into laminar and cools off, use multi-needle electrode and between this multi-needle electrode and molten resin thin slice, carry out the corona discharge of time corona state, the polyamide-based resin thin slice that can supply with molten condition enough makes it cling to the electric charge on mobile cooling body surface, and can not produce arc discharge, can enough low-voltages produce high electric current.At one stroke solved the above-mentioned existing many defectives that add in the static forming process thus, and can be produced at a high speed do not pile up on the mobile cooling body oligomer, thickness evenly, the transparency is good, the crystal degree is low and the crystal uneven phenomenon is few polyamide-based resin thin slice; And its system film is also more stable during with conventional speeds (existing speed) system film, thereby has reached the present invention.
In the present invention, the invention of technical scheme 1 record relates to a kind of with the manufacture method of the polyamide resin film roll below the above 3.0m of wide 0.2m, below the above 30000m of long 300m around the polyamide resin film roll that gets up to form, and it comprises following operation: the refrigerating work procedure that melt extrudes that polyamide-based resin is not extended thin slice on mobile cooling body surface with laminar melt extruded and cooling; With the above-mentioned along the longitudinal and laterally twin shaft extension process that extends of twin shaft of thin slice that do not extend; And will be wound into the coiling operation of roller shape by the double shaft extensioning film that twin shaft extends, melt extrude in the refrigerating work procedure above-mentioned, with above-mentioned polyamide-based resin on mobile cooling body surface with melt extruded and when cooling off, between the polyamide-based resin thin slice of electrode that applies high direct voltage and above-mentioned molten condition, carry out the corona discharge of time corona state, provide the polyamide-based resin thin slice that enough makes molten condition to cling to the electric charge on mobile cooling body surface, make the polyamide-based resin film that is wound into the roller shape begin 2m with the interior portion that cuts out that the 1st sample is set at coiling terminal point from film, this is external to begin 2m from the winding film starting point and with interior the final portion that cuts out is set, every about 100m sample is set since the 1st sample portion that cuts out simultaneously and cuts out portion, when these being set cutting out portion, satisfy following requirement (1), (2) also satisfy following requirement (3) time.
(1) for each sample that cuts out from the aforementioned respectively portion of cutting out, when measuring when being peaked maximum boiling water shrinkage in the boiling water shrinkage in all directions, average boiling water shrinkage as the mean value of these maximum boiling water shrinkages is 2%～6%, and the rate of change of the maximum boiling water shrinkage of all samples is being in ± 2%～± 10% the scope with respect to aforementioned average boiling water shrinkage simultaneously;
(2) for each sample that cuts out from the aforementioned respectively portion of cutting out, when obtain as with respect to length direction for the boiling water shrinkage of+45 degree directions with respect to length direction during for the boiling water shrinkage direction difference of absolute value of the difference of the boiling water shrinkage of-45 degree directions, below 1.5%, the rate of change of the boiling water shrinkage direction difference of all samples is being in ± 2%～± 10% the scope with respect to aforementioned average boiling water shrinkage direction difference simultaneously as the average boiling water shrinkage direction difference of the mean value of these boiling water shrinkage direction differences;
(3) thickness change on the total length of the length direction of the roller that winds up is being in ± 2%～± 10% the scope with respect to average thickness.
The invention of technical scheme 2 records is, on the basis of the invention that technical scheme 1 is put down in writing, the polyamide-based resin film that is wound into the roller shape is for each sample that cuts out from the aforementioned respectively portion of cutting out, when measuring the refractive index of thickness direction, more than 1.500 below 1.520, the variations in refractive index rate of all simultaneously samples is being ± 2% with interior scope with respect to aforementioned mean refractive index as the mean refractive index of the mean value of these refractive indexes.
The invention of technical scheme 3 records is, on the basis of the invention that technical scheme 1 is put down in writing, the polyamide-based resin film that is wound into the roller shape is for each sample that cuts out from the aforementioned respectively portion of cutting out, when measuring the refractive index of thickness direction, as the mean refractive index of the mean value of these refractive indexes more than 1.500 below 1.520, the variations in refractive index rate of all simultaneously samples with respect to aforementioned mean refractive index be ± 1% with interior scope in.
The invention of technical scheme 4 records is that on the basis of the invention that technical scheme 1 is put down in writing, the main component that constitutes the polyamide of polyamide-based resin film is a nylon 6.
The invention of technical scheme 5 record is, on the basis of the invention of technical scheme 1 record, will by the different polyamide resin film rolls that the mixture of polyamide forms more than 2 kinds around.
The invention of technical scheme 6 record is, on the basis of the invention of technical scheme 1 record, the polyamide-based resin film that winds up is the film with polyolefin resin film lamination.
The invention of technical scheme 7 record is, on the basis of the invention of technical scheme 1 record, the polyamide resin film roll that will extend by the tentering extension method is around getting up.
The invention of technical scheme 8 record is, on the basis of the invention of technical scheme 1 record, the polyamide-based winding film that twin shaft is one by one extended gets up.
The invention of technical scheme 9 records is, on the basis of the invention that technical scheme 1 is put down in writing, the sheet-like article that unoriented in fact polyamide-based resin is formed is under the high temperature more than vitrification point+20 of aforementioned polyamide-based resin ℃, by at least 2 stages after the multiplying power of longitudinal extension more than 3 times, to the multiplying power of horizontal extension more than 3 times, with this polyamide resin film roll around getting up.
The invention of technical scheme 10 record is, on the basis of the invention of technical scheme 1 record, will carry out final extension handle the fixing polyamide resin film roll of after heat around.
The invention of technical scheme 11 record is, on the basis of the invention of technical scheme 1 record, with the polyamide resin film roll that carried out relaxation processes behind the heat fixation around.
The invention of technical scheme 12 records is, on the basis of the invention that technical scheme 1 is put down in writing, in the polyamide-based resin film that winds up, add at least a kind in lubricant, anticaking agent, heat stabilizer, antioxidant, antistatic additive, photostabilizer, the resistance to impact modifying agent.
The invention of technical scheme 13 records is on the basis of the invention that technical scheme 1 is put down in writing, in the polyamide-based resin film that winds up, to add inorganic particle.
The invention of technical scheme 14 records is that on the basis of the invention that technical scheme 13 is put down in writing, inorganic particle is that average grain diameter is the silica dioxide granule of 0.5～5.0 μ m.
The invention of technical scheme 15 records is on the basis of the invention that technical scheme 1 is put down in writing, in the polyamide-based resin film that winds up, to add higher fatty acids.
The invention of technical scheme 16 records is, on the basis of the invention that technical scheme 1 is put down in writing, between the polyamide-based resin thin slice of multi-needle electrode that applies high direct voltage and molten condition, carry out the above-mentioned corona discharge that melt extrudes the time corona state in the refrigerating work procedure.
Manufacturing method according to the invention, can produce at a high speed thickness evenly, the crystal degree is low and transparent good, crystal inequality polyamide-based resin thin slice seldom, and the pollution that causes of the oligomer of the cooling body that can not be moved.Therefore, manufacturing method according to the invention can be with very high film speed, produce the uniform polyamide resin film roll of height described in the above-mentioned special 2004-262922 of hope extremely expeditiously.That is,, can almost there be obstacle ground to carry out bag processing, obtain the packing material that do not have the S type curling expeditiously by lamination glibly by the polyamide resin film roll that manufacture method of the present invention is made with very high productivity ratio.In addition, in back processing such as bag processing, can obtain processed finished products with high rate of finished products.In addition, comparatively tough if use the polyamide resin film roll of making by manufacture method of the present invention by the sack of the used for packing foods after the processing of lamination bag, and anti-pin hole is good.
Description of drawings
Fig. 1 expresses configured electrodes on mobile cooling body and the key diagram that carries out time state during corona discharge.
The specific embodiment
Preferable production process to the manufacture method of polyamide resin film roll of the present invention describes below.Manufacturing method according to the invention, polyamide resin film roll be by, polyamide-based resin (polyamide slice raw material) is melt extruded the not extension thin slice that obtains (length direction) and after laterally (width) twin shaft extends along the longitudinal, be wound into the roller shape and make.
As the polyamide-based resin that uses in the present invention, for example can enumerate, with the epsilon-caprolactams nylon 6 of main material.In addition, as other polyamide, the polyamide that can enumerate the above lactams of 3 yuan of rings, omega-amino acid, obtain by the polycondensation of binary acid and diamines etc.Specifically,, except the epsilon-caprolactams shown in before, also have oenantholcatam, spicy inner formyl amine, lauramide,, can enumerate 6-aminocaprolc acid, 7-aminoheptylic acid, 9 aminononanoic acid, the ten-acid of 11-amino as the omega-amino-acids as lactams.In addition, as the binary acids, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid, hexadecandioic acid (hexadecane diacid), eicosane diacid, eicosane two enedioic acids, 2,2,4-trimethyladipic acid, terephthalic acid (TPA), M-phthalic acid, 2,6-naphthalene dicarboxylic acids, xyxylene dicarboxylic acids.And then, as two amines, can enumerate ethylenediamine, propane diamine, butanediamine, hexamethylene diamine, pentanediamine, hendecane diamines, 2,2,4 (or 2,4,4)-trimethyl hexamethylene diamine, cyclohexanediamine, two-(4,4 '-aminocyclohexyl) methane, MXDP etc.Also have, can use polymer or its copolymer that its polycondensation is obtained, for example nylon 6,7,11,12,6.6,6.9,6.11,6.12,6T, 6I, MXD6 (an xyxylene adipoyl diamines 6), 6/6.6,6/12,6/6T, 6/6I, 6/MXD6 etc.In addition, when manufacturing polyamide film of the present invention is rolled up, can use above-mentioned polyamide individually, perhaps be mixed with two or more.
In addition, in the above-mentioned polyamide-based resin, the preferred especially relative viscosity of the present invention is the resin of 2.0～3.5 scope.The relative viscosity of polyamide-based resin is influential to the obdurability of the double shaft extensioning film that makes and ductility etc., resin for relative viscosity less than 2.0, its impact strength may be not enough, otherwise, surpass 3.5 resin for relative viscosity, because extend the increase of stress, the twin shaft extensibility has the tendency of variation one by one.In addition, so-called relative viscosity is meant among the present invention, uses with the solution of 0.5g polymer dissolution in 50ml, 97.5% sulfuric acid the value that obtains when measuring down for 25 ℃.
In melt extruding in the process of polyamide-based resin (polyamide-based resin slice raw material), by as extruding at flat board in the flat-dies such as T mould, I mould.The thin slice that is extruded cools off on the surface of chill roll mobile cooling bodies such as (metallic roll), obtains the non-directional thin slice in fact.In order to suppress the crystalization of sheet extrusion, the preferred range of the chilling temperature of sheet extrusion is below the above crystal maximum temperature-20 of dew point ℃.Above-mentioned crystal maximum temperature (Tc) is obtained by DSC (Differential Scanning Calorimeter, differential scanning calorimetry (DSC)), and nylon 6 is generally 180～200 ℃, but according to the various additives of the kind of polymer, interpolation and difference.When the chilling temperature of sheet extrusion is more than Tg+10 ℃ the time, the thin slice easy deformation that is cooled, thus in order to cool off below Tg+10 ℃, preferably carry out the cooling of 2 stages.The cooling of sheet extrusion can be used opposite side coating cooling fluid, spraying refrigerating gas, the impregnating cooling means the cooling liquid bath from mobile cooling body surface simultaneously.
The surface of mobile cooling body can mirror finish or roughing.Facing material preferably uses the material that can stand long-term use, but does not limit especially.Facing materials such as for example hard chromium plating, ceramic coating, special teflon (registration mark) coating.
Can overlapping how many alternating components in the HVDC that uses among the present invention, but the best dc source of working voltage or current stabilization, and peak-peak value of measuring when preferably artificial resistance being connected to output and ground is the dc source below 1.0%.The polarity of electrode does not limit, the preferred negative current potential.
Of the present invention being characterized as: by between the polyamide-based resin thin slice of electrode and melt extruded, generating the corona discharge of time corona state, thereby can utilize low pressure that high electric current is provided, compare the above-mentioned static forming process that adds electric current more than tens of times can be provided.Here, the corona discharge of time corona state is meant corona state stable behind electrode and ground connection flat board (molten resin thin slice) bridge joint (please refer to special public clear 62-41095 communique).When electrode is positive potential, form with bar-shaped concentrated corona at the fusion thin slice from the electrode front end; When electrode is negative potential, form hanging the corona that mitriform enlarges at the fusion thin slice from the electrode front end, can adopt above any corona discharge as the corona discharge of the time corona state among the present invention.
In order stably to generate the corona discharge of time corona state of the present invention, must discontinuous configuration point of discharge.For this reason, preferably, be not particularly limited among the present invention as multi-needle electrode (a plurality of spicules roughly not being had the gap and the electrode that is arranged in parallel towards same direction), saw blade shape electrode from the length shape supporter of insulants such as silicon-coating.The quantity of point of discharge and aligning method can be selected arbitrarily.The material of discharge body for example can be used metal (particularly stainless steel), carbon etc. so long as the words of the object of electric conductivity can be selected for use in addition.In addition, the preferred front end of the spicule in the multi-needle electrode is an acute angle shape.When the front end of above-mentioned spicule was acute angle shape, the part beyond the front end is of a size of the words time corona state of 0.5～5.0mm φ (diameter) can be more stable, therefore preferred, more preferably 1.0～3.0mm φ.In addition, do not need to discharge to the molten resin thin slice, by adjusting the interval that the voltage that is applied can suitably change the time corona discharge from whole spicules of multi-needle electrode.
In addition, in the method for the invention, in order stably to generate the corona discharge of time corona state, for example the gap between the point of discharge of preferred electrode and the molten resin thin slice is 2～20mm, the scope of preferred especially 2～10mm.When disposing point of discharge as mentioned above, between the polyamide-based resin thin slice of electrode and molten condition, generate together honorable and stable time corona discharge, produce high electric current simultaneously.In addition, though the thickness of the thin slice that is shaped by the present invention is not particularly limited preferred 50～500 μ m, more preferably 100～300 μ m.In addition, the draw speed for the thin slice that is shaped among the present invention does not limit especially.By the existing possible maximum speed that adds the draw speed of static forming process approximately is 50m/min, but in the method for the invention, can also can be close to cooling under this about 80m/min more than draw speed.In addition, as mentioned above, utilizing the time during corona discharge, though the possible maximum speed of draw speed increases at a gallop, but under common draw speed, utilize the time during corona discharge,, thereby reduced the frequency of fracture significantly because the system film is more stable.
In addition, as mentioned above, utilizing the time during corona discharge,, then can reduce the uneven thickness longitudinally of film volume, the variation and the deviation of rerum natura if the direct current negative electrical charge that adds is adjusted in the scope of 7～14kv, therefore preferred.In addition, in the manufacture method of film of the present invention volume, the deviation of the voltage that adds must be suppressed at average voltage (setting value) ± 20% in, more preferably be suppressed at ± 10% in.
In addition, as mentioned above, carry out the time during corona discharge, the electrode ambient air is adjusted in humidity 40～85%RH, 35～55 ℃ of scopes of temperature, do not make it become drying regime but more than humidification state, do not form the degree of dew point a little, can prevent that oligomer (oligomer of epsilon-caprolactams etc.) from attached to the needle point of electrode and the front end of saw blade, making that the time corona discharge is more stable this moment, thereby preferred.Preferred humidity range is 60～80%RH; Preferred temperature range is 40～50 ℃.
Below, with reference to the accompanying drawings, method of the present invention is described.Fig. 1 is the key diagram of an embodiment of manufacturing process of the thin slice of relevant the inventive method.In Fig. 1, extrude laminar molten mass 2, and be cooled to become after solidifying by chilling roll 3 and do not extend thin slice 4 from mould 1.Apply voltage by DC high-voltage power supply 5 to electrode 6, and time corona discharge 7 takes place on laminar molten mass by electrode 6.
Manufacturing method according to the invention, polyamide resin film roll be by, above-mentioned resin (polyamide thin slice) melt extruding the not extension thin slice that obtains (length direction) and after laterally (width) twin shaft extends along the longitudinal on the surface of mobile cooling body, is wound into the roller shape and makes.
Present inventors roll up the variation and the deviation of rerum naturas such as uneven thickness longitudinally (along the uneven thickness of the total length of film volume), boiling water shrinkage and study to film, found that this variation of uneven thickness and rerum natura longitudinally and deviation mainly are subjected to the considerable influence of the various key elements in the resin of fusion being made the forming process of extension film not.That is to say, found if the temperature of resin reduces when being fed to the direct-connected funnel-form hopper of extruder (being designated hereinafter simply as hopper), or be supplied to the moisture of the resin of hopper to raise, then not in the extension film longitudinally uneven thickness increase, the variation of rerum natura and deviation increase in the double shaft extensioning film.In addition, find when be wound on the resin of extruding from the T mould on the metallic roll, when the contact point of resin and metallic roll is chaotic, not in the extension film longitudinally uneven thickness increase, the variation of the rerum natura of double shaft extensioning film and deviation become greatly.And then, also found if the extension condition is not suitable in the twin shaft extension process then not extension film uneven thickness increase longitudinally, thereby the variation and the deviation of growth encourage rerum natura.
Further, based on the above-mentioned fact, present inventor etc. have carried out positive research, found that, when making the film volume, by following method is described, can obtain the less film volume of variation of rerum natura.
(1) homogenising of the shape of resin flake;
(2) suitableization of hopper shape;
Moisture when (3) reducing the resin flake drying;
Temperature when (4) hopper being supplied with resin keeps;
Attraction when (5) molten resin contacts with metallic roll;
(6) suitableization of extension condition.
Below above-mentioned each method is described in turn.
(1) homogenising of the shape of resin flake
In the manufacturing of film of the present invention volume, when adopting hybrid mode,, carry out melting mixing with after forming different plurality of raw materials polyamide thin slices and in hopper, mixing, from extruder, extrude filming.For example, be under 3 kinds the situation when polyamide as raw material, in 3 hoppers, supply with polyamide thin slice separately respectively continuously or off and on, in case of necessity by the buffering hopper, final by the extruder dead ahead or directly over hopper (hereinafter referred to as " final hopper ") one side mix the polyamide thin slice of 3 kinds, the extrusion capacity that cooperates extruder forms film quantitatively to extruder base feed thin slice on one side.
In addition, capacity or shape about final hopper, under the situation that the residual quantity of thin slice tails off in situation that thin slice amount in final hopper is more and the final hopper, find the phenomenon of raw material segregation, promptly be fed to the different phenomenon of composition of the thin slice of extruder from final hopper.In addition, this segregation phenomena occurs under the different situation of lamella shape or proportion especially significantly.And then because this segregation phenomena, when making rectangular film, maximum boiling water shrinkage, boiling water shrinkage direction are poor, the variations in refractive index of film thickness, thickness direction.
That is to say that if the size difference of thin slice, when the mixture of thin slice fell in the final hopper, because less thin slice falls earlier easily, if the thin slice residual quantity in the final hopper tails off, the ratio of then bigger thin slice increased, this is the reason of raw material segregation.Therefore, change less film volume, must cooperate the shape of employed multiple polyamide thin slice, thereby be suppressed at the raw material segregation phenomena in the final hopper in order to obtain rerum natura.
The material web of polyamide after polymerization, is taken out with wire by polyplant under molten condition usually, after the water-cooled, forms by the line material cutter cutting at once.Therefore, the cross section of the thin slice of polyamide becomes oval-shaped oval column.Wherein, after the shape of polymer flake and the relation between the raw material segregation studied, the average major diameter (mm) of the cross section ellipse of other polyamide thin slice by will being blended in the maximum polyamide thin slice of use amount, average minor axis (mm), average thin slice long (mm) be adjusted into respectively the polyamide maximum with respect to use amount material web the cross section ellipse average major diameter (mm), average minor axis (mm), average thin slice long (mm) ± 20% with interior scope in, can reduce the above-mentioned raw materials segregation.In addition, if will be blended in the average major diameter of the cross section ellipse of the long material web that is adjusted into the polyamide maximum respectively of the average major diameter of the cross section ellipse of the polyamide thin slice beyond the maximum polyamide thin slice of use amount, average minor axis, average thin slice, average minor axis, average thin slice length with respect to use amount ± 15% with interior scope in, then because segregation prevents that effect is extremely remarkable, therefore more preferably.
(2) suitableization of hopper shape
Use the funnel-form hopper as final funnel,, big thin slice and little thin slice are all fallen easily by making its inclination angle more than 65 °, because it is the upper end of inclusion descends when remaining on horizontal plane, therefore effective for the reduction of raw material segregation.More preferably the inclination angle is more than 70 °.In addition, the inclination angle of hopper is meant, the angle between funnelform hypotenuse and the horizontal line.Can use a plurality of hoppers in the upstream of final hopper, the inclination angle that at this moment must make any one hopper is more than 65 °, more preferably more than 70 °.
In addition, in order to suppress the variation of boiling water shrinkage, preferably the ratio of the fine powder body that will be caused by the cutting of employed material web etc. reduces.Because the fine powder body has promoted the generation of raw material segregation, therefore preferably remove the fine powder body that produces at in-process, reduce the ratio of fine powder body contained in the hopper.In the process that runs through whole operation that enters extruder up to material web, preferably with the proportion control of contained fine powder body in 1 weight %, more preferably be controlled in the 0.5 weight %.As the concrete grammar of the ratio that reduces the fine powder body, can enumerate when forming thin slice and pass through sieve, or when air transports material web, remove the method for fine powder body by circulating air cleaner etc. with line material cutter.
In addition, as the method that reduces the raw material segregation in the hopper, it also is preferable methods that the capacity of employed hopper is suitably changed.Wherein, the suitable capacity of hopper is, with respect to the per 1 hour discharge capacity of extruder in the scope of 15～120 weight %, more preferably with respect to the per 1 hour discharge capacity of extruder in the scope of 20～100 weight %.
As mixing the method for forming different polyamide raw materials thin slices more than 2 kinds, most preferably one side is metered into extruder from the hopper (final hopper) directly over the extruder continuously with each raw material, Yi Bian the method for mixing.In addition, also can be after the material web of size Control in aforementioned range with material web is pre-mixed, by several middle hoppers (buffering hopper), and be fed to final hopper and extruder.When mixing plurality of raw materials, can enumerate the method for when the device of continuous and quantitative base feed thin slice is fed to plurality of raw materials in the hopper, mixing, the method of perhaps using mixer or slurry formula drying machine etc. to mix in advance, when adopting the latter, in order when mixture is discharged, the raw material segregation not to take place, preferably reduce the size of material web.
Moisture when (3) reducing the resin flake drying
The thin slice that is fed in the hopper is heated and minimizing moisture by devices such as mixers usually.When this thin slice of drying, in making polyester film volume or polypropylene film volume, it is generally acknowledged when drying and fall moisture low more, the good film volume of the hydrolysis that in extrusion process, just can be inhibited.But, the result that present inventors study is, in making polyamide resin film roll, if be only merely to reduce when dry moisture, then extend the difficulty that becomes, can not get the uniform film volume of rerum natura, and by moisture being controlled at prescribed limit, guarantee moisture to a certain degree, in extrusion process, do not make its hydrolysis and make its moderately plasticization, can obtain the uniform film volume of rerum natura.That is to say,, the moisture of thin slice must be controlled at below the above 1000ppm of 800ppm in order to obtain the film volume of manufacturing method according to the invention.If the moisture of thin slice surpasses 1000ppm, then when making its fusion, can promote hydrolysis, viscosity reduces, not extension film longitudinally uneven thickness worsen, double shaft extensioning film uneven thickness longitudinally increases, and becomes the variation that causes rerum natura and the reason of deviation.Otherwise if the moisture of thin slice is lower than 800ppm, then viscosity is too high when making its fusion, system film (the easy degree of extension) variation.In addition, the optimal moisture that is fed to the thin slice in the hopper is below the above 950ppm of 850ppm.
Temperature when (4) hopper being supplied with resin keeps
As mentioned above, even be adjusted at below the above 1000ppm of 800ppm in moisture with thin slice, the thin slice after placing heat drying and reduce to normal temperature (room temperature) after when being fed in the hopper again, can not obtain the uniform film volume of rerum natura.That is to say,, must make thin slice remain on high temperature, be fed in the hopper by heat dryings such as mixers in order to obtain the film volume of manufacturing method according to the invention.Specifically, must remain on more than 80 ℃ by the thin slice of mixer heat drying and be fed in the hopper, more preferably remain on more than 90 ℃ and be fed in the hopper.If the thin slice temperature that is fed in the hopper is lower than 80 ℃, the engaging-in variation of resin becomes and causes uneven thickness and the variation of rerum natura and the reason of deviation longitudinally, can not get film volume of the present invention.In addition, when by device drying slices such as mixers, baking temperature must be adjusted at below 150 ℃.Some dry temperature surpass 150 ℃, may cause hydrolysis when then dry, and are therefore not preferred.In addition, when the temperature of the thin slice by the mixer heat drying is lower than 80 ℃, then must be warmed up to once more more than 80 ℃ and be fed in the hopper.
Attraction when (5) molten resin contacts with metallic roll
Melt extruding thin slice when obtaining not extension film, as mentioned above, under 200～300 ℃ temperature, make its fusion by extruder, from the T mould, extrude, shaping (being injection moulding) makes its chilling for behind the film shape (laminar) by the method that it is wound on the chill rolls such as metallic roll that are cooled to set point of temperature.In addition, from the variation of uneven thickness, rerum natura and the angle of deviation longitudinally, preferred melt extruded temperature is 240～290 degree.For manufacturing method according to the invention obtains the film volume, when being wound on the resin of fusion on the metallic roll, the air gap the distance of the gravity direction that exports to the chilled roll surface of T mould nozzle (promptly from) adjusted to 20～60mm, utilize the vacuum tank suction devices such as (vacuum chambers) of attraction mouth simultaneously with broad, on the whole width of molten resin, attract molten resin and the part that the chill roll surface contacts along the direction opposite, molten resin is close to metallic roll forcibly with coiling direction.In addition, at this moment attract the attraction wind speed of notch portion must be adjusted to 2.0～7.0m/sec, preferably be adjusted to 2.5～5.5m/sec.Further, vacuum tank can be and attract the pattern that fuses of mouth,, preferably attracts mouthful in the zone that laterally is divided into the regulation number pattern that can adjust the attraction wind speed in each zone in order easily to adjust the attraction wind speed that attracts mouthful.In addition, if increase the speed of injection moulding, then along with stream is followed in the rotation generation of metallic roll, the obstruction molten resin is close to metallic roll, therefore, and in order more effectively to attract by suction device, improve the be close to degree of molten resin to metallic roll, preferably form roomy baffle plate, be arranged on and the upstream side of suction device adjacency (with respect to a side of the direction of rotation of suction device and metallic roll), follow stream with blocking-up with soft materials such as special teflon.And then, for manufacturing method according to the invention obtains film volume, the deviation of the attraction wind speed of vacuum tank must be suppressed at average attraction wind speed (setting value) ± 20% with in the interior scope, more preferably be suppressed at ± 10% with in the interior scope.In addition, in order not allow the dust etc. of oligomer change the attraction wind speed of vacuum tank, filter preferably is set, in vacuum tank simultaneously by the pressure reduction before and after this filter of feedback, to regulate attraction.
(6) suitableization of extension condition
As extension film not being carried out the method that twin shaft extends, need to adopt by the roll-type elongator not extension film after horizontal extension, carry out that heat fixation is handled and the extension method in length and breadth of relaxation processes etc. by tentering formula elongator to longitudinal extension.And then, for manufacturing method according to the invention obtains the film volume,, need to adopt so-called indulging-vertical-horizontal extension method as the method that twin shaft extends.Should be meant by vertical-vertical-horizontal extension method, when unoriented in fact polyamide film being indulged extension, carry out the extension of phase I, be not cooled to below the Tg, then carry out the extension of second stage, then with more than 3.0 times, preferred multiplying power more than 3.5 times carries out horizontal extension, carries out the method for heat fixation again.Thus, for manufacturing method according to the invention obtains film volume, carry out above-mentioned vertical-vertical-during horizontal extension method, the vertical extension ratio of phase I must be higher than the vertical multiplying power of extending of second stage.That is to say, must be higher than the vertical multiplying power of extending of second stage by the vertical extension ratio that so makes the phase I, it is good to obtain rerum natura such as boiling water shrinkage, and the less film volume of the deviation of these rerum naturas.In addition, indulging-indulge-during horizontal extension, usually, if making the vertical extension ratio of phase I be lower than the vertical multiplying power of extending of second stage extends, then when the extension of phase I, can not produce the adhesion of pair roller, can easily extend, but by using the special rollers such as roller of special teflon (registration mark) system, even when the vertical extension ratio of phase I is higher than the vertical multiplying power of extending of second stage, also can produce the adhesion of pair roller and easily extend.
As above indulging-indulge-during horizontal extension, the vertical extension of phase I is preferably extended 2.0～2.4 times under 80～90 ℃ temperature.If the extension ratio of phase I exceeds above-mentioned scope, then uneven thickness increases longitudinally, and is therefore not preferred.In addition, the vertical extension of second stage is preferably extended 1.3～1.7 times under 65～75 ℃ temperature.If the extension ratio of second stage is lower than above-mentioned scope, then the boiling water distortion increases, become the material that does not have practicality, therefore not preferred, on the contrary, if the extension ratio of second stage exceeds above-mentioned scope, then intensity (intensity during 5% elongation etc.) reduces longitudinally, become the material that does not have practicality, therefore not preferred.
In addition, when as above indulge-indulge-during horizontal extension,, can adopt hot-rolling extension, infra-red radiation extension etc. as vertical method of extending.In addition, by so vertical-vertical-when horizontal extension method is made polyamide-based resin film, not only can reduce the variation and the deviation of uneven thickness, rerum natura longitudinally, can also reduce the variation and the deviation of horizontal rerum natura.In addition, indulging-indulge-during horizontal extension, preferably 3.0～4.5 times of always vertical extension conditions.
Indulging-indulge in addition ,-during horizontal extension, horizontal extension is preferably extended 4.0～5.5 times under 120～140 ℃ temperature.If the extension ratio of horizontal extension is lower than above-mentioned scope, then horizontal intensity (intensity during 5% elongation etc.) reduces, and becomes the material that does not have practicality, therefore not preferred, on the contrary, if the extension ratio of horizontal extension exceeds above-mentioned scope, then horizontal percent thermal shrinkage increases, and is therefore not preferred.On the other hand, if the temperature of horizontal extension is lower than above-mentioned scope, then the boiling water distortion increases, become the material that does not have practicality, therefore not preferred, on the contrary, if the temperature of horizontal extension is higher than above-mentioned scope, then horizontal intensity (intensity during 5% elongation etc.) reduces, and becomes the material that does not have practicality, and is therefore not preferred.
And then for manufacturing method according to the invention obtains the film volume, the heat fixation after vertical-vertical-horizontal extension is handled and is preferably carried out under 180～230 ℃ temperature.If the temperature that heat fixation is handled is lower than above-mentioned scope, then the percent thermal shrinkage of vertical and horizontal increases, and is therefore not preferred, and on the contrary, if the temperature that heat fixation is handled is higher than above-mentioned scope, then the impact strength of double shaft extensioning film reduces, and is therefore not preferred.
In addition, for manufacturing method according to the invention obtains the film volume, the relaxation processes behind the heat fixation preferably makes it relax 2%～10%.If the ratio of relaxation processes is lower than above-mentioned scope, then the percent thermal shrinkage of vertical and horizontal increases, and is therefore not preferred, on the contrary, if the ratio of relaxation processes is higher than above-mentioned scope, then the intensity of vertical and horizontal (intensity during 5% elongation etc.) reduces, become the material that does not have practicality, therefore not preferred.
In addition, the width of rolling up for film has no particular limits, and from maneuverable angle, the width lower limit of film volume is preferably more than 0.35m, more preferably more than 0.50m.On the other hand, the upper limit of the width of film volume is preferably below 2.5m, more preferably below 2.0m, further preferably below 1.5m.In addition, the volume of film volume is long also to be had no particular limits, and from easy coiling and maneuverable angle, the lower limit of the volume length of film volume is preferably more than 500m, more preferably more than 1000m.On the other hand, the upper limit of the volume length of film volume is preferably below 25000m, more preferably below 20000m, further preferably below 15000m.In addition, when film thickness is the 15 μ m left and right sides, below 12000m.In addition, as the coiling core, can use 3 inches, 6 inches, 8 inches etc. paper, plastic core or metal coremaking usually.
On the other hand, also there is no particular limitation to constitute the thickness of film of polyamide-based film volume, for example as packing polyamide-based resin film, preferred 8～50 μ m, more preferably 10～30 μ m.
In addition, in the scope of not damaging characteristic, in the manufacture method of polyamide resin film roll of the present invention, constitute in the polyamide-based resin film of film volume, can make it contain various additives such as lubricant, anticaking agent, heat stabilizer, antioxidant, antistatic additive, photostabilizer, resistance to impact modifying agent.Particularly, preferably make it contain various inorganic particles in order to improve the lubricity of double shaft extensioning film.In addition,, preferably has the particle of the average grain diameter (being average particulate diameter) of 0.5～5.0 μ m, preferred especially silica dioxide granule as inorganic particle.If average grain diameter is lower than 0.5 μ m, then can not get good lubricity, on the contrary, if average grain diameter is higher than 5.0 μ m, the transparency is bad, produces so-called " decolouring " during printing, and is therefore not preferred.In addition, the mensuration of average grain diameter can adopt the method that calculates weight average particle diameter according to the size distribution that obtains by Coulter-counter, can measure the particle before adding to polyamide, also can be to measuring by the particle of separating out with acid dissolving polyamide resin membrane of lipoprotein.In addition,, the lubricity of the film that constitutes the film volume is become better if add the organic lubricants such as ethylenebis stearic acid that can bring into play the effect that reduces the surface energy, therefore preferred.
And then, in the polyamide-based resin film that constitutes the film volume,,, can heat-treat with damping and handle in order to improve dimensional stability according to purposes.In addition,, can carry out that sided corona treatment, coating are handled and flame treatment etc., also can print, processing such as deposition in order to improve the zygosity of film surface.
In addition, we think in the method for above-mentioned (1)～(6) is not to have only a specific rerum natura that can reduce the film volume effectively to change, but by being used in combination the method for (1)～(6), the rerum natura that can reduce the film volume very effectively changes.Thus, when thin slice is not extended in formation, as mentioned above, powerful ground of molten resin thin slice static is close on the chill roll, when making film at a high speed, also can reduces the rerum natura variation of film volume like this by utilizing the time corona discharge.
In addition, the polyamide resin film roll of manufacturing method according to the invention manufacturing has characteristic highly uniformly on coiling direction.Be that the polyamide-based film that manufacturing method according to the invention obtains is rolled up when cutting out sample by method described later, for all samples, measuring when being peaked maximum boiling water shrinkage in the boiling water shrinkage in all directions, will be adjusted into as the average boiling water shrinkage of the mean value of these maximum boiling water shrinkages more than 3% below 6%.
In addition, the polyamide resin film roll that manufacturing method according to the invention obtains is when cutting out sample by method described later, for all samples, when obtain as with respect to length direction for the boiling water shrinkage of+45 degree directions with respect to length direction during for the boiling water shrinkage direction difference of absolute value of the difference of the boiling water shrinkage of-45 degree directions, will be adjusted to below 1.5% as the average boiling water shrinkage direction difference of the mean value of these boiling water shrinkage direction differences.
The operation that cuts out of sample is among the present invention, at first begin 2m and cut out portion with interior the 1st sample that is provided with at coiling terminal point from film, begin 2m in coiling starting point then and the final portion that cuts out is set, every about 100m sample is set since the 1st sample portion that cuts out and cuts out portion with interior from film.Wherein, " every about 100m " is meant and can cuts out sample in the place about 100m ± 1m.
Below cutting out of said sample is described in detail, for example, when the polyamide resin film roll of long 498m when getting up, begin 2m from the coiling terminal point of film and cut out initial sample (1) with interior place.In addition, for convenience's sake, cutting out of sample adopts the mode (not carrying out oblique cutting) that cuts to rectangular shape, this rectangular shape to have along the limit of the length direction of film with along the limit of hanging down as for length direction.Then, in the part that cuts of distance to the coiling origination side near the 100m place, cut the 2nd sample (2).Similarly,, cut the 3rd sample (3),, cut the 4th sample (4),, cut the 5th sample (5) to the close 400m place of coiling origination side to the close 300m place of coiling origination side to the close 200m place of coiling origination side.When so cutting sample, because remainder is less than 100m, the 6th (finally) sample (6) cuts on partly with interior arbitrarily at the coiling starting point 2m of distance film.Then, for each sample that cuts, measure boiling water shrinkage (hereinafter referred to as BS), maximum boiling water shrinkage (hereinafter referred to as BSx), average boiling water shrinkage (hereinafter referred to as BSax), boiling water shrinkage direction poor (hereinafter referred to as BSd), average boiling water shrinkage direction poor (hereinafter referred to as BSad) by following method.
[assay method of boiling water shrinkage (BS), maximum boiling water shrinkage (BSx), average boiling water shrinkage (BSax), boiling water shrinkage direction poor (BSd), average boiling water shrinkage direction poor (BSad)]
The double-axle orientation polyamide based resin film that will cut out from the respectively portion of cutting out of polyamide resin film roll is cut into square, places more than 2 hours in 23 ℃, the atmosphere of 65%RH.Central authorities with this sample are that circle (diameter is about about 20cm) is drawn at the center, with vertically (pull-out direction of film) as 0 °, with 15 ° serves as that the straight line by the center of circle is deasil made at the interval on 0～165 ° of direction, measures the diameter of all directions, as the length before handling.Then, with the sample that cuts out heat treated after 30 minutes in boiling water, with its taking-up, wipe away attached to lip-deep moisture, air-dry back is placed more than 2 hours in 23 ℃, the atmosphere of 65%RH, measure length as the above-mentioned straight line of on each diametric(al), being done, with it as the length after handling, by following formula 1～5, calculate BS (boiling water shrinkage), BSx (maximum boiling water shrinkage), BSax (average boiling water shrinkage), BSd (the boiling water shrinkage direction is poor), BSad (average boiling water shrinkage direction is poor).
Length after length-processing before BS=[(handles)/the preceding length of processing] * 100 (%) 1
BSx=15 ° is the shrinkage factor (%) 2 of the maximum in measuring on 0～165 ° of direction at interval
The quantity 3 of summation/sample of the BSx of all samples of BSax=
BSd=| (BS of 45 ° of directions)-(BS of 135 ° of directions) | 4
The quantity 5 of summation/sample of the BSd of all samples of BSad=
In addition, the value of the BSx of the polyamide film of formation polyamide resin film roll, hear resistance (being also referred to as lamination strength or heat-resisting lamination strength) when guaranteeing that biaxially oriented polyamide-based resin film is configured as bag shape and carries out hot water treatment, all be important aspect the anti-pin hole of obdurability that improves film self simultaneously, if BSx value less than 3%, then the anti-pin hole of obdurability is insufficient, on the other hand, if surpass 6%, then lamination is bad, heat-resisting lamination strength during hot water treatment is insufficient, and is therefore not preferred.From helping improving the angle of the anti-pin hole of obdurability and plyability and heat-resisting lamination strength, the scope of the BSx that is more preferably is 3.5～5.0%.
In addition, the curling phenomenon that the value of BSd of polyamide film that constitutes polyamide resin film roll produces during to boiling water treating has bigger influence, the BSd value is big more, the easy more bending of sack, curling becomes significantly, if BSd is suppressed at below 1.5%, more preferably below 1.2%, the bending of sack is suppressed as much as possible when boiling water treating, can prevent the S type phenomenon of curling.
In addition, the polyamide resin film roll that obtains of manufacturing method according to the invention must be adjusted at the rate of change of the maximum boiling water shrinkage (BSx) of all samples of cutting out in the scope of average boiling water shrinkage (BSax) ± 2%～± 10% (more than ± 2% ± below 10%).Wherein, the rate of change of the maximum boiling water shrinkage (BSx) of all samples is meant, obtain the maximin in the maximum boiling water shrinkage (BSx) of all samples, obtain in these maximins with average boiling water shrinkage between poor the greater and on average during boiling water shrinkage poor, this poor ratio with respect to average boiling water shrinkage.
That is to say, in the polyamide resin film roll that manufacturing method according to the invention obtains, when the boiling water shrinkage of sample (1)～(6) note is made Xn (n=1～6), in the difference of the difference of the maximum Xmax of Xn and average boiling water shrinkage (BSax) and minimum of a value Xmin and average boiling water shrinkage (BSax) any one all must be in ± 10%, in other words, any one | BSax-Xn| (wherein || expression absolute value) must be in 10%.
In addition, the rate of change of the maximum boiling water shrinkage (BSx) of all samples that the polyamide resin film roll that manufacturing method according to the invention obtains cuts out preferably average boiling water shrinkage (BSax) ± 9% with interior scope in, more preferably ± 8% with interior scope in, further preferably ± 7% with interior scope in.
In addition, though the rate of change of the maximum boiling water shrinkage (BSx) of all samples that the polyamide resin film roll that manufacturing method according to the invention obtains cuts out is wished the smaller the better, but consider the precision of measurement, think that the boundary of lower limit of this rate of change is about 2%.
In addition, the polyamide resin film roll that obtains of manufacturing method according to the invention must be adjusted at the rate of change of the boiling water shrinkage direction poor (BSd) of all samples of cutting out in the scope of average boiling water shrinkage direction poor (BSad) ± 2%～± 10% (more than ± 2% ± below 10%).Wherein, the rate of change of the boiling water shrinkage direction poor (BSd) of all samples is meant, obtain the maximin in the boiling water shrinkage direction of all samples poor (BSd), when obtaining in these maximins with the poor the greater of average boiling water shrinkage direction difference and average boiling water shrinkage direction difference poor, this poor ratio with respect to average boiling water shrinkage direction difference.
That is to say, in the polyamide resin film roll that manufacturing method according to the invention obtains, when the boiling water shrinkage direction difference of sample (1)～(6) note is made Yn (n=1～6), in the difference of the difference of the maximum Ymax of Yn and average boiling water shrinkage direction poor (BSad) and minimum of a value Ymin and average boiling water shrinkage direction poor (BSad) any one all must be in ± 10%, in other words, any one | BSad-Yn| (wherein || expression absolute value) must be in 10%.
In addition, the rate of change of the boiling water shrinkage direction poor (BSd) of all samples that the polyamide resin film roll that manufacturing method according to the invention obtains cuts out preferably average boiling water shrinkage direction poor (BSad) ± 9% with interior scope in, more preferably ± 8% with interior scope in, further preferably ± 7% with interior scope in.
In addition, though the rate of change of the boiling water shrinkage direction poor (BSd) of all samples that the polyamide resin film roll that manufacturing method according to the invention obtains cuts out is wished the smaller the better, but consider the precision of measurement, think that the boundary of lower limit of this rate of change is about 2%.
Also have, the polyamide resin film roll that manufacturing method according to the invention obtains must be adjusted to the thickness change of total length alongst with respect in average thickness be ± 2%～± 10% scope of (more than ± 2% ± below 10%).Wherein, alongst the thickness change of total length is meant, obtain the maximin in the thickness of total length alongst, when obtaining in these maximins with the poor the greater of average thickness and average thickness poor, this differs from the ratio with respect to average thickness.
That is to say, in the polyamide-based film volume that manufacturing method according to the invention obtains, alongst any one in the difference of the difference of the maximum of T max of the thickness of total length and average thickness (the average thickness Ta of total length alongst) and minimum of a value Tmin and average thickness (Ta) all must be in ± 10%.
In addition, the polyamide resin film roll that manufacturing method according to the invention obtains alongst total length thickness change preferably average thickness (Ta) ± 8% with interior scope in, more preferably ± 6% with interior scope in.
In addition, though the polyamide resin film roll that manufacturing method according to the invention obtains alongst the thickness change of total length wish the smaller the betterly, from the aspect of performance of film forming apparatus, think that the boundary of lower limit of this rate of change is about 2%.
Further, when the polyamide resin film roll that manufacturing method according to the invention obtains cuts out sample by said method, for all samples, when the refractive index of obtaining thickness direction (Nz), preferably will be adjusted to more than 1.500 below 1.520 as the mean refractive index (Nza) of the mean value of these refractive indexes.In addition, mean refractive index is calculated by following formula 6.
The quantity 6 of summation/sample of the Nz of all samples of Nza=
In addition, the value of the Nz of the polyamide film of formation polyamide resin film roll has bigger influence for the quality aspect of films such as lamination strength and uneven thickness.Therefore, when biaxial oriented polyester based resin film and the use of polyolefin resin film lamination, mean refractive index is the requirement that must satisfy in the requirement of this below 1.520 more than 1.500.Therefore, then insufficient if Nz less than 1.500 with the lamination strength of polyolefin resin film etc., between laminate substrate, cause easily in the boiling water treating behind bag etc. and peel off.On the other hand, this Nz reduces in the process of the polyamide-based resin film that does not extend being carried out the twin shaft extension in turn.In other words, Nz can be thought one of index of extending,,, then, can not get the quality of gratifying film because twin shaft extends generations significantly such as insufficient uneven thickness that causes if Nz surpasses 1.520 if Nz more then shows and extends insufficiently.Consider lamination strength and membrane quality two aspects, the scope of particularly preferred Nz is 1.507～1.516.
Also have, the rate of change of the refractive index of all samples that the polyamide resin film roll that manufacturing method according to the invention obtains preferably will cut out (Nz) is adjusted at mean value (hereinafter referred to as mean refractive index) with respect to these refractive indexes for ± 2% with in the interior scope.Wherein, the rate of change of the refractive index of all samples (Nz) is meant, obtain the maximin in the rate of change of the refractive index (Nz) at all samples, when obtaining in these maximins with the poor the greater of mean refractive index and mean refractive index poor, this differs from the ratio with respect to mean refractive index.
That is to say, in the polyamide resin film roll that manufacturing method according to the invention obtains, when the refractive index of sample (1)～(6) note being made Nz1～Nz6, in the minimum of a value Nzmin of the maximum Nzmax of Nz1～Nz6 and the difference of mean refractive index and Nz1～Nz6 and the difference of mean refractive index any one all must be in ± 2%, in other words, any one | mean refractive index-Nz1|～| mean refractive index-Nz6| is preferably in 2%.In addition, the rate of change of the refractive index (Nz) of the polyamide resin film roll that obtains of manufacturing method according to the invention all samples that more preferably will cut out is adjusted at respect to mean refractive index to ± 1% with in the interior scope.
In addition, the rate of change of the refractive index of all samples that the polyamide resin film roll that manufacturing method according to the invention obtains cuts out (Nz) is wished the smaller the better, but, think that the boundary of lower limit of this rate of change is about 0.1% from the aspect of certainty of measurement and mechanical precision.
As mentioned above, with the maximum boiling water shrinkage of 1 polyamide resin film roll, the value that boiling water shrinkage direction difference is adjusted to prescribed limit, simultaneously by reducing the variation of these maximum boiling water shrinkages, boiling water shrinkage direction difference, can prevent the variation of outward appearance in bag processing and lamination process, can process glibly with good yield rate.
Embodiment
Below, the present invention will be described in detail by embodiment.The present invention is not limited to the mode of this embodiment, in the scope that does not break away from purport of the present invention, can suitably change.At embodiment, comparative example, reference example and the proterties of the material web A～E that uses in reference to comparative example, embodiment, comparative example, reference example and with reference to comparative example in the creating conditions respectively shown in table 1～3 of film volume in composition, embodiment and the comparative example of material web A～E of using.In addition, thin slice A, C, D are nylon 6 (relative viscosity=2.8 by 97.00 weight %, Tg=41 ℃) and the silica dioxide granule of 3.00 weight % form, thin slice B, E are formed by xyxylene adipamide (relative viscosity=2.1), the ethylenebis stearic amide of 0.15 weight % and the silica dioxide granule of 0.40 weight % between the nylon 6 of 96.45 weight % (relative viscosity=2.8, Tg=41 ℃), 3.00 weight % poly-.In addition, the average grain diameter of the silica dioxide granule that adds in thin slice A, C is about 3.0 μ m, and the average grain diameter of the silica dioxide granule that adds in thin slice B is about 1.8 μ m, and the average grain diameter of the silica dioxide granule that adds in thin slice D, E is about 2.0 μ m.In addition, any one all is oval column for the shape of thin slice A～E, and thin slice A is the same with thin slice D, thin slice B with thin slice E cross section major diameter, cross section minor axis and thin slice length separately.
Table 1
Table 2
| The cooling condition of fusion thin slice | |||||||
| The draw speed of fusion thin slice (m/min) | Static is close to method | The atmosphere of region of discharge | |||||
| Electrode | Discharge | Voltage (kv) | Electric current (mA) | Temperature (℃) | Humidity (%RH) | ||
| | 66 | 0.5mm φ spininess | The time corona | 11.0±1.1 | 100 | 45 | 75 |
| | 75 | 0.5mm φ spininess | The time corona | 11.0±1.1 | 100 | 45 | 75 |
| | 66 | 0.5mm φ spininess | The time corona | 11.0±1.1 | 100 | 45 | 75 |
| | 66 | 0.5mm φ spininess | The time corona | 11.0±1.1 | 100 | 45 | 75 |
| | 66 | 0.5mm φ spininess | The time corona | 11.0±1.1 | 100 | 45 | 75 |
| | 66 | 0.5mm φ spininess | The time corona | 11.0±1.1 | 100 | 45 | 75 |
| Embodiment 7 | 66 | 0.5mm φ spininess | The time corona | 11.0±1.1 | 100 | 45 | 75 |
| Embodiment 8 | 66 | 0.5mm φ spininess | The time corona | 11.0±1.1 | 100 | 45 | 75 |
| Comparative example 1 | 66 | 0.5mm φ needle-like metal line | Aura | 11.0±1.1 | 100 | - | - |
Table 3
| Material web mixing ratio (weight %) | Film forming condition | The system film | ||||||||||||
| Hopper inclination angle (degree) | The moisture of thin slice (ppm) | The attraction wind speed (m/min) of vacuum tank | Thin slice temperature when hopper is supplied (℃) | First vertical the extension | Second vertical the extension | Horizontal extension | Heat fixation (℃) | Relaxation processes (%) | ||||||
| Temperature (℃) | Multiplying power | Temperature (℃) | Multiplying power | Temperature (℃) | Multiplying power | |||||||||
| Embodiment 1 | A/B＝5/95 | 70 | 800 | 5.0±0.5 | 91 | 85 | 2.1 | 70 | 1.6 | 130 | 4.0 | 213 | 5.0 | Well |
| Embodiment 2 | A/B＝5/95 | 70 | 800 | 5.0±0.5 | 91 | 85 | 2.1 | 70 | 1.6 | 130 | 4.0 | 216 | 5.0 | Well |
| Embodiment 3 | A/B＝5/95 | 70 | 800 | 5.0±0.5 | 91 | 90 | 2.2 | 70 | 1.5 | 130 | 4.0 | 213 | 5.0 | Well |
| Embodiment 4 | A/B＝5/95 | 70 | 800 | 5.0±0.5 | 91 | 85 | 2.1 | 70 | 1.6 | 130 | 3.6 | 216 | 3.0 | Well |
| Embodiment 5 | A/B＝15/85 | 70 | 800 | 5.0±0.5 | 91 | 85 | 2.1 | 70 | 1.6 | 130 | 4.0 | 213 | 5.0 | Well |
| Embodiment 6 | D/E＝5/95 | 70 | 800 | 5.0±0.5 | 91 | 85 | 2.1 | 70 | 1.6 | 130 | 4.0 | 213 | 5.0 | Well |
| Embodiment 7 | A/B＝5/95 | 65 | 800 | 5.0±0.5 | 91 | 85 | 2.1 | 70 | 1.6 | 130 | 4.0 | 213 | 5.0 | Well |
| Embodiment 8 | A/B＝5/95 | 70 | 800 | 3.0±0.5 | 91 | 85 | 2.1 | 70 | 1.6 | 130 | 4.0 | 213 | 5.0 | Well |
| Comparative example 1 | A/B＝5/95 | 70 | 800 | 5.0±0.5 | 91 | - | - | - | - | - | - | - | - | Bad * |
*The system film is bad: fracture when the fusion thin slice stretches
[embodiment 1]
Carried out predrying through about 8.0 hours while being warming up to about 120 ℃ with the agitating device of 15kl above-mentioned thin slice A, B respectively.Collect a certain amount of each thin slice in mixer, measure its moisture, the moisture of thin slice A, B is 800ppm.In addition, the mensuration of moisture is used Ka Er-Fei Xier moisture meter (MKC-210 that KYOTO electronics, inc. makes), and at sample weight 1g, the sample heating-up temperature is to carry out under 230 ℃ the condition.
Then, continuously the thin slice in each mixer is fed to respectively in the hopper directly over the extruder by quantitative screw feeder.In addition, the supply of thin slice A is 5.0 weight %, and the supply of thin slice B is 95.0 weight %.Hopper has the material web capacity of 150kg, and the discharge rate of extruder is per 1 hour 450kg.In addition, the inclination angle with hopper is adjusted into 70 °.In addition, in embodiment 1, the average major diameter of the polyamide-based resin thin slice (thin slice A) beyond the polyamide-based resin thin slice that use amount is maximum, average minor axis and average thin slice length are adjusted into, make the average major diameter of its maximum with respect to use amount respectively polyamide-based resin thin slice (thin slice B), average minor axis and average thin slice length its ± 20% with interior scope in.
In addition, when being fed to thin slice A, B in the hopper, in the short time that begins from drying, be fed to the hopper, fall lowly excessively not make the thin slice temperature in each mixer.Be fed to that the temperature of thin slice A, B is 91 ℃ before the hopper.Gong Ying thin slice A, B mixes in hopper then, melt extrudes from the T mould under 270 ℃ by the single axle extruder, by carrying out chilling on the metallic roll that is wound on the rotation that is cooled to 17 ℃, obtains the not extension film of thick 257 μ m.In addition, the draw speed of extension film (rotary speed of metallic roll) is not about 66m/min.
In addition, when the resin of fusion is wound on the metallic roll, the air gap is adjusted into 40mm, the needle electrode of the many spicules by being set up in parallel 1.5mm φ under 11 ± 1.1kv to fused films (sheet-like article) the direct current negative electrical charge of 100mA in addition, by making its time corona discharge, the resin static of fusion is close on the metallic roll.In above-mentioned time corona discharge, with wall components surround electrode and metallic roll around, make itself and outside blocking, make multi-needle electrode around humidity be maintained at about 75%RH, the temperature around the multi-needle electrode is maintained at about 45 ℃.Further, when the resin of fusion is wound on the metallic roll,, utilize vacuum tank on the total length of molten resin, resin to fusion attracts along the direction opposite with the resin coiling with the part of metallic roll contact, promotes resin being close to metallic roll of fusion.In addition, the attraction wind speed of vacuum tank being adjusted on the whole width (being the whole width of molten resin) that attracts mouthful is 5.0 ± 0.5m/sec.In the manufacture process of above-mentioned not extension film, do not find oligomer attached on the multi-needle electrode, and static to be close to state highly stable.
Then, with the roller of special teflon system the not extension film that will obtain under about 85 ℃ elongating temperature is vertical extend (the 1st vertical the extension) to about 2.1 times after, with the roller of pottery system under about 70 ℃ elongating temperature vertical extension the (the 2nd vertical the extension) to about 1.6 times.And then, the vertical thin slice that extends is imported stenter continuously, down horizontally extend to about 4.0 times at about 130 ℃, at about 213 ℃ of following heat fixations, carry out cooling off after 5.0% the horizontal relaxation processes, by severing two edges part, make the double shaft extensioning film that film is made the above about 15 μ m of 2000m continuously, make undressed volume.In addition, the amplitude of variation of the surface temperature of film was when continuously 2000m made film, in preheating procedure in mean temperature ± 0.8 ℃, in extension process in mean temperature ± 0.6 ℃, in heat treatment step in the scope of mean temperature ± 0.5 ℃.And then, the undressed volume that obtains is cut to wide 400mm, long 2000m, be wound on 3 inches paper tubes, obtain 2 polyamide resin film rolls (cutting volume).Then, use 2 the cutting volumes (i.e. the volume that obtains from same undressed volume) that obtain, carry out the evaluation of characteristic by following method.In addition, in the mensuration of following BS (boiling water shrinkage), BSx (maximum boiling water shrinkage), BSd (the boiling water shrinkage direction is poor), refractive index, begin 2m from the coiling terminal point of film and cut out portion with interior the 1st sample that is provided with, every about 100m the 2nd to the 20th sample is set since the 1st sample portion that cuts out and cuts out portion, begin 2m from the coiling starting point of film and cut out portion, cut out the sample film from these each sample portions of cutting out of the 1st to the 21st with interior the 21st sample that is provided with.Evaluation result is shown in table 4～8.When the expression evaluation result,, the mean value of each specimen sample numerical value of measuring and the mobility scale of each design sample numerical value have been expressed for impact strength, lamination strength.In addition, curl, expressed each and estimated the number of other specimen sample of level and the overall merit rank of all specimen sample for the S type.
[boiling water shrinkage]
The double-axle orientation polyamide based resin film (sample film) that will cut out from the respectively portion of cutting out of cutting volume cuts out the square of length of side 21cm, places more than 2 hours in 23 ℃, the atmosphere of 65%RH.Central authorities with this sample are the circle that diameter 20cm is drawn at the center, as 0 °, serve as that interval deasil on 0～165 ° direction make straight line by the center of circle with 15 ° with vertical (pull-out direction of film), measure the diameter of all directions, as the length before handling.Then, with the sample that cuts out heat treated after 30 minutes in boiling water, with its taking-up, wipe away attached to lip-deep moisture, air-dry back is placed more than 2 hours in 23 ℃, the atmosphere of 65%RH, measure length as the above-mentioned straight line of on each diametric(al), being done, with it as the length after handling, by following formula 1～5, calculate BS (boiling water shrinkage), BSx (maximum boiling water shrinkage), BSax (average boiling water shrinkage), BSd (the boiling water shrinkage direction is poor), BSad (average boiling water shrinkage direction is poor).
Then, obtain the maximin in the maximum boiling water shrinkage (BSx) of all samples, obtain in these maximins with average boiling water shrinkage (BSax) between poor the greater and average boiling water shrinkage poor, calculate the ratio (%) of this difference, obtain the rate of change of maximum boiling water shrinkage (BSx) thus with respect to average boiling water shrinkage (BSax) with respect to average boiling water shrinkage (BSax).In addition, obtain the maximin in the boiling water shrinkage direction of all samples poor (BSd), obtain in these maximins with average boiling water shrinkage direction poor (BSad) between poor the greater and average boiling water shrinkage direction difference poor, calculate the ratio (%) of this difference, obtain the rate of change of boiling water shrinkage direction poor (BSd) thus with respect to average boiling water shrinkage direction poor (BSad) with respect to average boiling water shrinkage direction poor (BSad).
[longitudinal thickness inequality]
With its width that is cut to about 3cm, make the cutting volume that uneven thickness is measured usefulness along cutting volume length direction total length.The uneven thickness determinator made from An Li company (wide scope high sensitivity electronic microcalliper K-313A) is then obtained average thickness, maximum ga(u)ge, minimum thickness on the total length alongst.Then by following formula 7, calculate in these maximum ga(u)ge minimum thickness poor with the difference the greater of average thickness and average thickness, calculate the ratio (%) of this difference with respect to average thickness, calculate the rate of change of thickness on total length alongst thus.
Thickness change=| maximum ga(u)ge or minimum thickness-average thickness |/average thickness 7
[lamination process]
Use and measured above-mentioned boiling water shrinkage, the longitudinal thickness inequality, another cutting volume (volume that comes from same undressed volume) that the cutting volume of refractive index and impact strength is different, after polyurethane coating class AC agent on the double-axle orientation polyamide based resin film that constitutes this cutting volume (" EL443 " that Japan モ-ト Application company makes), single test laminating machine (the single test laminator) device that uses modern machines company to make, under 315 ℃, extrude LDPE (low density polyethylene (LDPE)) film of thick 15 μ m, and then, the LLDPE of the thick 40 μ m of lamination (straight chain shape low density polyethylene (LDPE)) film continuously thereon obtains the laminate roll of the 3 layer laminate structures that are made of polyamide-based resin/LDPE/LLDPE.Processability when in addition, making laminate roll is estimated by 3 following grades.
Zero: on volume, fold does not take place, do not need regularization condition
△: the fold by the regularization condition volume is eliminated
*: regularization condition come what may produces fold on volume
[refractive index]
Use to like " abbe's refractometer 4T type " that (ATAGO) company that delays makes, after each sample film that will cut out from each sample portion of cutting out is placed more than 2 hours, measure the refractive index (Nz) of thickness direction 23 ℃, the atmosphere of 65%RH.Then, calculate the average mean refractive index of all sample films, as shown in table 6, calculate in all samples the poor of maximum or minimum Nz and mean refractive index, calculate the ratio of this difference simultaneously with respect to mean refractive index, with it as rate of change.
[S type curl phenomenon]
Test sealer with the manufacturing of western Mechanology Inc., the laminated film that as above the form with laminate roll is wound up is along the length direction doubling that is parallel to coiling, in the vertical, in 150 ℃ of partial continuous ground heat-sealings with each two ends 20mm, 150mm obtains the semi-finished product of wide 200mm discontinuously with the part heat-sealing of 10mm at interval on vertical with it direction.On the length direction of reeling it is cut off, the part that makes two edges portion be heat-sealed becomes 10mm, at hot blast portion boundary place it is cut off on vertical with it direction then, makes 3 limit sealing bag (sealed widths: 10mm).In these 3 limit sealing bags, to begin 3 limit sealing bags that 2m makes with interior part from the coiling terminal point of laminate roll as the 1st sample, will from the preparing department of the 1st sample divide begin to depart from about 100,200 ... the 3 limit sealing bags that the part of 1900m is made are respectively as the 2nd～the 20th sample, will begin 3 limit sealing bags that 2m makes with interior part from the coiling starting point of laminate roll as the 21st sample.Then, with the heat treatment after 30 minutes in boiling water of these 21 3 limit sealing bags, under 23 ℃, the atmosphere of 65%RH, keep diel, and then it is these 21 3 limit sealing bags are overlapping, the heavy burden of 1kg in addition above these sacks whole, remove heavy burden after the maintenance 1 round the clock, the warpage degree (the S type curls) of the back sack that bears a heavy burden is removed in following evaluation.
◎: do not have warpage fully
Zero: find small warpage
*: find tangible warpage
* *: warpage is serious
[impact strength]
After each sample film that will cut out from each sample portion of cutting out is placed more than 2 hours 23 ℃, the atmosphere of 65%RH, use the smart mechanism of Japan to make " the film shock machine TSS type " of manufacturing, hemispherical collision by diameter 12.7mm is measured fracture strength, with it as impact strength.In addition, also calculate the average impact strength of all samples.
[lamination strength]
To be cut into the test film of wide 15mm, long 200mm from the laminated film that this laminate roll cuts out, with " rising the imperial UMT-II-500 type of happiness " of Japan BALDWIN company manufacturing, in the peel strength of measuring under the condition of 23 ℃ of temperature, relative humidity 65% between polyamide-based laminated polyester film and the LDPE layer.In addition, making draw speed is 10cm/ minute, and making peel angle is 180 degree, makes water attached to measuring on the released part.In addition, the mensuration of lamination strength is that the coiling terminal point from laminate roll begins 2m with interior the 1st coupons that cuts out, the portion that cuts out cuts out the 2nd to the 20th coupons every about 100m since the 1st coupons, begin 2m with interior the 21st coupons that cuts out from the coiling starting point of film, measure from these each coupons of the 1st to the 21st.In addition, also calculate the mean value of these measured values.
[embodiment 2]
Except the draw speed with the thin slice of molten condition changes to 75m/min, beyond the heat fixation temperature after twin shaft extended changed to roughly 216 ℃, all the other obtained the polyamide resin film roll of embodiment 2 similarly to Example 1.The characteristic of the film that obtains being rolled up by method is similarly to Example 1 estimated then.Evaluation result is shown in table 4～8.
[embodiment 3]
With the roller of special teflon system will obtain under about 90 ℃ elongating temperature that extension film is vertical by method similarly to Example 1 and extend (the 1st vertical the extension) to about 2.2 times after, with the roller of pottery system about 70 ℃ of vertical down extensions (the 2nd vertical the extension) to about 1.5 times.And then, with the vertical thin slice that extends similarly to Example 1, import stenter continuously, down horizontally extend to about 4.0 times at about 130 ℃, at about 213 ℃ of following heat fixations, carry out cooling off after 5% the horizontal relaxation processes,, make the double shaft extensioning film that film is made the above about 15 μ m of 2000m continuously by severing two edges part.The amplitude of variation of the surface temperature of film is identical with embodiment 1 when in addition, making film continuously.Wind up after by the film that will obtain, obtain the polyamide resin film roll of embodiment 3 thus according to method cutting similarly to Example 1.The characteristic of the film that obtains being rolled up by method is similarly to Example 1 estimated then.Evaluation result is shown in table 4～8.
[embodiment 4]
To obtain not similarly to Example 1 by method similarly to Example 1, extension film carries out the vertical extension of two-stage.The thin slice that to indulge extension then imports stenter continuously, down horizontally extend to 3.6 times at about 130 ℃,, carry out cooling off after 3.0% the horizontal relaxation processes at about 216 ℃ of following heat fixations, by severing two edges part, make the double shaft extensioning film that film is made the above about 15 μ m of 2000m continuously.The amplitude of variation of the surface temperature of film is identical with embodiment 1 when in addition, making film continuously.Wind up after by the film that will obtain, obtain the polyamide resin film roll of embodiment 4 thus according to method cutting similarly to Example 1.The characteristic of the film that obtains being rolled up by method is similarly to Example 1 estimated then.Evaluation result is shown in table 4～8.
[embodiment 5]
Except the mixed proportion with material web A and material web B changes thin slice A into is 15.0 weight %, and thin slice B is that all the other obtain the polyamide resin film roll of embodiment 5 similarly to Example 1 beyond the 85.0 weight %.In addition, in embodiment 5, the average major diameter of the polyamide-based resin thin slice (thin slice A) beyond the polyamide-based resin thin slice that use amount is maximum, average minor axis and average thin slice length are adjusted into, make the average major diameter of its maximum with respect to use amount respectively polyamide-based resin thin slice (thin slice B), average minor axis and average thin slice length its ± 20% with interior scope in.The characteristic of the film that obtains being rolled up by method is similarly to Example 1 estimated then.Evaluation result is shown in table 4～8.
[embodiment 6]
Except using material web D, E replacement material web A, B respectively, all the other similarly to Example 1, obtain the polyamide resin film roll (promptly in embodiment 6, making polyamide resin film roll) of embodiment 6 with the thin slice D of 5.0 weight % and the thin slice E of 95.0 weight %.In addition, in embodiment 6, the average major diameter of the polyamide-based resin thin slice (thin slice D) beyond the polyamide-based resin thin slice that use amount is maximum, average minor axis and average thin slice length are adjusted into, make the average major diameter of its maximum with respect to use amount respectively polyamide-based resin thin slice (thin slice E), average minor axis and average thin slice length its ± 20% with interior scope in.The characteristic of the film that obtains being rolled up by method is similarly to Example 1 estimated then.Evaluation result is shown in table 4～8.
[embodiment 7]
Except when the material web in the agitator becomes the inclination angle of hopper beyond 65 ° when being supplied to hopper directly over the extruder, all the other obtain the polyamide resin film roll of embodiment 7 similarly to Example 1.The characteristic of the film that obtains being rolled up by method is similarly to Example 1 estimated then.Evaluation result is shown in table 4～8.
[embodiment 8]
When the resin with fusion was wound on the metallic roll, being adjusted into the attraction wind speed of vacuum tank on the whole width that attracts mouthful was 3.0 ± 0.5m/sec, and in addition all the other obtain the polyamide resin film roll of embodiment 8 similarly to Example 1.The characteristic of the film that obtains being rolled up by method is similarly to Example 1 estimated then.Evaluation result is shown in table 4～8.
[comparative example 1]
When the resin static of fusion is close to metallic roll, the rotary speed of metallic roll is maintained at about 66m/min similarly to Example 1, electrode is changed to the metal wire of 0.5mm φ, and the direct current negative electrical charge of 11 ± 1.1kv, 100mA is applied to molten resin and during glow discharge, molten resin is reeled attached on the metal wire and can not be close on the metallic roll by static, thus the not extension film that can not obtain extending.
Table 4
| The characteristic of polyamide resin film roll | |||
| Average boiling water shrinkage (BSax:%) | Maximin (%) in the maximum boiling water shrinkage of all samples | The rate of change of the maximum boiling water shrinkage of average relatively boiling water shrinkage * (％) | |
| | 4.3 | 4.6 | 7.0 |
| | 4.5 | 4.7 | 4.4 |
| | 3.9 | 3.6 | 7.7 |
| | 3.5 | 3.8 | 8.6 |
| | 3.7 | 4.0 | 8.1 |
| | 4.0 | 4.2 | 5.0 |
| Embodiment 7 | 4.2 | 4.5 | 7.1 |
| Embodiment 8 | 4.8 | 4.5 | 6.3 |
| Comparative example 1 | - | - | - |
*The rate of change of the maximum boiling water shrinkage of average relatively boiling water shrinkage: with in the maximin of the maximum boiling water shrinkage of all samples, the rate of change that calculates with difference the greater of average boiling water shrinkage.
Table 5
| The characteristic of polyamide resin film roll | |||
| Average boiling water shrinkage direction poor (BSad:%) | The maximin (%) of all sample boiling water shrinkage direction differences | The rate of change of the boiling water shrinkage direction difference of average relatively boiling water shrinkage direction difference * (％) | |
| | 1.3 | 1.2 | 7.7 |
| | 1.2 | 1.3 | 8.3 |
| | 1.2 | 1.3 | 8.3 |
| | 1.3 | 1.2 | 7.7 |
| | 1.0 | 1.1 | 10.0 |
| | 1.1 | 1.1 | 0.0 |
| Embodiment 7 | 1.4 | 1.5 | 7.1 |
| Embodiment 8 | 1.4 | 1.3 | 7.1 |
| Comparative example 1 | - | - | - |
*The rate of change of the boiling water shrinkage direction difference of average relatively boiling water shrinkage direction difference: with in the maximin of the boiling water shrinkage direction difference of all samples, the rate of change that calculates with difference the greater of average boiling water shrinkage direction difference.
Table 6
| The characteristic of polyamide resin film roll | |||
| Average thickness (μ m) | The maximin of thickness on total length (μ m) | Rate of change with respect to the thickness of average thickness *(％) | |
| | 15.01 | 4.45 | 3.7 |
| | 14.98 | 15.88 | 6.0 |
| | 15.05 | 14.31 | 4.9 |
| | 15.05 | 14.25 | 5.3 |
| | 14.95 | 15.98 | 6.9 |
| | 14.98 | 15.70 | 4.8 |
| Embodiment 7 | 15.02 | 16.15 | 7.5 |
| Embodiment 8 | 15.03 | 16.25 | 8.1 |
| Comparative example 1 | - | - | - |
*Thickness change with respect to average thickness: in the maximin with thickness on total length, the rate of change that calculates with difference the greater of average thickness.
Table 7
| The characteristic of polyamide resin film roll | |||
| Mean refractive index (Nz) | Maximin in the refractive index of all samples | The change of refractive rate of relative mean refractive index *(％) | |
| | 1.511 | 1.518 | 0.5 |
| | 1.510 | 1.505 | 0.3 |
| | 1.512 | 1.505 | 0.5 |
| | 1.512 | 1.508 | 0.3 |
| | 1.510 | 1.515 | 0.3 |
| | 1.512 | 1.518 | 0.4 |
| Embodiment 7 | 1.512 | 1.507 | 0.3 |
| Embodiment 8 | 1.511 | 1.519 | 0.5 |
| Comparative example 1 | - | - | - |
*Change of refractive rate with respect to mean refractive index: in the maximin with the refractive index in all samples, the rate of change that calculates with difference the greater of mean refractive index.
Table 8
[reference example 1]
The draw speed of the resin flake when being close to metallic roll except the resin static with fusion (rotary speed of metallic roll) changes to 60m/min, and the wire electrode generation glow discharge that the method that static is close to is changed to by 0.5mm φ (applies 11 ± 1.1kv, the direct current negative electrical charge of 100mA) method, the temperature of the heat fixation after simultaneously twin shaft being extended changes to beyond about 210 ℃, the same with embodiment 1, the polyamide resin film roll that obtains reference example 1 in addition, the amplitude of variation of the surface temperature of film and embodiment 1 are the same when continuously making film is: in preheating procedure in mean temperature ± 0.8 ℃, in extension process in mean temperature ± 0.6 ℃, in heat treatment step in the scope of mean temperature ± 0.5 ℃.The characteristic of the film that obtains being rolled up by method is similarly to Example 1 estimated then.Creating conditions shown in table 9,10 of film volume in the reference example 1, the evaluation result of the characteristic of film volume is shown in table 11～15.
[reference example 2]
With the roller of special teflon system will obtain under about 90 ℃ elongating temperature that extension film is vertical by method similarly to Example 1 and extend (the 1st vertical the extension) to about 2.2 times after, with the roller of pottery system about 70 ℃ of vertical down extensions (the 2nd vertical the extension) to about 1.5 times.And then, with the vertical thin slice that extends and reference example 1 similarly, import stenter continuously, down horizontally extend to about 4.0 times at about 130 ℃, at about 210 ℃ of following heat fixations, carry out cooling off after 5% the horizontal relaxation processes,, make the double shaft extensioning film that film is made the above about 15 μ m of 2000m continuously by severing two edges part.The amplitude of variation of the surface temperature of film is identical with reference example 1 when in addition, making film continuously.By the film that will obtain according to the same method cutting of reference example 1 after wind up, obtain the polyamide resin film roll of reference example 2 thus.The characteristic of the film that obtains being rolled up by method is similarly to Example 1 estimated then.Creating conditions shown in table 9,10 of film volume in the reference example 2, the evaluation result of the characteristic of film volume is shown in table 11～15.
[reference example 3]
With reference example 1 similarly will extension film carries out the vertical extension of two-stage by obtaining not with the same method of reference example 1.The thin slice that to indulge extension then imports stenter continuously, down horizontally extend to 3.6 times at about 130 ℃,, carry out cooling off after 3.0% the horizontal relaxation processes at about 215 ℃ of following heat fixations, by severing two edges part, make the double shaft extensioning film that film is made the above about 15 μ m of 2000m continuously.The amplitude of variation of the surface temperature of film is identical with reference example 1 when in addition, making film continuously.By the film that will obtain according to the same method cutting of reference example 1 after wind up, obtain the polyamide resin film roll of reference example 3 thus.The characteristic of the film that obtains being rolled up by method is similarly to Example 1 estimated then.Creating conditions shown in table 9,10 of film volume in the reference example 3, the evaluation result of the characteristic of film volume is shown in table 11～15.
[reference example 4]
Except the mixed proportion with material web A and material web B changes thin slice A into is 15.0 weight %, and thin slice B is that all the other and reference example 1 similarly obtain the polyamide resin film roll of reference example 4 beyond the 85.0 weight %.In addition, in reference example 4, the average major diameter of the polyamide-based resin thin slice (thin slice A) beyond the polyamide-based resin thin slice that use amount is maximum, average minor axis and average thin slice length are adjusted into, make the average major diameter of its maximum with respect to use amount respectively polyamide-based resin thin slice (thin slice B), average minor axis and average thin slice length its ± 20% with interior scope in.The characteristic of the film that obtains being rolled up by method is similarly to Example 1 estimated then.Creating conditions shown in table 9,10 of film volume in the reference example 4, the evaluation result of the characteristic of film volume is shown in table 11～15.
[reference example 5]
Except using material web D, E replacement material web A, B respectively, all the other and reference example 1 are similarly, obtain the polyamide resin film roll (promptly in reference example 5, making polyamide resin film roll) of reference example 5 with the thin slice D of 5.0 weight % and the thin slice E of 95.0 weight %.In addition, in reference example 5, the average major diameter of the polyamide-based resin thin slice (thin slice D) beyond the polyamide-based resin thin slice that use amount is maximum, average minor axis and average thin slice length are adjusted into, make the average major diameter of its maximum with respect to use amount respectively polyamide-based resin thin slice (thin slice E), average minor axis and average thin slice length its ± 20% with interior scope in.The characteristic of the film that obtains being rolled up by method is similarly to Example 1 estimated then.Creating conditions shown in table 9,10 of film volume in the reference example 5, the evaluation result of the characteristic of film volume is shown in table 11～15.
[reference example 6]
Except when the material web in the agitator becomes the inclination angle of hopper beyond 65 ° when being supplied to hopper directly over the extruder, all the other and reference example 1 similarly obtain the polyamide resin film roll of reference example 6.The characteristic of the film that obtains being rolled up by method is similarly to Example 1 estimated then.Creating conditions shown in table 9,10 of film volume in the reference example 6, the evaluation result of the characteristic of film volume is shown in table 11～15.
[reference example 7]
When the resin with fusion was wound on the metallic roll, being adjusted into the attraction wind speed of vacuum tank on the whole width that attracts mouthful was 3.0 ± 0.5m/sec, and in addition all the other and reference example 1 similarly obtain the polyamide resin film roll of reference example 7.The characteristic of the film that obtains being rolled up by method is similarly to Example 1 estimated then.Creating conditions shown in table 9,10 of film volume in the reference example 7, the evaluation result of the characteristic of film volume is shown in table 11～15.
[with reference to comparative example 1]
With the roller of special teflon system under about 90 ℃ elongating temperature will by with the same method of reference example 1 obtain that extension film is vertical and extend (the 1st vertical the extension) to about 1.5 times after, with the roller of pottery system about 70 ℃ of vertical down extensions (the 2nd vertical the extension) to about 2.2 times.And then, the vertical thin slice that extends is imported stenter continuously, with reference example 1 similarly, carry out horizontal extension, carry out cooling off after heat fixation and the horizontal relaxation processes, by severing two edges part, make the double shaft extensioning film that film is made the above about 15 μ m of 2000m continuously.The amplitude of variation of the surface temperature of film is identical with reference example 1 when in addition, making film continuously.By the film that will obtain according to the same method cutting of reference example 1 after wind up, obtain polyamide resin film roll with reference to comparative example 1.The characteristic of the film that obtains being rolled up by method is similarly to Example 1 estimated then.With reference to creating conditions shown in table 9,10 of the volume of the film in the comparative example 1, the evaluation result of the characteristic of film volume is shown in table 11～15.
[with reference to comparative example 2]
Except replace material web A with material web C, all the other and reference example 1 similarly obtain the polyamide resin film roll with reference to comparative example 2.In addition, in reference comparative example 2, the average major diameter of the polyamide-based resin thin slice (chips C) beyond the polyamide-based resin thin slice that use amount is maximum, average minor axis and average thin slice length are adjusted into, make the average major diameter of its maximum with respect to use amount respectively polyamide-based resin thin slice (thin slice B), average minor axis and average thin slice length its ± 20% with interior scope in.The characteristic of the film that obtains being rolled up by method is similarly to Example 1 estimated then.With reference to creating conditions shown in table 9,10 of the volume of the film in the comparative example 2, the evaluation result of the characteristic of film volume is shown in table 11～15.
[with reference to comparative example 3]
Be warming up to about 100 ℃ in about 4.0 hours except the predrying condition with material web A, B becomes process, all the other and reference example 1 similarly obtain the polyamide resin film roll with reference to comparative example 3.In addition, predrying after, when collecting a certain amount of each thin slice measure moisture in mixer, the moisture of thin slice A, B is 1500ppm, the temperature that is fed to thin slice A, B before the hopper all is about 85 ℃.The characteristic of the film that obtains being rolled up by method is similarly to Example 1 estimated then.With reference to creating conditions shown in table 9,10 of the volume of the film in the comparative example 3, the evaluation result of the characteristic of film volume is shown in table 11～15.
[with reference to comparative example 4]
Before the hopper that behind predrying material web A, the B it is fed to directly over the extruder, except placing about 5 hours in each mixer, all the other and reference example 1 similarly obtain the polyamide resin film roll with reference to comparative example 4.In addition, be fed to hopper thin slice A, B moisture before and be 800ppm, the temperature that is fed to hopper thin slice A, B before all is about 30 ℃.The characteristic of the film that obtains being rolled up by method is similarly to Example 1 estimated then.With reference to creating conditions shown in table 9,10 of the volume of the film in the comparative example 4, the evaluation result of the characteristic of film volume is shown in table 11～15.
[with reference to comparative example 5]
Except attracting without vacuum tank when the resin with fusion is wound on the metallic roll, all the other and reference example 1 similarly obtain the polyamide resin film roll with reference to comparative example 5.The characteristic of the film that obtains being rolled up by method is similarly to Example 1 estimated then.With reference to creating conditions shown in table 9,10 of the volume of the film in the comparative example 5, the evaluation result of the characteristic of film volume is shown in table 11～15.
Table 9
| The cooling condition of fusion thin slice | |||||
| The draw speed of fusion thin slice (m/min) | Static is close to method | ||||
| Electrode | Discharge | Voltage (kv) | Electric current (mA) | ||
| Reference example 1 | 60 | 0.5mm φ needle-like metal line | Aura | 11.0±1.1 | 100 |
| Reference example 2 | 60 | 0.5mm φ needle-like metal line | Aura | 11.0±1.1 | 100 |
| Reference example 3 | 60 | 0.5mm φ needle-like metal line | Aura | 11.0±1.1 | 100 |
| Reference example 4 | 60 | 0.5mm φ needle-like metal line | Aura | 11.0±1.1 | 100 |
| Reference example 5 | 60 | 0.5mm φ needle-like metal line | Aura | 11.0±1.1 | 100 |
| Reference example 6 | 60 | 0.5mm φ needle-like metal line | Aura | 11.0±1.1 | 100 |
| Reference example 7 | 60 | 0.5mm φ needle-like metal line | Aura | 11.0±1.1 | 100 |
| With reference to comparative example 1 | 60 | 0.5mm φ needle-like metal line | Aura | 11.0±1.1 | 100 |
| With reference to comparative example 2 | 60 | 0.5mm φ needle-like metal line | Aura | 11.0±1.1 | 100 |
| With reference to comparative example 3 | 60 | 0.5mm φ needle-like metal line | Aura | 11.0±1.1 | 100 |
| With reference to comparative example 4 | 60 | 0.5mm φ needle-like metal line | Aura | 11.0±1.1 | 100 |
| With reference to comparative example 5 | 60 | 0.5mm φ needle-like metal line | Aura | 11.0±1.1 | 100 |
Table 10
| Material web mixing ratio (weight %) | Split the film condition | The system film | ||||||||||||
| Hopper inclination angle (degree) | The moisture of thin slice (ppm) | The attraction wind speed (m/min) of vacuum tank | Thin slice temperature when hopper is supplied (℃) | First vertical the extension | Second vertical the extension | Horizontal extension | Heat fixation (℃) | Relaxation processes (%) | ||||||
| Temperature (℃) | Multiplying power | Temperature (℃) | Multiplying power | Temperature (℃) | Multiplying power | |||||||||
| Reference example 1 | A/B＝5/95 | 70 | 800 | 5.0±0.5 | 91 | 85 | 2.1 | 70 | 1.6 | 130 | 4.0 | 210 | 5.0 | Well |
| Reference example 2 | A/B＝5/95 | 70 | 800 | 5.0±0.5 | 91 | 90 | 2.2 | 70 | 1.5 | 130 | 4.0 | 210 | 5.0 | Well |
| Reference example 3 | A/B＝5/95 | 70 | 800 | 5.0±0.5 | 91 | 85 | 2.1 | 70 | 1.6 | 130 | 3.6 | 215 | 3.0 | Well |
| Reference example 4 | A/B＝15/85 | 70 | 800 | 5.0±0.5 | 91 | 85 | 2.1 | 70 | 1.6 | 130 | 4.0 | 210 | 5.0 | Well |
| Reference example 5 | D/E＝5/95 | 70 | 800 | 5.0±0.5 | 91 | 85 | 2.1 | 70 | 1.6 | 130 | 4.0 | 210 | 5.0 | Well |
| Reference example 6 | A/B＝5/95 | 65 | 800 | 5.0±0.5 | 91 | 85 | 2.1 | 70 | 1.6 | 130 | 4.0 | 210 | 5.0 | Well |
| Reference example 7 | A/B＝5/95 | 70 | 800 | 3.0±0.5 | 91 | 85 | 2.1 | 70 | 1.6 | 130 | 4.0 | 210 | 5.0 | Well |
| With reference to comparative example 1 | A/B＝5/95 | 70 | 800 | 5.0±0.5 | 91 | 90 | 1.5 | 70 | 2.2 | 130 | 4.0 | 210 | 5.0 | Well |
| With reference to comparative example 2 | C/B＝5/95 | 70 | 800 | 5.0±0.5 | 91 | 85 | 2.1 | 70 | 1.6 | 130 | 4.0 | 210 | 5.0 | Well |
| With reference to comparative example 3 | A/B＝5/95 | 70 | 1500 | 5.0±0.5 | 85 | 85 | 2.1 | 70 | 1.6 | 130 | 4.0 | 210 | 5.0 | Well |
| With reference to comparative example 4 | A/B＝5/95 | 70 | 800 | 5.0±0.5 | 30 | 85 | 2.1 | 70 | 1.6 | 130 | 4.0 | 210 | 5.0 | Well |
| With reference to comparative example 5 | A/B＝5/95 | 70 | 800 | - | 91 | 85 | 2.1 | 70 | 1.6 | 130 | 4.0 | 210 | 5.0 | Well |
Table 11
| The characteristic of polyamide resin film roll | |||
| Average boiling water shrinkage (BSax:%) | Maximin (%) in the maximum boiling water shrinkage of all samples | The rate of change of the maximum boiling water shrinkage of average relatively boiling water shrinkage * (％) | |
| Reference example 1 | 4.2 | 4.5 | 7.1 |
| Reference example 2 | 3.8 | 4.1 | 7.9 |
| Reference example 3 | 3.2 | 3.0 | 6.3 |
| Reference example 4 | 3.5 | 3.7 | 5.7 |
| Reference example 5 | 4.0 | 4.3 | 7.5 |
| Reference example 6 | 4.0 | 3.7 | 7.5 |
| Reference example 7 | 5.1 | 5.5 | 7.8 |
| With reference to comparative example 1 | 5.0 | 4.6 | 8.0 |
| With reference to comparative example 2 | 5.7 | 5.1 | 10.5 |
| With reference to comparative example 3 | 6.3 | 6.9 | 9.5 |
| With reference to comparative example 4 | 5.5 | 5.0 | 9.1 |
| With reference to comparative example 5 | 4.2 | 4.7 | 11.9 |
*The rate of change of the maximum boiling water shrinkage of average relatively boiling water shrinkage: with in the maximin of the maximum boiling water shrinkage of all samples, the rate of change that calculates with difference the greater of average boiling water shrinkage.
Table 12
| The characteristic of polyamide resin film roll | |||
| Average boiling water shrinkage direction poor (BSad:%) | The maximin (%) of all sample boiling water shrinkage direction differences | The rate of change of the boiling water shrinkage direction difference of average relatively boiling water shrinkage direction difference *(％) | |
| Reference example 1 | 1.2 | 1.3 | 8.3 |
| Reference example 2 | 1.4 | 1.5 | 7.1 |
| Reference example 3 | 1.4 | 1.5 | 7.1 |
| Reference example 4 | 1.1 | 1.0 | 9.1 |
| Reference example 5 | 1.1 | 1.0 | 9.1 |
| Reference example 6 | 1.3 | 1.4 | 7.7 |
| Reference example 7 | 1.4 | 1.3 | 7.1 |
| With reference to comparative example 1 | 1.6 | 1.4 | 12.5 |
| With reference to comparative example 2 | 1.3 | 1.5 | 15.4 |
| With reference to comparative example 3 | 1.8 | 1.6 | 11.1 |
| With reference to comparative example 4 | 1.5 | 1.7 | 13.3 |
| With reference to comparative example 5 | 1.7 | 1.9 | 11.8 |
*The rate of change of the boiling water shrinkage direction difference of average relatively boiling water shrinkage direction difference: with in the maximin of the boiling water shrinkage direction difference of all samples, the rate of change that calculates with difference the greater of average boiling water shrinkage direction difference.
Table 13
| The characteristic of polyamide resin film roll | |||
| Average thickness (μ m) | The maximin of thickness on total length (μ m) | Rate of change with respect to the thickness of average thickness *(％) | |
| Reference example 1 | 15.03 | 15.80 | 5.1 |
| Reference example 2 | 15.05 | 15.82 | 5.1 |
| Reference example 3 | 15.03 | 15.75 | 4.8 |
| Reference example 4 | 15.05 | 16.05 | 6.6 |
| Reference example 5 | 15.05 | 15.64 | 3.9 |
| Reference example 6 | 15.04 | 16.18 | 7.6 |
| Reference example 7 | 15.04 | 16.24 | 8.0 |
| With reference to comparative example 1 | 15.05 | 17.32 | 15.1 |
| With reference to comparative example 2 | 15.05 | 15.99 | 6.2 |
| With reference to comparative example 3 | 15.03 | 13.75 | 8.6 |
| With reference to comparative example 4 | 15.05 | 13.51 | 10.2 |
| With reference to comparative example 5 | 15.05 | 16.92 | 12.4 |
*Thickness change with respect to average thickness: in the maximin with thickness on total length, the rate of change that calculates with difference the greater of average thickness.
Table 14
| The characteristic of polyamide resin film roll | |||
| Mean refractive index (Nz) | Maximin in the refractive index of all samples | The change of refractive rate of relative mean refractive index * (％) | |
| Reference example 1 | 1.510 | 1.518 | 0.5 |
| Reference example 2 | 1.512 | 1.505 | 0.5 |
| Reference example 3 | 1.514 | 1.508 | 0.4 |
| Reference example 4 | 1.510 | 1.518 | 0.5 |
| Reference example 5 | 1.510 | 1.515 | 0.3 |
| Reference example 6 | 1.512 | 1.519 | 0.5 |
| Reference example 7 | 1.510 | 1.519 | 0.6 |
| With reference to comparative example 1 | 1.511 | 1.494 | 1.1 |
| With reference to comparative example 2 | 1.511 | 1.519 | 0.5 |
| With reference to comparative example 3 | 1.508 | 1.517 | 0.6 |
| With reference to comparative example 4 | 1.512 | 1.523 | 0.7 |
| With reference to comparative example 5 | 1.510 | 1.525 | 1.0 |
*Change of refractive rate with respect to mean refractive index: in the maximin with the refractive index in all samples, the rate of change that calculates with difference the greater of mean refractive index.
Table 15
| Evaluation result | |||||||
| The S type curls | Impact strength (kg/cm) | Lamination strength (g/15mm) | Lamination process | ||||
| Comprehensively | ◎, zero, * each sample number | On average | Mobility scale | On average | Mobility scale | ||
| Reference example 1 | ◎ | ◎ 19，○ 2 | 11.4 | 10.6～12.0 | 200 | 190～210 | ○ |
| Reference example 2 | ○ | ◎ 8，○ 13 | 10.7 | 10.1～11.3 | 210 | 200～220 | ○ |
| Reference example 3 | ◎ | ◎ 21 | 13.8 | 12.9～14.2 | 300 | 280～320 | ○ |
| Reference example 4 | ◎ | ◎ 19，○ 2 | 10.2 | 9.9～10.6 | 200 | 180～220 | ○ |
| Reference example 5 | ◎ | ◎ 19，○ 2 | 11.2 | 10.8～11.9 | 200 | 180～210 | ○ |
| Reference example 6 | ◎ | ◎ 17，○ 4 | 10.8 | 10.2～11.5 | 230 | 220～240 | ○ |
| Reference example 7 | ◎ | ◎ 13，○ 8 | 10.9 | 10.4～11.5 | 230 | 220～240 | ○ |
| With reference to comparative example 1 | × | ◎ 2，○ 6，×13 | 11.5 | 10.2～12.8 | 200 | 150～220 | × |
| With reference to comparative example 2 | ○ | ◎ 3，○ 18 | 11.0 | 10.1～12.5 | 200 | 170～250 | △ |
| With reference to comparative example 3 | × | ○ 3，×18 | 10.5 | 9.5～11.2 | 210 | 170～240 | △ |
| With reference to comparative example 4 | × | ◎ 1，○ 8，×12 | 11.2 | 10.3～12.6 | 230 | 170～260 | × |
| With reference to comparative example 5 | × | ○ 5，×16 | 11.3 | 10.5～13.2 | 220 | 180～280 | △ |
[effect of the film among the embodiment]
From table 4～8 as can be seen, in the manufacture method of embodiment 1～8, be not subjected to the draw speed size restriction (66m/min of fusion thin slice, 75m/min), the film of manufacturing twist in along volume whole vertically on uneven thickness very little, the variation of rerum naturas such as boiling water shrinkage and refractive index is also very little.In addition, any one its lamination process in the film of embodiment 1～8 volume is good.In addition, can also see that constitute in the film volume of embodiment 1～8 any one the S type phenomenon of curling does not take place, and constitute the film volume of embodiment 3～7, its impact strength (obdurability, anti-pin hole) is good, lamination strength is higher.Contrast this situation, molten resin is not carried out the time corona discharge and carry out in the comparative example 1 of glow discharge when metallic roll static is close to, as mentioned above, the not extension film that can not obtain extending, thus can not be with speed system film similarly to Example 1.
In the film of reference example 1～7 volume any one is very little at whole along the volume uneven thickness on vertically as can be seen from table 11～15, the variation of rerum natura such as boiling water shrinkage and refractive index is also very little, the curling phenomenon of S type does not take place, and its lamination process is good.In addition, can also see, any one in the film of the film volume of formation reference example 1～7, its impact strength (obdurability, anti-pin hole) is good, and lamination strength is higher.On the other sidely be, as can be seen with reference to the film of comparative example 1～5 twist in along roller integral body vertically on the variation of rerum naturas such as uneven thickness, boiling water shrinkage and refractive index bigger, the phenomenon that the S type curls appears, lamination process is bad.
Industrial applicibility
Because manufacture method of the present invention, as mentioned above, it has good effect aspect boosting productivity, can perform well in the manufacturing of polyamide resin film roll. In addition, because the polyamide resin film roll that obtains of manufacturing method according to the invention has aforesaid good processing characteristics, can perform well in the purposes of packed processing of food.
Claims (16)
1. the manufacture method of a polyamide resin film roll, its by with the polyamide resin film roll below the above 3.0m of wide 0.2m, below the above 30000m of long 300m around getting up to form the film volume, it is characterized in that, comprising:
Polyamide-based resin is not extended melt extruding refrigerating work procedure, will be described not extending thin slice along the longitudinal and the twin shaft extension process of laterally twin shaft extension and will be wound into the coiling operation of roller shape by the double shaft extensioning film that twin shaft extends of thin slice with laminar melt extruded and cooling on mobile cooling body surface;
Describedly melt extrude in the refrigerating work procedure, with described polyamide-based resin melt extruded and when cooling off on mobile cooling body surface, between the polyamide-based resin thin slice of electrode that applies high direct voltage and described molten condition, carry out the corona discharge of time corona state, thereby provide the polyamide-based resin thin slice that enough makes molten condition to cling to the electric charge on mobile cooling body surface;
Be wound into the polyamide-based resin film of roller shape, begin 2m at coiling terminal point and cut out portion with interior the 1st sample that is provided with from film, begin 2m in coiling starting point then and the final portion that cuts out is set with interior from film, every about 100m sample is set since the 1st sample portion that cuts out and cuts out portion, also satisfy following requirement (3) when satisfying following requirement (1), (2)
(1) for each sample that cuts out from the described respectively portion of cutting out, when measuring when being peaked maximum boiling water shrinkage in the boiling water shrinkage in all directions, greater than 3% and less than 6%, the rate of change of the maximum boiling water shrinkage of all samples is being in ± 2%～± 10% the scope with respect to described average boiling water shrinkage simultaneously as the average boiling water shrinkage of the mean value of these maximum boiling water shrinkages;
(2) for each sample that cuts out from the described respectively portion of cutting out, when obtain as with respect to length direction for the boiling water shrinkage of+45 degree directions with respect to length direction during for the boiling water shrinkage direction difference of absolute value of the difference of the boiling water shrinkage of-45 degree directions, below 1.5%, the rate of change of the boiling water shrinkage direction difference of all samples is being in ± 2%～± 10% the scope with respect to described average boiling water shrinkage direction difference simultaneously as the average boiling water shrinkage direction difference of the mean value of these boiling water shrinkage direction differences;
(3) thickness change on the total length of the length direction of the roller that winds up is being in ± 2%～± 10% the scope with respect to average thickness.
2. the manufacture method of polyamide resin film roll as claimed in claim 1, it is characterized in that: be wound in the polyamide-based resin film of roller shape, for the sample that cuts out from the described respectively portion of cutting out, when measuring the refractive index of thickness direction, as the mean refractive index of the mean value of these refractive indexes more than 1.500 below 1.520, the variations in refractive index rate of all simultaneously samples with respect to described mean refractive index be ± 2% with interior scope in.
3. the manufacture method of polyamide resin film roll as claimed in claim 1, it is characterized in that: be wound in the polyamide-based resin film of roller shape, for the sample that cuts out from the described respectively portion of cutting out, when measuring the refractive index of thickness direction, as the mean refractive index of the mean value of these refractive indexes more than 1.500 below 1.520, the variations in refractive index rate of all simultaneously samples with respect to described mean refractive index be ± 1% with interior scope in.
4. the manufacture method of polyamide resin film roll as claimed in claim 1 is characterized in that: the main component that constitutes the polyamide of polyamide-based resin film is a nylon 6.
5. the manufacture method of polyamide resin film roll as claimed in claim 1 is characterized in that: will by the different polyamide resin film rolls that the mixture of polyamide-based resin forms more than 2 kinds around.
6. the manufacture method of polyamide resin film roll as claimed in claim 1 is characterized in that: the polyamide-based resin film that winds up is the film with polyolefin resin film lamination.
7. the manufacture method of polyamide resin film roll as claimed in claim 1 is characterized in that: the polyamide resin film roll that will extend by the tentering extension method around.
8. the manufacture method of polyamide resin film roll as claimed in claim 1 is characterized in that: incite somebody to action one by one the polyamide-based winding film that twin shaft extends.
9. the manufacture method of polyamide resin film roll as claimed in claim 1, it is characterized in that: will be unoriented in fact the sheet-like article that forms of polyamide-based resin under the high temperature more than vitrification point+20 of described polyamide-based resin ℃, by at least 2 stages after the multiplying power of longitudinal extension more than 3 times, to the multiplying power of horizontal extension more than 3 times, with this polyamide resin film roll around getting up.
10. the manufacture method of polyamide resin film roll as claimed in claim 1 is characterized in that: will carry out final extension handle the fixing polyamide resin film roll of after heat around.
11. the manufacture method of polyamide resin film roll as claimed in claim 1 is characterized in that: the polyamide-based resin film that has carried out relaxation processes behind the heat fixation is wound up.
12. the manufacture method of polyamide resin film roll as claimed in claim 1, it is characterized in that: in the polyamide-based resin film that winds up, add at least a kind in lubricant, anticaking agent, heat stabilizer, antioxidant, antistatic additive, photostabilizer, the resistance to impact modifying agent.
13. the manufacture method of polyamide resin film roll as claimed in claim 1 is characterized in that: in the polyamide-based resin film that winds up, add inorganic particle.
14. the manufacture method of polyamide resin film roll as claimed in claim 13 is characterized in that: inorganic particle is that average grain diameter is the silica dioxide granule of 0.5～5.0 μ m.
15. the manufacture method of polyamide resin film roll as claimed in claim 1 is characterized in that: in the polyamide-based resin film that winds up, add higher fatty acids.
16. the manufacture method of polyamide resin film roll as claimed in claim 1, it is characterized in that: the described corona discharge that melt extrudes the time corona state in the refrigerating work procedure, carry out between the polyamide-based resin thin slice of multi-needle electrode that applies high direct voltage and molten condition.
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| JP2004164971 | 2004-06-02 | ||
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| JP2008239654A (en) * | 2007-03-26 | 2008-10-09 | Unitika Ltd | Method for producing polyamide film |
| EP3685986B1 (en) * | 2017-09-22 | 2023-06-14 | Denka Company Limited | Resin film for vacuum forming, manufacturing method and usage thereof |
| WO2019116600A1 (en) * | 2017-12-14 | 2019-06-20 | 硬化クローム工業株式会社 | Cooling roll and method for producing thermoplastic resin sheet using same |
| CN110406083B (en) * | 2019-05-22 | 2021-02-26 | 浙江大学 | Method for improving mechanical property of block copolymer thermoplastic elastomer |
| CN113665145B (en) * | 2021-07-23 | 2023-08-25 | 山东双健新材料有限公司 | Corona treatment device for film preparation |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6241095B2 (en) * | 1978-07-25 | 1987-09-01 | Toyo Boseki | |
| JPH04103335A (en) * | 1990-08-23 | 1992-04-06 | Toyobo Co Ltd | Biaxially oriented polyamide film and its manufacture |
| CN1133235A (en) * | 1994-12-22 | 1996-10-16 | 东洋纺绩株式会社 | Double-axle orientation polyamide series resin film and preparation method |
| JP6241095B2 (en) * | 2013-07-02 | 2017-12-06 | 株式会社リコー | Information processing apparatus, print data evaluation method, and program |
-
2005
- 2005-06-02 CN CNB2005100742498A patent/CN100339205C/en not_active Expired - Fee Related
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6241095B2 (en) * | 1978-07-25 | 1987-09-01 | Toyo Boseki | |
| JPH04103335A (en) * | 1990-08-23 | 1992-04-06 | Toyobo Co Ltd | Biaxially oriented polyamide film and its manufacture |
| CN1133235A (en) * | 1994-12-22 | 1996-10-16 | 东洋纺绩株式会社 | Double-axle orientation polyamide series resin film and preparation method |
| JP6241095B2 (en) * | 2013-07-02 | 2017-12-06 | 株式会社リコー | Information processing apparatus, print data evaluation method, and program |
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