CN1721286A - Polyamide resin film roll, and production method therefor - Google Patents

Abstract

A biaxially oriented polyamide resin roll film capable of smooth and good-yield bag-making by laminating and efficiently producing S-curl-free package. A polyamide resin film roll which is provided with a first sample cutout portion within 2m of the film rolling end and the last cutout portion within 2m of the film rolling start, and which is adjusted such that, when sample cutout portions are provided about every 100m from the first sample cutout portion, the physical properties such as priming shrinkage percentage and thickness-direction refractive index of all samples cut out from respective cutout portions fall within specified ranges of variation widths.

Description

Polyamide resin film roll and manufacture method thereof

Technical field

The present invention relates to a kind of by batching the uniform high-quality film rolling of elongated and rerum natura that polyamide resin film forms, specifically, relate to the good polyamide resin film roll of processing characteristics a kind of and that the polyolefin resin film carries out lamination and uses when packings 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 packing 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 shrinkage 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, the timer-operated temperature of thermosetting must be improved 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 ratio of refraction 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 be finely tuned according to the film rolling of each use, therefore, even the aviation value that is wound into physics values such as the boiling water shrinkage of film of film rolling and ratio of refraction is in the scope of patent documentation 2, when the variable quantity of a film rolling 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 dynamic friction coefficient 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 extrusion press, 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 film rolling and ratio of refraction 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, ratio of refraction 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.

According to uniform polyamide resin film rolls of rerum natura height such as above-mentioned film thickness, boiling water shrinkage and ratio of refraction, can not damage the good obdurability and the anti-pin hole of polyamide-based resin film, do not produce the curling phenomenon of S type, processing characteristics is good when lamination process.But the film of being made up of this polyamide-based resin only, anti-pin hole is limited, not necessarily is fit to comprise the packing purposes of the food of moisture such as big quantity of fluid meat soup.And, as the measure of the anti-pin hole that improves polyamide-based resin film, with elastomer-filled be that the method for polyamide-based resin is known to film raw material.In this hybrid resin film rolling, not only can reduce the change of rerum naturas such as film thickness, boiling water shrinkage and ratio of refraction, when lamination process, can not obtain good processing properties, and occur fluctuation on the anti-pin hole in the 3 limit sealing bags after lamination process.

Summary of the invention

The inventor has carried out making great efforts research to the uniform production technology of height that the twin shaft of being made up of the hybrid resin of elastic body and polyamide-based resin extends the hybrid resin film, obtain following result, the purpose of this invention is to provide a kind of biaxially oriented polyamide resin film roll, can solve the problem of existing polyamide resin film roll, can be used in the packing purposes of very high anti-pin hole requirement, can implement trouble free and the bag processing of lamination successfully, can obtain does not efficiently have the packing material that the S type curls.But also provide a kind of double-axle orientation polyamide class hybrid resin film rolling that in back processing such as bag processing, can obtain the high finished product rate processed goods.A kind of manufacture method that can effectively make this biaxially oriented polyamide resin film roll is provided in addition.

The invention that the present invention program 1 is put down in writing is a kind of polyamide resin film roll, its be by the hybrid resin by polyamide-based resin and thermoplastic elastomer is formed, width is below the above 3.0m of 0.2m, length is that film below the above 30000m of 300m batches the film rolling that forms.The 1st sample portion of cutting out is arranged on apart from coiling terminal 2m with interior position, the final sample portion of cutting out is arranged on apart from coiling starting point 2m with interior position, every about 100m a sample is set from described the 1st sample portion that cuts out and cuts out portion, it is characterized in that satisfying following condition (1) and (2).

(1) each sample to cutting out from above-mentioned each portion that cuts out, measure the content of thermoplastic elastomer composition, when the aviation value that calculates these content is average content, the rate of change of the thermoplastic elastomer component content of all samples with respect to average content ± 10% scope in

(2) thickness change on the whole length of volume length direction of being batched with respect to mean thickness ± 2%～± 10% scope in.

The invention that scheme 2 is put down in writing is a kind of polyamide resin film roll, its be by the hybrid resin by polyamide-based resin and thermoplastic elastomer is formed, width is below the above 3.0m of 0.2m, length is that film below the above 30000m of 300m batches the film rolling that forms.The 1st sample portion of cutting out is arranged on apart from coiling terminal 2m with interior position, the final sample portion of cutting out is arranged on apart from coiling starting point 2m with interior position, every about 100m a sample is set from described the 1st sample portion that cuts out simultaneously and cuts out portion, it is characterized in that satisfying following condition (3)

(3) each sample to cutting out from above-mentioned each portion that cuts out, the tensile elasticity rate of MEASUREMENTS OF THIN take-up direction, the aviation value of these tensile elasticity rates are that average tensile elasticity rate is greater than 1.30GPa (1300N/mm ²) and less than 2.50GPa (2500N/mm ²), the rate of change of the tensile elasticity rate of all samples with respect to above-mentioned average tensile elasticity rate ± 10% scope in.

The invention of scheme 3 record is a kind of polyamide resin film roll, its be by the hybrid resin by polyamide-based resin and thermoplastic elastomer is formed, width is below the above 3.0m of 0.2m, length is that film below the above 30000m of 300m batches the film rolling that forms.The 1st sample portion of cutting out is arranged on apart from coiling terminal 2m with interior position, the final sample portion of cutting out is arranged on apart from coiling starting point 2m with interior position, every about 100m a sample is set from described the 1st sample portion that cuts out simultaneously and cuts out portion, it is characterized in that satisfying following condition (4)

(4) each sample to cutting out from above-mentioned each portion that cuts out, use back-and-forth bending test machine (GELVO TYPE FLEX-CRACKING TESTER), the pin hole number when carrying out the crooked test in 3000 cycles continuously with the speed in 1 minute about 40 cycle all is below 10.

The invention that scheme 4 is put down in writing is in scheme 1～3 in each described invention, to each sample that cuts out from above-mentioned each portion that cuts out, when the maxim in the boiling water shrinkage of measuring all directions is maximum boiling water shrinkage, the aviation value of these maximum boiling water shrinkages is that average boiling water shrinkage is 3%～6%, simultaneously the rate of change of the maximum boiling water shrinkage of all samples with respect to above-mentioned average boiling water shrinkage ± 2%～± 10% scope in.

The invention that scheme 5 is put down in writing is in scheme 1～3 in each described invention, to each sample that cuts out from above-mentioned each portion that cuts out, obtaining when being boiling water shrinkage direction difference with respect to the boiling water shrinkage of length direction+45 ° direction with respect to the absolute value of the difference of the boiling water shrinkage of length direction-45 ° direction, the aviation value of these boiling water shrinkage direction differences is that average boiling water shrinkage direction difference is below 1.5%, simultaneously, the rate of change of the sample boiling water shrinkage direction difference of all samples with respect to above-mentioned average boiling water shrinkage direction difference ± 2%～± 10% scope in.

The invention that scheme 6 is put down in writing is in scheme 1～3 in each described invention, to each sample that cuts out from above-mentioned each portion that cuts out, when measuring the ratio of refraction of thickness direction, the aviation value of these ratio of refraction is that mean refractive index is more than 1.500 below 1.520, simultaneously the variations in refractive index rate of all samples with respect to above-mentioned mean refractive index ± 2% scope in.

The invention that scheme 7 is put down in writing is in scheme 1～3 in each described invention, and the main component of polyamide-based resin is a nylon 6.

The invention that scheme 8 is put down in writing is in scheme 1～3 in each described invention, and the main component of thermoplastic elastomer is at least a in polyamide-based elastic body, the polyolefins elastic body.

The invention that scheme 9 is put down in writing is in scheme 1～3 in each described invention, and the polyamide resin film that is batched is the article with the polyolefin resin film laminating.

The invention that scheme 10 is put down in writing is in scheme 1～3 in each described invention, from the T mould, the polyamide-based hybrid resin of fusion is extruded, it is contacted with metallic roll and cool off, will batch the polyamide resin film of thus obtained not directed sheet-like article after biaxial stretch-formed.

The invention that scheme 11 is put down in writing is in scheme 1～3 in each described invention, and the polyamide resin film after will being stretched by the tentering extension method batches.

The invention that scheme 12 is put down in writing is in each described invention, will the polyamide resin film after twin shaft extends one by one to be batched in scheme 1～3.

The invention that scheme 13 is put down in writing is in each described invention, the polyamide resin film after longitudinally and laterally twin shaft extends to be batched in scheme 1～3.

The invention that scheme 14 is put down in writing is in scheme 1～3 in each described invention, under than the high temperature more than glass temperature+20 of the main component of above-mentioned polyamide-based hybrid resin ℃, at least after with two stages the sheet-like article of being made up of unoriented in fact polyamide-based hybrid resin longitudinally being stretched with the multiplying power more than 3 times,, the polyamide resin film that experiences after the above-mentioned stretching is batched along laterally stretching with the multiplying power more than 3 times.

The invention that scheme 15 is put down in writing is in scheme 1～3 in each described invention, to implement after the final stretch processing and heat fixation polyamide resin film batch.

The invention that scheme 16 is put down in writing is in each described invention, the polyamide resin film of having implemented relaxation processes behind the heat fixation to be batched in scheme 1～3.

The invention that scheme 17 is put down in writing is in scheme 1～3 in each described invention, in the polyamide resin film after batching, add at least a in lubricant, antiblocking agent, heat stabilizer, antioxidant, antistatic additive, photostabilizer, the Dent resistance modifier.

The invention that scheme 18 is put down in writing is in each described invention, in the polyamide resin film after batching, to add inorganic particle in scheme 1～3.

The invention that scheme 19 is put down in writing is in scheme 1～3 in each described invention, and inorganic particle is that mean grain size is the silica dioxide granule of 0.5～5.0 μ m.

The invention that scheme 20 is put down in writing is in each described invention, in the polyamide resin film after batching, to add higher fatty acid in scheme 1～3.

The invention that scheme 21 is put down in writing is a kind of manufacture method that is used for fabrication scheme 1～3 each described polyamide resin film roll, comprise the filming operation, the not extension film that this filming operation is obtained longitudinally and laterally carries out the twin shaft extension process that twin shaft extends, film after the twin shaft extension is batched the operation of volumeization, described filming operation is on one side to the thin slice is made up of polyamide-based resin with carry out melt extruded by the thin slice that thermoplastic elastomer is formed and also make film in one side, it is characterized in that satisfying following condition (1) and (2)

(1) in above-mentioned filming operation, to carrying out melt extruded after polyamide-based resin thin slice and the mixing of thermoplastic elastomer thin slice, the shape of each thin slice that uses is the oval column with the elliptic jet that comprises major diameter and minor axis, and, with the average major diameter of thermoplastic elastomer thin slice, average minor axis and average sheet length adjust to the average major diameter with respect to the polyamide-based resin thin slice, average minor axis and average sheet length ± 20% with interior scope

(2) in above-mentioned filming operation,, simultaneously, add the sublimability segregation and prevent agent and carry out the mixing of polyamide-based resin thin slice and thermoplastic elastomer thin slice carrying out melt extruded after polyamide-based resin thin slice and the mixing of thermoplastic elastomer thin slice.

The invention that scheme 22 is put down in writing is to put down in writing in the invention in scheme 21, above-mentioned twin shaft extension process is a kind of like this operation, it is back along cross directional stretch promptly longitudinally to carry out the stretching of two stages, and in above-mentioned two stages longitudinally stretched, the stretching ratio of F/s was than the stretching ratio height of subordinate phase.

The invention that scheme 23 is put down in writing is to put down in writing in the invention in scheme 21, above-mentioned filming operation comprises using and is provided with the operation of carrying out melt extruded as the extrusion press of the infundibulate hopper of material web supply unit, the angle of inclination of above-mentioned hopper is adjusted to more than 65 °, and, adjust to below the above 1000ppm of 800ppm supplying to the polyamide-based resin thin slice before the above-mentioned hopper and the moisture rate of thermoplastic elastomer thin slice, adjust to more than 80 ℃ supplying to the polyamide-based resin thin slice before the above-mentioned hopper and the temperature of thermoplastic elastomer thin slice.

The invention that scheme 24 is put down in writing is to put down in writing in the invention in scheme 21, above-mentioned twin shaft extension process is included in the preheating procedure implemented before the above-mentioned longitudinal stretching and the heat treatment step of enforcement above-mentioned longitudinal stretching after, with the rangeability of the film surface temperature of at a point in above-mentioned preheating procedure, heat treatment step and the longitudinal stretching operation adjust to along the mean temperature of the whole length of film ± 1 ℃ of scope in.

The invention that scheme 25 is put down in writing is to put down in writing in the invention in scheme 21, above-mentioned filming operation comprises by the molten resin that will extrude from above-mentioned extrusion press and being wound on the chill roll and the roller refrigerating work procedure that cools off, in described roller refrigerating work procedure, molten resin is attracted along the direction opposite with described coiling direction by suction device on the whole width of molten resin with the chill roll surface contact portion.

The invention effect

According to polyamide resin film roll of the present invention, even add man-hour at the bag of 3 limit sealing bags of the liquid meat soup of implementing to be used for the anti-pin hole of packing requirements height etc., almost trouble free ground is successfully implemented the lamination bag and is processed.Can efficiently obtain does not have the packing material that the S type curls.And in the following process of bag processing etc., can obtain processed goods with high finished product rate.In addition, if use polyamide resin film roll of the present invention, the food pack after the bag processing of being undertaken by lamination has also reduced the fluctuation of the anti-pin hole of each bag except having very high anti-pin hole.

According to the manufacture method of polyamide resin film roll of the present invention, can be cheap, obtain except having very high anti-pin hole the polyamide resin film roll that lamination process is also good efficiently.

The specific embodiment

Polyamide resin film roll of the present invention is cut out sample by method hereinafter described, to each sample that is cut out, measure the content of thermoplastic elastomer composition, when this content aviation value of calculating was average content, the rate of change of the thermoplastic elastomer component content of all samples must be in the scope with respect to average content ± 10%.

Sample of the present invention cuts out the employing following manner, promptly at first in the coiling terminal point 2m of distance film, first sample is set and cuts out portion, in the coiling starting point 2m of distance film, the portion that finally cuts out is set then, approximately sample is set from the first sample portion of cutting out and cuts out portion every 100m.And so-called " approximately every 100m " is meant and can cuts out sample in 100 ± 1m degree.

Hereinafter cutting out more specifically of said sample being introduced, for example is the polyamide-based film rolling of 498m on roller the time with length, within described coiling terminal 2m, cuts out initial sample (1).And for facility, it is to cut out (not tilting to cut out) in a rectangular shape that sample cuts out, this rectangular shape have along the limit of film length direction and along with the limit of this length direction vertical direction.Leaving coiling starting point side 100m position from cut out part then, cut out for the second time sample (2), cut out sample (3) for the third time in 200 meters positions of distance coiling starting point side equally, cut out sample (4) the 4th time in 300 meters positions of distance coiling starting point side, cut out sample (5) the 5th time in 400 meters positions of distance coiling starting point side, carrying out this sample when cutting out, because stump is less than 100m, the 6th (finally) sample (6) is to cutting out with interior arbitrary portion from coiling starting point 2m.

Content for each sample quantitative analysis thermoplastic elastomer composition that is cut out, when this content aviation value of calculating was average content, the rate of change of the thermoplastic elastomer component content of all samples must be in the scope with respect to average content ± 10%.At this moment, the rate of change of the thermoplastic elastomer component content of so-called all samples is meant, obtain the maximin in the thermoplastic elastomer component content (observed reading) of all samples, the ratio of a bigger difference and average content in the difference with the above-mentioned maximin obtained and average content.And the thermoplastic elastomer component content can this method of employing as mentioned below be measured, and promptly the apparent surface vertically cuts film, forms ultrathin section.By predetermined substance elastic body is dyeed, calculate this coloured portions and single-piece area ratio, by measuring at additive methods such as the infrared analysis of the distinctive peak value of elastic body or NMR analyses.

For polyamide resin film roll of the present invention, the elastic body component content rate of change of all samples that cut out preferably average content ± 9% with interior scope, more preferably ± 8% with interior scope, further preferably ± 7% with interior scope.

In addition, for polyamide resin film roll of the present invention, the elastic body component content rate of change of all samples that cut out is the smaller the better, if but consider survey precision, the lower limit of this rate of change is preferably about 2%.

Polyamide resin film roll of the present invention, during each sample measurement tensile elasticity rate that portion that cuts out from each is cut out, the just average tensile elasticity rate of the aviation value of this tensile elasticity rate is 1.30GPa (1300N/mm ²) above 2.50GPa (2500N/mm ²) below, the rate of change of the tensile elasticity rate of all samples is preferably adjusted in the scope with respect to above-mentioned average tensile elasticity power ± 10%.This moment, the rate of change of tensile elasticity rate of so-called all samples was meant, obtained maximin in the tensile elasticity rate of all samples, with in the difference of the maximin obtained and average tensile elasticity rate than the ratio of big difference with average tensile elasticity rate.

The tensile elasticity rate of polyamide resin film that constitutes polyamide resin film roll is extremely important for the anti-pin hole of obdurability that improves film self, and when tensile elasticity rate during less than 1.30GPa, the anti-pin hole of obdurability is insufficient.Opposite to tensile elasticity rate during greater than 2.50GPa, when forming 3 limit sealing bags, owing to the splitting resistance variation, so not preferred.Splitting resistance when forming in order to improve anti-pin hole of obdurability and tripartite sealing bag, tensile elasticity rate is more preferably 1.50GPa～2.30GPa.

And, for polyamide resin film roll of the present invention, by the rate of change of all sample tensile elasticity rates of being cut out preferably average tensile elasticity rate ± 9% with interior scope, be more preferably ± 8% with interior scope, further preferred ± 7% is with interior scope.

And, for polyamide resin film roll of the present invention,, consider survey precision, about following being limited to ± 2% of this rate of change though the rate of change of all sample tensile elasticity rates that cut out is the smaller the better.

And, in polyamide resin film roll of the present invention, each sample that cuts out for the portion that cuts out from each, by following method, use back-and-forth bending test machine, preferably will carry out pin hole the number average of 3000 cycles during crooked test continuously and adjust to below 10 with the speed in 1 minute about 40 cycle.

Anti-pin hole measuring method

The film that will be cut to given size (27.9 centimetres of 20.3 cm x) batches rectangular testing film behind process specified time pretreatment under the set point of temperature humidity, becomes the cylindric of specified length.These cylindrical thin-film two ends are separately fixed on the periphery of disc fixed head of described back-and-forth bending test machine and on the periphery of discoid moving head.The axis of parallel relative two statures is close to and rotates predetermined angular (440 °) within the specified length (7.6 centimetres) in the direction upper edge of fixed head to make moving head, after directly not advancing specified length (6.4 centimetres) rotationally then, along oppositely implementing above-mentioned these actions, make moving head return initial position, the crooked test that above-mentioned these actions is called 1 cycle, with specified speed (1 minute 40 cycle), successive reciprocation is implemented specified period (3000 cycles), then, the pin hole quantity to being produced in the specialized range (497 sq cm) outside the part of described testing film on being fixed on described fixed head and moving head periphery.

And, in polyamide resin film roll of the present invention, when cutting out by the aftermentioned method, in all samples, when the maxim in the boiling water shrinkage is maximum boiling water shrinkage on all directions by following method measurement, preferably the just average boiling water shrinkage of the aviation value of described maximum boiling water shrinkage is adjusted into the scope below 6% more than 3%.

And, in polyamide resin film roll of the present invention, when cutting out by the aftermentioned method, in all samples, by following method obtain with respect to length direction for the boiling water shrinkage on+45 ° the direction with respect to the absolute value of length direction for the difference between the boiling water shrinkage on-45 ° the direction, when just obtaining boiling water shrinkage direction difference, preferably the aviation value with described boiling water shrinkage direction difference is that average boiling water shrinkage direction difference is adjusted into below 1.5%.

" method of measurement 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 each portion that cuts out of polyamide resin film roll cuts into square, places more than 2 hours under 23 ℃, the atmosphere of 65%RH.Central authorities with this sample are that circle (about 20 centimetres of diameter) is drawn at the center, with vertically (film is drawn direction) is 0 °, with 15 ° be interval, picture passes through the straight line in the center of circle of described circle on 0～165 ° of direction along clockwise direction, measure the diameter of all directions, as the length before handling.Then, the sample furnace run in boiling water that is cut out was taken out after 30 minutes, to wipe out attached to the moisture on the specimen surface, after air-dry, under 23 ℃, the atmosphere of 65%RH, place more than 2 hours, measurement along the length of drawn straight line on above-mentioned each diametric(al) and with it as the length after handling, 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) by following formula 1～5.

BS=((length before handling-processing back length)/length before handling) * 100 (%) ... 1

BSx=with 15 ° of intervals on 0～165 ° of direction measured in maximum shrinkage percentage (%) ... 2

BSx summation/sample the number of all samples of BSax=... 3

BSd=| (BS of 45 ° of directions)-(BS of 135 ° of directions) | ... 4

BSd summation/sample the number of all samples of BSad=... 5

And, the BSx value that constitutes the polyamide resin film of polyamide resin film roll is guaranteed with biaxially oriented polyamide resin film shape pouch and the resistance to effect of heat (being called lamination strength or heat-resisting lamination strength) when implementing heat treatment, extremely important to the anti-pin hole of obdurability that improves film self simultaneously, when the BSx value less than 3% the time, the anti-pin hole of obdurability is insufficient, on the other hand, when the BSx value surpasses 6%, because it is bad lamination to occur, heat-resisting lamination strength when hot water treatment is insufficient, so not preferred.In order further to improve the anti-pin hole of obdurability and plyability and heat-resisting lamination strength, preferably the scope of BSx is 3.5～5.0%.

And the value of the BSd of the polyamide resin film of formation polyamide resin film roll brings very big influence for the curling phenomenon that is produced when boiling water treating, and the value of BSd is big more, the easy more warpage of bag, and curling becomes remarkable.If make BSd less than 1.5%, best less than 1.2%, the warpage of bag in the time of can containing boiling water treating as much as possible can prevent the generation of the curling phenomenon of S type.

In polyamide resin film roll of the present invention, the rate of change of the maximum boiling water shrinkage (BSx) of all samples that cut out preferably adjust to average boiling water shrinkage (BSa) ± scope of 2%～± 10% (more than ± 2% ± below 10%).Herein, the rate of change of the maximum boiling water shrinkage (BSx) of so-called all samples is meant, obtain maximin in the maximum boiling water shrinkage (BSx) of all samples, in the difference with described maximin and average boiling water shrinkage bigger one with the average ratio of boiling water shrinkage.

Just in polyamide resin film roll of the present invention, when the boiling water shrinkage with sample (1)～(6) is Xn (n=1～6), any must be in ± 10% in the difference of the difference of the maxim Xmax of Xn and average boiling water shrinkage (BSax), minimum value Xmin and average boiling water shrinkage (BSax), in other words, | any is preferably all less than 10% among the BSax-Xn| (at this moment || expression absolute value).

And in polyamide resin film roll of the present invention, the rate of change of the maximum boiling water shrinkage (BSx) of all samples that cut out preferably average boiling water shrinkage (BSa) ± 9% with interior scope, be more preferably at ± 8% with interior scope, further preferably ± 7% with interior scope.

In addition, in polyamide resin film roll of the present invention, the rate of change of the maximum boiling water shrinkage (BSx) of all samples that cut out is the smaller the better, still, considers survey precision, about following being limited to ± 2% of this rate of change.

And in polyamide resin film roll of the present invention, the rate of change of the boiling water shrinkage direction poor (BSd) of all samples that cut out preferably adjust to average boiling water shrinkage direction poor (BSad) ± scope of 2%～± 10% (more than ± 2% ± below 10%) in.At this moment, the rate of change of the boiling water shrinkage direction poor (BSd) of so-called all samples is meant, obtain maximin in the boiling water shrinkage direction poor (BSd) of all samples, in the difference of described maximin and average boiling water shrinkage direction difference bigger one with the average ratio of boiling water shrinkage direction difference.

Just in polyamide resin film roll of the present invention, when the boiling water shrinkage direction difference with sample (1)～(6) is Yn (n=1～6), any must be in ± 10% in the difference of the difference of the maxim Ymax of Yn and average boiling water shrinkage direction poor (BSad), minimum value Ymin and average boiling water shrinkage (BSad), in other words, | any is preferably all less than 10% among the BSad-Yn| (at this moment || expression absolute value).

And in polyamide resin film roll of the present invention, the rate of change of the boiling water shrinkage direction poor (BSd) of all samples that cut out preferably average boiling water shrinkage direction poor (BSad) ± 9% with interior scope, be more preferably at ± 8% with interior scope, further preferably ± 7% with interior scope.

And in polyamide resin film roll of the present invention, the rate of change of the boiling water shrinkage direction poor (BSd) of all samples that cut out is the smaller the better, still, considers survey precision, about following being limited to ± 2% of this rate of change.

Thickness change on the whole along its length length of polyamide resin film roll of the present invention must adjust to respect to mean thickness ± scope of 2%～± 10% (more than ± 2% ± below 10%) in.At this moment, the thickness change on the so-called whole along its length length is meant: obtain maximin in the thickness on the whole along its length length, a bigger ratio with mean thickness in the difference with described maximin and mean thickness.

Just in polyamide resin film roll of the present invention, any must be in ± 10% in the difference of difference, minimum value Tmin and the mean thickness (Ta) of the maximum of T max of thickness and mean thickness on the whole along its length length (the mean thickness Ta on the whole along its length length).

And in polyamide resin film roll of the present invention, on the whole along its length length thickness change preferably mean thickness (Ta) ± 8% with interior scope, be more preferably at ± 6% with interior scope.

And in polyamide resin film roll of the present invention, though thickness change is the smaller the better on the whole along its length length,, consider survey precision, about following being limited to ± 2% of this rate of change.

As mentioned above, the content by reducing by an elastic body composition in the polyamide resin film roll and the variation of film thickness, even the bag at the 3 limit closing bags of liquid meat soup that is used for the anti-pin hole of packing requirements height etc. adds man-hour, also can in bag processing and lamination process, prevent degraded appearance, can successfully carry out the good processing of yield rate.

As the amilan that uses in the present invention, for example can enumerate, with the epsilon-caprolactams nylon 6 of main material.In addition, as other amilan, the amilan that can enumerate the above lactams of 3 yuan of rings, omega-amino acid, obtain by the polycondensation of dibasic acid and diamines etc.Specifically, as lactams, except the epsilon-caprolactams shown in before, also have oenantholcatam, spicy inner formyl amine, lauramide, as the omega-amino-acids, can enumerate 6-aminocaprolc acid, 7-aminoheptylic acid, 9 aminononanoic acid, 11-aminoundecanoic acid.In addition, as the binary acids, adipic acid, glutaric acid, heptandioic 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, isophthalic acid, 2,6-naphthalene dicarboxylic acids, xylylene dicarboxylic acid.And then, as two amines, can enumerate ethylene diamine, propane diamine, butanediamine, hexamethylenediamine, pentanediamine, undecane diamines, 2,2,4 (or 2,4,4)-trimethyl hexamethylenediamine, cyclohexanediamine, two-(4,4 '-aminocyclohexyl) methane, MXDP etc.Also have, can use poly-mer 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 xylylene adipamide 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 amilan 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 strength under shock 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 ℃.

As the thermoplastic elastomer that uses in the present invention, for example can compatibly use the ionomer etc. of the olefine kind resins such as polyolefins elastic bodys such as copolymer, vinyl ionomer of copolymer, styrene and the butadidenne of polyamide-based elastic body, ethylene methacrylic acid copolymer, ethene and butylene such as the block of polyamide-based resin such as nylon 6 or nylon 12 and PTMG (polytetramethylene ethylene glycol) and PEC (carbowax) etc. or random copolymers.

In addition, the amount of the thermoplastic elastomer that in polyamide-based resin, adds, there is no particular limitation, but more than the preferred 1 weight % of the lower limit of addition, be more preferably more than the 2 weight %, further more than the preferred 3 weight %.On the other hand, the upper limit of addition is preferably below the 15 weight %, is more preferably below the 10 weight %, further preferred 6 weight % teachings of the deceased Ah.If the addition of thermoplastic elastomer less than 1 weight %, then can not get good anti-pin hole, thus not preferred, in contrast, if the addition of thermoplastic elastomer greater than 15 weight %, then the obdurability of film can be impaired, so not preferred.

Hereinafter introduce the preferable production process that is used to obtain polyamide resin film roll of the present invention.Polyamide resin film roll of the present invention is by following method manufacturing, will be the extruding of polyamide-based resin flakes melt and the not extension film that obtains longitudinally (length direction) and after laterally (Width) carries out the twin shaft extension to raw material just, is rolled into the roller shape.

The inventor studies the variation and the fluctuation of rerum naturas such as film rolling longitudinal thickness inequality (along the uneven thickness of the whole length of film rolling), boiling water shrinkage, thinks that the variation of described longitudinal thickness inequality, rerum natura and fluctuation mainly are because of being subjected to the very big influence of various factors in that molten resin is become in the casting operation of extension film not.If just the temperature when the infundibulate hopper (hereinafter referred is a hopper) that directly links to each other with extrusion press is supplied with resin is low and be fed to resin moisture rate height in the hopper, then longitudinal thickness is uneven on extension film not becomes big, and the variation of the rerum natura in double shaft extensioning film and fluctuation become big.And in the time will being wound on the metallic roll from the resin that the T mould is extruded, when the contact point of resin and metallic roll was disorderly, longitudinal thickness is not uneven in the extension film becomes big, and the change of rerum natura and fluctuation become big in the double shaft extensioning film.And if the stretching condition in the twin shaft extension process is not suitable for, longitudinal thickness is not uneven in the extension film increases, and has encouraged the change and the fluctuation of rerum natura.

The inventor has carried out making great efforts research according to the above-mentioned fact, by adopt following measure when making film rolling, can obtain rerum natura and change little film rolling.

(1) polyamide-based resin thin slice and elastomer sheet shape are unitized

Moisture rate when (2) resin flake is dry descends

(3) insulation when hopper is supplied with resin

(4) shape of hopper is fit to

(5) when mixed with resin, add segregation and prevent agent

(6) eliminate to add that resin prevents agent and the baneful influence that causes

(7) suitableization of stretching condition

Hereinafter above-mentioned various measures are introduced item by item.

(1) polyamide-based resin thin slice and elastomer sheet shape are unitized

In polyamide resin film roll manufacturing process of the present invention, be after polyamide-based resin thin slice and elastomer sheet are mixed in hopper with raw material, carry out fusion and stir, extrude filming (so-called hybrid mode) by extrusion press.Just the polyamide-based resin thin slice is fed in the different hoppers with elastomer sheet continuously or indirectly, as required, by the buffering hopper finally the extrusion press dead ahead or directly over hopper (hereinafter referred is " final hopper ") in one side polyamide-based resin thin slice and elastomer sheet are mixed, amount of compression with extrusion press as one man supplies to material web in the extrusion press quantitatively on one side, forms film.

By the capacity or the shape of final hopper, remaining thin slice quantity the raw material segregation phenomena occurs after a little while in the many and final hopper of the thin slice quantity in final hopper, just occurs forming different phenomenons from the thin slice that final hopper is supplied with to extrusion press.And under the different occasion of chip shape or proportion, this segregation phenomena is remarkable all the more.By this segregation phenomena, when making the film of long size, tensile elasticity rate, anti-pin hole, maximum boiling water shrinkage, boiling water shrinkage direction are poor, film thickness, thickness direction variations in refractive index.

In case just the size of the size of polyamide-based resin thin slice and elastomer sheet is different, when falling flake mixture in the final hopper, because undersized thin slice at first falls easily, if the quantitative change of thin slice residual is few in the final hopper, large-sized thin slice ratio is many, and this becomes the reason of raw material segregation.But in order to obtain rerum natura film rolling with low uncertainty, must be consistent so that contain raw material segregation phenomena in the final hopper by the shape that makes polyamide-based resin thin slice and elastomer sheet.

The polyamide thin slice is being discharged with wire from coincidence arrangement under molten condition after the coincidence usually, just by after the water cooling, is cut on line material cutter and forms.Thereby the polyamide thin slice is that section is oval-shaped oval column.On the other hand, the elastic body material web forms mostly has the discoid of elliptical section, study closing class between the shape of polyamide-based resin thin slice and elastic body material web and the raw material segregation, it found that, by average major diameter (millimeter) with the section ellipse of elastic body material web, average minor axis (millimeter), average sheet length (millimeter) is adjusted to the average major diameter (millimeter) with respect to the material web section ellipse of polyamide-based resin respectively, average minor axis (millimeter), average sheet length (millimeter) is in ± 25%, and the above-mentioned raw materials segregation is descended.And, because in case with the average major diameter of the section ellipse of elastic body material web, average minor axis, average sheet length adjust to respectively the average major diameter with respect to the material web section ellipse of polyamide-based resin, average minor axis, average sheet length ± 20% in, segregation prevents that effect is more remarkable, so be more preferably.

Moisture rate when (2) resin flake is dry descends

The thin slice that is fed in the hopper is heated and reduction moisture by devices such as mixers usually.When carrying out the thin slice drying, when making mylar volume or polypropylene film volume, in general, moisture rate reduction more can be contained to add water decomposition in extrusion process more when drying, obtains the good film volume.But the result that the inventor studies is, when making polyamide-based film rolling, only reduces moisture rate merely when drying, and the difficulty that then stretches can not obtain the uniform film rolling of rerum natura.By moisture rate is controlled at specialized range, guarantee moisture to a certain degree, water decomposition does not appear adding in extrusion process, and suitably plasticization can obtain the uniform film rolling of rerum natura.Just in order to obtain film rolling of the present invention, the chip moisture rate must be controlled below the above 1000ppm of 800ppm.In case the chip moisture rate is greater than 1000ppm, add water decomposition when having encouraged fusion, viscosity descends, and the film longitudinal thickness that extends is uneven worsens, and the double shaft extensioning film longitudinal thickness is uneven to be increased, and becomes that rerum natura changes and the reason of fluctuation.On the contrary, in case the chip moisture rate less than 800ppm, viscosity is excessive when fusion, system film (stretching easiness) worsens.And, below the above 950ppm of the preferred 850ppm of optimum moisture rate of the thin slice of in hopper, supplying with.

Insulation when (3) in hopper, supplying resin

Even under the above-mentioned occasion of like that moisture rate of thin slice being adjusted to below the above 1000ppm of 80ppm,, can not obtain the uniform film rolling of rerum natura in that the placement of the thin slice behind the heat drying is dropped to normal temperature (room temperature) back when hopper is supplied with until temperature.Just, must remain under the condition of high temperature at the thin slice of heat dryings such as mixer and supply with to hopper in order to obtain film rolling of the present invention.Specifically, must remain on by the thin slice behind the mixer heat drying and to supply to hopper more than 80 ℃, preferably remain on and supply to hopper more than 90 ℃.If the thin slice temperature that supplies to hopper is less than 80 ℃, the engaging-in deterioration of resin becomes the reason that longitudinal thickness is uneven and rerum natura changes and fluctuates, and can not obtain film rolling of the present invention.And when thin slice being carried out drying, baking temperature must be adjusted to below 150 ℃ by devices such as mixers.In case baking temperature is greater than 150 ℃, owing to there is the possibility that adds water decomposition when drying, preferably baking temperature is not more than 150 ℃.And, when being lower than 80 ℃,, must be heated once more more than 80 ℃ when hopper is supplied with by the thin slice temperature behind the mixer heat drying.

(4) suitableization of hopper shape

Use infundibulate hopper,, large scale thin slice and small size thin slice are fallen equally easily,, can reduce the raw material segregation effectively while the upper end of built-in thing keeps level to descend by making its leaning angle greater than 70 ° as final hopper.Best above-mentioned leaning angle is greater than 75 °.And so-called hopper leaning angle is meant the angle between funnelform hypotenuse and the horizon.Also can a plurality of hoppers be set in the upstream of final hopper.Must make leaning angle greater than 70 °, more preferably greater than 75 ° this moment in any one hopper.

And, preferably also contain the variation of boiling water shrinkage by the ratio that reduces the powder body that produces by the reduction of using material web.Because powder body encourages the generation of raw material segregation, so the powder body of preferably removing in operation to be produced reduces the ratio of the powder body that is comprised in the thin slice.Be preferably in the 1 weight % in all process steps of powder body ratio before material web enters extrusion press that is comprised, be more preferably in the 0.5 weight %.As the concrete grammar that is used to reduce the powder body ratio, for example can adopt following method, when promptly on line material cutter, forming thin slice,, when sky send material web, pass through swirler formula air filter on one side, and remove described powder body on one side by sieve.

(5) add segregation during mixed with resin and prevent agent

And, when in hopper, polyamide-based resin and elastic body being mixed, preferably add the sublimability segregation and prevent agent as the measure that reduces raw material segregation in the hopper.Prevent agent as this sublimability segregation, can use the ethylene glycol of low melting point.Wherein, also can compatibly use polyoxyethylene polyoxy third rare ethylene glycol.And the sublimability segregation of adding in polyamide-based resin material web and the elastic body material web prevents that the amount of agent from preferably accounting for 0.02%～2.0% of polyamide-based resin and elastomeric total weight.If less than 0.02%, then can not obtain sufficient segregation and prevent effect, on the contrary when greater than 2% the time, then worry can not distil fully and use up.

And, preferably adopt the suitable measure of hopper capacity that is utilized that makes as the measure that reduces raw material segregation in the hopper.At this moment, the suitable capacity of hopper is preferably extrusion press and per hour discharges in 20～100 weight % scopes of quantity in extrusion press is per hour discharged 15～120 weight % scopes of quantity.

And, can be by mixing as the method that polyamide-based resin material web and elastic body material web are mixed with the method for middle hopper (buffering hopper) to final hopper and extrusion press feed.

And, though can use following method, promptly when mixing as polyamide-based resin and elastomeric plurality of raw materials respectively, plurality of raw materials is fed to quantitatively the method for mixing in the hopper on one side on one side from the device of fixed supply material web continuously, or the method for using mixer or paddle dryer etc. to mix in advance, but after use, during a kind of method,, preferably reduce the size of material web in order when discharging compound, not produce the raw material segregation.

(6) eliminate to add that segregation prevents agent and the baneful influence (attraction when molten resin contacts with metallic roll) that causes

When obtaining not extension film melt extruding thin slice, make thin slice fusion and extrude under 200～300 ℃ of temperature by extrusion press from the T mould, and form (casting just) for after the film like (laminar), carry out chilling by the method that is wound on the chill rolls such as metallic roll that are cooled to set point of temperature.And from aspect considerations such as longitudinal thickness inequality, rerum natura variation and fluctuations, the preferred molten extrusion temperature is 240～290 ℃.In order to obtain film rolling of the present invention, when twisting in molten resin on the metallic roll, preferably a. g. the distance along gravity direction of exporting to till the chill roll surface of T mould (just from) is adjusted to 20～60 millimeters, has the vacuum tank suction devices such as (vacuum chambers) that wide cut attracts mouth by utilization simultaneously, on the whole width of molten resin, on the direction opposite, molten resin and chill roll surface contact portion are attracted, make molten resin force to be close on the metallic roll with take-up direction.

At this moment, prevent that in order to prevent above-mentioned sublimability segregation agent from hindering described molten resin and being close on the chill roll, must preferably adjust to 2.5～5.5 meter per seconds attracting the attraction wind speed of notch portion to adjust to 2.0～7.0 meter per seconds.And, though vacuum tank preferably sucking hole be a series of vacuum tank, in order to adjust easily the attraction wind speed in attracting mouthful, preferably will attract mouth in the part that laterally is divided into specified quantity, thereby can adjust the attraction wind speed each part.And in case the casting rate increase, the rotation that is accompanied by metallic roll produces follows stream, is close on the metallic roll because it hinders molten resin, in order further to bring into play the attraction effect that is caused by suction device.On metallic roll, be close to degree in order to improve molten resin, preferably will be arranged on suction device and the upstream side that adjoins (relative and with metallic roll direction of rotation side) by the wide cut shield that special teflon soft materials such as (registered trade mark (RTM)s) forms, interdict the described stream of following with suction device.And, in order to obtain film rolling of the present invention, the fluctuation of the attraction wind speed of vacuum tank must be contained in average attraction wind speed (setting value) ± 20% in, preferably be contained in ± 10% in.And, filter is set in vacuum tank preferably in order not make oligomer dust etc. that the attraction wind speed of vacuum tank is changed, by feeding back pressure reduction before and after this filter, attractive force is adjusted.

In order to obtain film rolling of the present invention, when being wound on molten resin on the chill roll, need be applied on the molten resin sheet material by the direct current negative charge of needle electrode 2～15kv, 90～105mA, Yi Bian glow discharge, Yi Bian make resin on metallic roll, be close to chilling continuously.And in a single day adjust to 7～14kv with the direct current negative charge that is applied this moment, because longitudinal thickness inequality, rerum natura variation and fluctuation are all very little, so preferably apply the direct current negative charge of 7～14kv.And, in order to obtain film rolling of the present invention, the fluctuation of the direct current negative charge that applied must be contained in average negative charge (setting value) ± 20% in, preferably be contained in ± 10% in.

(7) suitableization of stretching condition

As extension film not being carried out the method that twin shaft extends, need to adopt following vertically and horizontally stretching method, be about to not extension film longitudinal stretching on the roll-type stretcher, after carrying out cross directional stretch on the stenter formula stretcher, implement heat fixation and handle and relaxation processes.And, in order to obtain film rolling of the present invention,, must adopt so-called indulging-vertical-horizontal drawing process as the twin shaft extension method.So-called indulging-vertical-horizontal drawing process comes down to a kind of like this method, promptly when unoriented polyamide resin film being indulged stretching, the enforcement F/s stretches, implement subordinate phase when following continuously and stretch not being cooled to Tg, preferably carry out cross directional stretch with 3 times then, implement heat fixation then with the multiplying power more than 3.5 times.Thereby, in order to obtain film rolling of the present invention, state on the implementation vertical-vertical-during horizontal stretchings, must make the stretching ratio height of the stretching ratio of the vertical stretching of F/s than the vertical stretching of subordinate phase.Just by this stretching ratio height that makes the vertical stretching ratio that stretches of F/s than vertical stretchings of subordinate phase, can obtain not only rerum natura such as boiling water shrinkage well but also these rerum naturas also little film rolling that fluctuates.And state on the implementation vertical-vertical-during horizontal stretching, though the vertical stretching ratio that stretches of F/s is lower than the stretching ratio of the vertical stretching of subordinate phase usually, when the vertical stretching of F/s, can not stick on the roller and stretching easily, but by using the special rollers of making by special teflon (registered trade mark (RTM)) such as roller, even the vertical stretching ratio that stretches of F/s also can not cause on roller adhesively to stretch easily than the stretching ratio height of the vertical stretching of subordinate phase.

State on the implementation vertical-vertical-during horizontal stretchings, make preferably that F/s is vertical to be stretching under 80～90 ℃ of temperature about 2.0～2.4 times of stretching.In case the vertical stretching stretching ratio of F/s is greater than above-mentioned scope, because longitudinal thickness is uneven big, preferably the vertical stretching stretching ratio of F/s does not exceed above-mentioned scope.In addition, vertical being stretching under 65～75 ℃ of temperature of subordinate phase stretched about 1.3～1.7 times, in case the vertical stretching stretching ratio of subordinate phase is less than above-mentioned scope, because the boiling water distortion becomes big, practicality is bad, and the vertical stretching stretching ratio of subordinate phase preferably is not less than above-mentioned scope.On the contrary, in case the vertical stretching stretching ratio of subordinate phase greater than above-mentioned scope, longitudinal strength (extend 5% o'clock intensity etc.) reduces, practicality is bad, so the vertical stretching stretching ratio of subordinate phase preferably is not more than above-mentioned scope.

State on the implementation vertical-vertical-during horizontal stretching,, can adopt hot-rolling stretching, infrared ray roller radiation stretching etc. as longitudinal stretching.And by this vertical-vertical-when horizontal drawing process is made polyamide resin film of the present invention, not only can reduce the longitudinal thickness inequality, rerum natura changes and fluctuation, and can reduce that horizontal rerum natura changes and fluctuation.And implement vertical-vertical-during horizontal stretchings, preferably indulging stretching condition is 3.0～4.5 times.

And implement vertical-vertical-during horizontal stretching, preferably under 120～140 ℃, carry out about 4.0～5.5 times cross directional stretch.In case the cross directional stretch multiplying power is lower than above-mentioned scope, transverse strength (extend 5% o'clock intensity etc.) reduces, and practicality is bad, so the cross directional stretch multiplying power had better not be lower than above-mentioned scope.On the contrary, in case the cross directional stretch multiplying power greater than above-mentioned scope because laterally percent thermal shrinkage becomes big, so the cross directional stretch multiplying power had better not be greater than above-mentioned scope.On the other hand, if the cross directional stretch temperature is lower than above-mentioned scope, because the boiling water distortion becomes big, practicality is bad, therefore the cross directional stretch temperature had better not be lower than above-mentioned scope, if opposite cross directional stretch temperature greater than above-mentioned scope, transverse strength (extend 5% o'clock intensity etc.) reduces, practicality is bad, so the cross directional stretch temperature had better not be greater than above-mentioned scope.

And, in order to obtain film rolling of the present invention, be preferably in 180～230 ℃ of heat fixations of implementing down after vertical-vertical-horizontal stretching and handle.If the heat fixation treatment temperature is lower than above-mentioned scope, because the vertical and horizontal percent thermal shrinkage becomes big, so the heat fixation treatment temperature had better not be lower than above-mentioned scope.In case opposite heat fixation treatment temperature is greater than above-mentioned scope, because the film strength under shock step-down that twin shaft extends, so the heat fixation treatment temperature had better not be greater than above-mentioned scope.

And, in order to obtain film rolling of the present invention, after being preferably in heat fixation and handling, implement 2～10% relaxation processes.In case lax ratio is lower than above-mentioned scope, because the vertical and horizontal percent thermal shrinkage becomes big, therefore lax ratio had better not be lower than above-mentioned scope.Opposite in case lax ratio is greater than above-mentioned scope, and vertical and horizontal intensity (extend 5% o'clock intensity etc.) reduces, and practicality is bad, and therefore lax ratio had better not be greater than above-mentioned scope.

Though the width to film rolling of the present invention is not particularly limited, calm easy to operate setting out, the width lower limit of film rolling is preferred more than 0.35 meter, is more preferably more than 0.50 meter.On the other hand, the width upper limit of film rolling is preferred below 2.5 meters, is more preferably below 2.0 meters, and is further preferred below 1.5 meters.In addition, though unqualified to the volume length of film rolling, calm easy to operate setting out, the volume length lower limit of film rolling is preferably greater than 1000 meters more preferably greater than 500 meters.On the other hand, the volume length upper limit of film rolling is preferably less than 25000 meters, and is preferably less than 20000 meters, best less than 15000 meters.And when film thickness is 15 μ m, preferably less than 12000 meters.As batching core, the core that can use 3 inches (7.62 centimetres), 6 inches, 8 inches etc. paper, plastic core or metal to make usually.

Though there is no particular limitation to the film thickness that constitutes polyamide resin film roll of the present invention, for example as the polyamide-based film of packaging, preferred thickness is 8～50 μ m, is more preferably 10～30 μ m.

And in the polyamide-based resin film that constitutes film rolling of the present invention, in the scope that does not hinder characteristic, also can contain various additives such as lubricant, antiblocking agent, heat stabilizer, antioxidant, antistatic additive, photostabilizer, Dent resistance modifier.Particularly good for the slickness of double shaft extensioning film, preferably contain various inorganic particles.In addition,, preferably contain the mean grain size (average particulate diameter just) of 0.5～5.0 μ m, preferred silica dioxide granule as inorganic particle.If mean grain size is lower than 0.5 μ m, then can not get good lubricity, on the contrary, if mean grain size 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 mean grain size can adopt the method that calculates weight average particle diameter according to the particle size distribution that obtains by Coulter-counter, can measure the particle before adding to amilan, 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 film rolling is become better if add the organic lubricants such as ethylenebis stearic acid that can bring into play the effect that reduces surface energy, therefore preferred.

And in the polyamide-based resin film that constitutes film rolling of the present invention,, can implement heat treatment and damping and handle in order to make dimensional stability good according to purposes.In addition, in order to make the film surface property followed good, on one side can implement Corona discharge Treatment, coating processing or flame treatment etc., Yi Bian implement processing such as printing, deposition.

Any measure can both reduce the rerum natura variation of film rolling effectively in the measure of not only above-mentioned (1)～(7), and by using the combination of (1)～(7) measure, the rerum natura that also can reduce film rolling very effectively changes.

Embodiment

Below, introduce the present invention in detail by embodiment, but the present invention is not limited to these embodiments, in not breaking away from essential scope of the present invention, the variation that can be fit to.The film forming condition of film rolling in composition, embodiment and the comparative example of the material web of using in shape, embodiment and the comparative example of the material web A～H that in table 1 and 2, uses in expression embodiment and the comparative example respectively.And thin slice A is made up of the nylon 6 (relative viscosity=2.8, Tg=41 ℃) of 99.70 weight %, the silica dioxide granule of 0.30 weight %.Thin slice B, H are made up of nylon 12 and the copolymer (relative viscosity=2.0) of PTMG (polytetramethylene ethylene glycol), the two stearic amides of ethene of 0.15 weight % of 99.85 weight %.Chips C is made up of 99.85% nylon 6 and the copolymer (relative viscosity=2.4) of PEC (carbowax), the two stearic amides of ethene of 0.15 weight %.Thin slice D is made up of 99.85% ethylene methacrylic acid copolymer (at 190 ℃ of following MFR (melt flow rate)=2.4g/10 minute), the two stearic amides of ethene of 0.15 weight %.Thin slice E is made up of the ethylene-butylene copolymer (MFR=2.0g/10 minute) of 99.85 weight %, the two stearic amides of ethene of 0.15 weight %.Thin slice F is made up of the vinyl ionomer (MFR=2.4g/10 minute) of 99.85 weight %, the two stearic amides of ethene of 0.15 weight %.Thin slice G is made up of the styrene-butadiene-copolymer (MFR=2.8g/10 minute) of 99.85 weight %, the two stearic amides of ethene of 0.15 weight %.In addition, the silica dioxide granule that adds in the thin slice A is that mean grain size is the particle of 3.0 μ m.And the shape of thin slice A～H all is an elliptical cylinder-shape, and section major diameter, the section minor axis of thin slice B～G are identical with sheet length.

Table 1

Table 2

Embodiment 1

Use the mixing device of 15 kilolitres on one side to carry out predrying in about 8.0 hours above-mentioned thin slice A heating under about 120 ℃ on one side.On the other hand, Yi Bian use the mixing device of another 15 kilolitre to carry out predrying in about 8.0 hours above-mentioned thin slice B heating under about 80 ℃ on one side.Quantitatively take out various thin slices from mixing device, measure moisture rate, the moisture rate of thin slice A, B all is 800ppm.And, use Ka Er-Fei Xier moisture meter (MKC-210 that KYOTO electronics, inc. makes), weight 1g sample is carried out the measurement of moisture rate under 230 ℃ of sample heating-up temperatures.

Then that the thin slice in the mixer after predrying is without interruption in mixing agitator by quantitative feeding screw.The supply of thin slice A is 97.0 weight %, and the supply of thin slice B is 3.0 weight %.To add in the hopper of having supplied thin slice A and B as the two stearic amides of the ethene of lubricant (common prosperity chemical company makes, ラ イ ト ァ マ イ De WE-183),, add 1.5 (0.15 weight portions) if be 1000 with the total weight of thin slice A and B.And segregation prevents agent as sublimability, if be 1000 with the total weight of thin slice A and B, adds polyoxyethylene polyoxy third rare ethylene glycol (Sanyo chemical company makes, ニ ユ Port-Le PE-64) of 1000ppm.

Then, the mixed material of thin slice A that will mix in above-mentioned mixing agitator and B is fed in the hopper directly over the extrusion press continuously.Hopper has the capacity that can hold 150 kilograms of material web.The discharge rate of extrusion press is per hour 450 kilograms.And, the leaning angle of hopper is adjusted to 70 °.In embodiment 1, the average major diameter of elastomer sheet (thin slice B), average minor axis, average sheet length the average major diameter of the maximum polyamide-based resin thin slice of use amount (thin slice A), average minor axis, average sheet length ± 20% in.

And, when hopper supply thin slice A, B that the thin slice temperature step-down within reason ground in each mixer is dry, be fed in the hopper at short notice.The temperature that is fed to hopper thin slice A, B before all approximately is 91 ℃.The thin slice A, the B that are supplied are fully mixed in hopper, under 270 ℃, from the T mould, melt extrude, be wrapped on the metallic roll of the rotation that is cooled to 17 ℃, cool off rapidly by the single axle extrusion press.Obtaining thickness is the not extension film of 257 μ m.And the draw speed of described not extension film (velocity of rotation of metallic roll) approximately is 60m/min.

A. g. when being wrapped in molten resin on the metallic roll is adjusted to 40 millimeters, is applied on the fused films by the direct current negative charge of needle electrode with 11 ± 1.1kv, 100mA, by glow discharge, molten resin is close on the metallic roll.And when being wrapped in molten resin on the metallic roll, utilize vacuum tank on the whole width of molten resin, and along the direction opposite molten resin and metallic roll contact portion are attracted with the resin coiling direction, promote being close to of molten resin thus.And the attraction wind speed of vacuum tank is along attracting a mouthful whole width (the whole width of molten resin just) to adjust to 5.0 ± 0.5 meter per seconds.

Then, with the not extension film that obtained by special teflon system roller behind about 2.1 times of longitudinal stretching under about 85 ℃ draft temperature (the 1st longitudinal stretching), by ceramic roller about 1.5 times of longitudinal stretching (the 2nd longitudinal stretching) under about 70 ℃ draft temperature.And the sheet material behind the longitudinal stretching is directed to stenter continuously, 4 times of about 130 ℃ of following cross directional stretchs, at about 210 ℃ of following heat fixations, after implementing the processing of 5.0% transverse relaxation, cool off,, the double shaft extensioning film of about 15 μ m is made film continuously by two edge portions are cut off, make 2000 meters, make undressed volume.And when making 2000 meters films continuously, the film surface temperature rangeability is mean temperature ± 0.8 ℃ at preheating procedure, at stretching process is mean temperature ± 0.6 ℃, at heat treatment step be ± 0.5 ℃, and, the undressed volume that is obtained is cut into 2000 meters of wide 400 millimeters, length, is wound on 3 inches the paper tube, obtain 2 polyamide resin film rolls (cutting volume).Then, use 2 cuttings volumes being obtained (just from product that same undressed volume obtained), carry out performance evaluation by following method.And, in the measurement of following elastic body component content, tensile elasticity rate, anti-pin hole, BS (boiling water shrinkage), BSx (maximum boiling water shrinkage), BSd (the boiling water shrinkage direction is poor), ratio of refraction, first sample is set in distance coiling terminal 2m cuts out portion, approximately the 2nd～20th sample be set from the described first sample portion of cutting out and cut out portion, in distance coiling starting point 2m, the 21st sample be set and cut out portion, cut out each sample portion of cutting out that portion's to the 21 samples cut out portion from described first sample and cut out the sample film every 100m.Evaluation result in strength under shock, lamination strength, has shown the aviation value of the numerical value of each measured specimen sample, the numerical value change scope of each specimen sample shown in table 3～9.And, curl for the S type, shown the number of the specimen sample that becomes each evaluation criterion, the comprehensive evaluation standard of all specimen sample.

The content of elastic body composition

Along polyamide resin film being cut off perpendicular to the surface and perpendicular to take-up direction ground, make ultrathin section, utilize phosphotungstic acid and ruthenium-oxide to dye by described superthin section, sample is adjusted.The transmission electron microscope (TEM) of being made by company of NEC (JEM2010) is observed under 10000 times then, has taken electron micrograph (about 220 millimeters of the about 160 millimeters * take-up direction of thickness direction).The image-processing system (analy SIS) that utilizes company of NEC to make then, the elastomer portion area that phosphotungstic acid and ruthenium-oxide have been dyeed accounts for the ratio of the gross area and calculates as the elastic body component content.

Tensile elasticity rate

Polyamide resin film is sampled, obtain 150 millimeters of length, wide 15 millimeters sample, damping is 24 hours under the atmosphere of 23 ℃ of temperature, relative humidity 50%.Then under the condition of 23 ℃ of temperature, relative humidity 50%, according to JIS K-7127, the mileage meter AG-100E type that utilizes Shimadzu Corporation to make, the film of damping is clamped between the chuck every 100 meters, draw speed with 200 millimeters/minute stretches, and the ratio of drawing stress in the stretch ratio limit and cooresponding strain is calculated as tensile elasticity rate.

Anti-pin hole

To be cut to 20.3 centimetres (8 inches) * film of 27.9 centimetres of (11 inches) sizes, under the condition of 23 ℃ of temperature, relative humidity 50%, place more than 24 hours, carry out pretreatment.Then, the oblong testing film is batched, become the cylindric of 20.32 centimetres of length (8 inches).One end of this cylinder is fixed on the periphery of discoid fixed head of back-and-forth bending test machine (the NO.901 type that industrial of science makes) (according to the MIL-B-131C specification), the other end of discoid film is fixed on and this fixed head at interval on the discoid moving head periphery of 17.8 centimetres (7 inches) and experimental engine respect to one another.The axis of parallel relative two statures is close within 7.6 centimetres (3.5 inches) and rotates 440 ° in the direction upper edge of fixed head to make moving head, after directly not advancing 6.4 centimetres (2.5 inches) rotationally then, along oppositely implementing above-mentioned action, make moving head return initial position, the crooked test that above-mentioned these actions is called 1 cycle, speed with 1 minute 40 cycle, successive reciprocation is implemented 3000 cycles, then, the pin hole quantity that is produced in 17.8 centimetres of the specialized ranges outside the part of described testing film on being fixed on described fixed head and moving head periphery (7 inches) * 27.9 centimetres (11 inches) part is calculated (just the pin hole quantity of per 497 sq cms (77 sq in) being measured).

Boiling water shrinkage

The double-axle orientation polyamide based resin film (sample film) that each portion that cuts out from the cutting volume is cut off cuts out, cut out into the square shape that every limit is 21 centimeter length, under the atmosphere of 23 ℃ of temperature, 65%RH, place more than 2 hours, central authorities with this sample are that center picture diameter is 20 centimetres a circle, with vertical (film is drawn direction) is 0 °, on 0～165 ° of direction, draw the straight line in the center of circle of passing through described circle along clockwise direction with 15 ° intervals, measure the diameter of all directions, as the length before handling.Then, the sample furnace run in boiling water that is cut out was taken out after 30 minutes, to wipe out attached to the moisture on the specimen surface, after air-dry, under 23 ℃, the atmosphere of 65%RH, place above 2 hours, measurement along the length of drawn straight line on above-mentioned each diametric(al) and with it as the length after handling, 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) by following formula 1～5.

Subsequently, by maximin in the maximum boiling water shrinkage (BSx) of obtaining all samples, by in the difference of calculating described maximin and average boiling water shrinkage (BSax) bigger one with the average ratio (%) of boiling water shrinkage, obtain the rate of change of maximum boiling water shrinkage (BSx) with respect to average boiling water shrinkage (BSax).And, by maximin in the boiling water shrinkage direction of obtaining all samples poor (BSd), by in the difference of calculating described maximin and average boiling water shrinkage direction poor (BSad) bigger one with the average ratio (%) of boiling water shrinkage direction poor (BSad), obtain the rate of change of boiling water shrinkage direction poor (BSd) with respect to average boiling water shrinkage direction poor (BSad).

The longitudinal thickness inequality

With about 3 centimetres width described cutting is involved in row on the whole length along its length and shear, make the uneven thickness measurement and roll up with cutting.Then, the uneven thickness measurement mechanism (wide scope high sensitivity electronic microcalliper K-313A) that utilizes An Li company to make is obtained mean thickness, maximum ga(u)ge, minimum thickness on the whole along its length length.Utilize following formula 7 subsequently, calculate one bigger in the difference of described maximum ga(u)ge, minimum thickness and mean thickness, calculate this ratio (%), thereby calculate the thickness change on along its length the whole length than big difference and mean thickness.

Thickness change=| maximum ga(u)ge or minimum thickness-mean thickness |/mean thickness ... 7

Ratio of refraction

Use " the Abbe refractometer 4T type " of liking that (ATAGO) company that delays makes, each sample film that will be cut out from each sample cut-out portion place under the atmosphere of 23 ℃ of temperature, 65%RH surpass more than 2 hours after, measure the ratio of refraction (Nz) of thickness direction, and, calculate the mean refractive index of all sample films.As shown in table 8, calculate in all samples the poor of maximum or minimum Nz and mean refractive index, calculate simultaneously this difference with respect to the ratio of described mean refractive index as rate of change.

Strength under shock

Each sample film that will be cut out from each sample cut-out portion place under the atmosphere of 23 ℃ of temperature, 65%RH surpass 2 hours after, use " the film shock test machine TSS formula " of the manufacturing of Japan precision equipment manufacturing company, by diameter is that 12.7 millimeters dome-type impulse member is measured rupture strength, as strength under shock.And, calculate the average strength under shock of all sample films.

Lamination process

Use and the different cutting volume (from the identical product that undressed volume obtained) of above-mentioned cutting volume of measuring boiling water shrinkage, longitudinal thickness inequality, ratio of refraction, strength under shock, coating polyurethanes AC agent (" EL443 " that Japan モ-ト Application company makes) on the biaxially oriented polyamide resin film that constitutes this cutting volume.Then, the single test laminating machine (single test laminator) that uses modern machines company to make, under 315 ℃, extrude the LDPE that thickness is 15 μ m (low density polyethylene (LDPE)) film, then, laminate thickness is LLDPE (directly the locking the shape low density polyethylene (LDPE)) film of 40 μ m continuously in the above, obtains the laminate roll of the 3 layer laminate structures be made up of polyamide-based resin/LDPE/LLDPE.In addition, by the processability of following 3 grade evaluations when making above-mentioned laminate roll.

Zero: on volume, do not produce fold, also do not need regularization condition

△:, eliminate described fold by condition is adjusted

*: even carried out the adjustment of various conditions, on volume, still produce fold.

Lamination strength

And, to cut out from the laminated film that above-mentioned laminate roll cuts off into 200 millimeters of wide 15 millimeters, length as test piece, " the rising the imperial UMT-II-5000 type of happiness " of using Japan BALDWIN company to make is in the peel strength of measuring under the condition of 23 ℃ of temperature, relative humidity 65% between polyamide-based resin film layer and the LDPE layer.And, draw speed 10 cm per minute, peel angle 180 is spent, and water is coated on the described released part measures.And, following coupons is carried out the measurement of lamination strength, the position that is about in the coiling terminal point 2m of laminate roll cuts out the 1st coupons, approximately the 2nd～19 coupons is cut out from described the 1st sample every the 100m order, in distance coiling starting point 2m, the 20th coupons is cut out, the the 1st～the 20th coupons is carried out the measurement of above-mentioned lamination strength, and calculate the aviation value of described observed reading.

The S type phenomenon of curling

The test sealer that uses western Mechanology Inc. to make, batch the laminated film doubling that length direction will batch as above-mentioned laminate roll along being parallel to, on vertical every two ends, 20 millimeters scopes are carried out heat seal with 150 ℃ at every turn, discontinuously 10 millimeters scopes are carried out 10 millimeters of heat seals in perpendicular direction every 150 millimeters, the acquisition width is 200 millimeters a half-blank.On the coiling length direction, be after 10 millimeters ground cut off two edge portions, on perpendicular direction, to cut off with hermetic unit at the hermetic unit intersection, make 3 limit leak free bags (sealed width: 10 millimeters).From this tripartite sealing bag, to be chosen as the 1st sample by the inner 3 limit sealing bags of made that divide of the coiling terminal point 2m of distance laminate roll, will by about 100,200 apart from described the 1st sample making part ..., 1800,3 limit sealing bags of the part manufacturing of 1900m are chosen as the 2nd～20 sample respectively, will be chosen as the 21st sample by the inner 3 limit sealing bags of made that divide of distance laminated wound starting point 2m.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 1 round the clock, and it is 21 3 limit sealing bags are overlapping, from top whole bag face is applied 1 kilogram load, after keeping described load 1 round the clock, load is removed, the warpage degree (the S type curls) of bag is estimated by following manner.

◎: at all do not have warpage

Zero: see seldom warpage

*: find tangible warpage

* *: warpage is serious

Embodiment 2

The not extension film that will obtain in the same manner with embodiment 1 by teflon system roller under about 90 ℃ draft temperature with about 2.2 times of vertical stretchings (the 1st vertical the stretching) after, by the ceramic roller after indulge stretchings (the 2nd indulges stretching) with about 1.5 times under about 70 ℃ draft temperature.And then, identical with the 1st embodiment, sheet material after vertical the stretching is directed to stenter continuously, 4.0 times of about 130 ℃ of following cross directional stretchs, at about 210 ℃ of following heat fixations, after the horizontal relaxation processes of enforcement 5%, cool off, go to two edges portion by sanction, make film continuously, obtain the double shaft extensioning film of 15 μ m more than 2000 meters.Identical with embodiment 1, the rangeability of the film surface temperature when continuously making film is mean temperature ± 0.8 ℃ in preheating procedure, is mean temperature ± 0.6 ℃ in stretching process, is mean temperature ± 0.5 ℃ in heat treatment step.Identical with embodiment 1 then, by the film that is obtained is sheared and batched, obtain the polyamide resin film roll of embodiment 2.Adopt the method identical that the characteristic of the film rolling that obtained is estimated with embodiment 1.Evaluation result is shown in table 3～9.

Embodiment 3

Except the blending ratio that makes material web A and material web B is 90.0 weight % for material web A, material web B is outside the 10.0 weight %, and other is identical with embodiment 2, obtains the polyamide resin film roll of embodiment 3.And in embodiment 3, the average major diameter of elastomer sheet (material web B), average minor axis, average sheet length also respectively the average major diameter of polyamide-based resin thin slice (material web A), average minor axis, average sheet length ± 20% in.Subsequently, adopt the method identical that the characteristic of the film rolling that obtained is estimated with embodiment 1.Evaluation result is shown in table 3～9.

Embodiment 4

Except using material web C to replace material web B, the blending ratio of material web A and material web C is that material web A is 95.0 weight %, material web C is outside the 5.0 weight %, and is identical with embodiment 2, obtains the polyamide resin film roll of embodiment 4.And in embodiment 4, the average major diameter of elastomer sheet (material web C), average minor axis, average sheet length also respectively the average major diameter of polyamide-based resin thin slice (material web A), average minor axis, average sheet length ± 20% in.Adopt the method identical that the characteristic of the film rolling that obtained is estimated with embodiment 1.Evaluation result is shown in table 3～9.

Embodiment 5

Except using material web D to replace material web B, the blending ratio of material web A and material web D is that material web A is 95.0 weight %, material web D is outside the 5.0 weight %, and is identical with embodiment 2, obtains the polyamide resin film roll of embodiment 5.And in embodiment 5, the average major diameter of elastomer sheet (material web D), average minor axis, average sheet length also respectively the average major diameter of polyamide-based resin thin slice (material web A), average minor axis, average sheet length ± 20% in.Adopt the method identical that the characteristic of the film rolling that obtained is estimated with embodiment 1.Evaluation result is shown in table 3～9.

Embodiment 6

Except using material web E to replace material web B, the blending ratio of material web A and material web E is that material web A is 95.0 weight %, material web E is outside the 5.0 weight %, and is identical with embodiment 2, obtains the polyamide resin film roll of embodiment 6.And in embodiment 6, the average major diameter of elastomer sheet (material web E), average minor axis, average sheet length also respectively the average major diameter of polyamide-based resin thin slice (material web A), average minor axis, average sheet length ± 20% in.Adopt the method identical that the characteristic of the film rolling that obtained is estimated with embodiment 1.Evaluation result is shown in table 3～9.

Embodiment 7

Except using material web F to replace material web B, the blending ratio of material web A and material web F is that material web A is 95.0 weight %, material web F is outside the 5.0 weight %, and is identical with embodiment 2, obtains the polyamide resin film roll of embodiment 7.And in embodiment 7, the average major diameter of elastomer sheet (material web F), average minor axis, average sheet length also respectively the average major diameter of polyamide-based resin thin slice (material web A), average minor axis, average sheet length ± 20% in.Adopt the method identical that the characteristic of the film rolling that obtained is estimated with embodiment 1.Evaluation result is shown in table 3～9.

Embodiment 8

Except using material web G to replace material web B, the blending ratio of material web A and material web G is that material web A is 95.0 weight %, material web G is outside the 5.0 weight %, and is identical with embodiment 2, obtains the polyamide resin film roll of embodiment 8.And in embodiment 8, the average major diameter of elastomer sheet (material web G), average minor axis, average sheet length also respectively the average major diameter of polyamide-based resin thin slice (material web A), average minor axis, average sheet length ± 20% in.Adopt the method identical that the characteristic of the film rolling that obtained is estimated with embodiment 1.Evaluation result is shown in table 3～9.

Comparative example 1

Except raw material only adopts material web A, identical with embodiment 2, the polyamide resin film roll of acquisition comparative example 1.Adopt the method identical that the characteristic of the film rolling that obtained is estimated with embodiment 1.Evaluation result is shown in table 3～9.

Comparative example 2

Except the blending ratio (weight ratio) with material web A and material web B changed to 95: 5, and the preparation drying condition of material web A and material web B changed to outside heating about 4.0 hours under about 100 ℃, identical with embodiment 2, the polyamide resin film roll of acquisition comparative example 2.And after predrying, from mixer, take out the various thin slices of specified quantity, and measure moisture rate, the moisture rate of material web A and material web B all is 1500ppm.Be fed to thin slice A before the hopper and the temperature of thin slice B and all approximately be 85 ℃.Adopt the method identical that the characteristic of the film rolling that obtained is estimated then with embodiment 1.Evaluation result is shown in table 3～9.

Comparative example 3

Except with material web A and material web B in predrying back and before being fed in the hopper directly over the extrusion press, in each mixer, place outside about 5 hours, identical with embodiment 2, obtain the polyamide resin film roll of comparative example 3.And be fed to material web A before the hopper and the moisture rate of material web B all is 800ppm, be fed to thin slice A before the hopper and the temperature of thin slice B and all approximately be 30 ℃.Adopt the method identical that the characteristic of the film rolling that obtained is estimated then with embodiment 1.Evaluation result is shown in table 3～9.

Comparative example 4

The leaning angle of hopper is changed into 45 degree in the time of in the hopper directly over the material web A in the mixer and B being fed to extrusion press, and is identical with embodiment 2, obtains the polyamide resin film roll of comparative example 4.Adopt the method identical that the characteristic of the film rolling that obtained is estimated then with embodiment 1.Evaluation result is shown in table 3～9.

Comparative example 5

During except the hopper directly over material web A and B being fed to extrusion press, in hopper, add segregation and prevent outside the agent, identical with embodiment 2, obtain the polyamide resin film roll of comparative example 5.Adopt the method identical that the characteristic of the film rolling that obtained is estimated then with embodiment 1.Evaluation result is shown in table 3～9.

Comparative example 6

Except using material web A and material web H and both blending ratio (weight ratio) being changed to 95: 5, identical with embodiment 2, obtain the polyamide resin film roll of comparative example 6.And, in comparative example 6, the average major diameter of elastomer sheet (material web H), average minor axis, average sheet length respectively the average major diameter of polyamide-based resin thin slice (material web A), average minor axis, average sheet length ± 20% in.Adopt the method identical that the characteristic of the film rolling that obtained is estimated with embodiment 1.Evaluation result is shown in table 3～9.

Table 3

^*Content is with respect to the rate of change of average content: utilize bigger in the difference of the maximin in the elastomer content and average content in all samples one to calculate rate of change.

Table 4

^*Thickness is with respect to the rate of change of mean thickness: utilize along a bigger calculating rate of change in the difference of the maximin of thickness on the whole length and mean thickness.

Table 5

^*Pulling strengrth is with respect to the rate of change of average tensile strength: utilize bigger in the difference of the maximin in the pulling strengrth and average tensile strength in all samples one to calculate rate of change.

Table 6

^*Maximum boiling water shrinkage is with respect to the rate of change of average boiling water shrinkage: utilize bigger in the difference of maximin and average boiling water shrinkage in the maximum boiling water shrinkage in all samples one to calculate rate of change.

Table 7

^*Boiling water shrinkage direction difference is with respect to the rate of change of average boiling water shrinkage direction difference: bigger one is calculated rate of change in the maximin that utilizes boiling water shrinkage direction difference in all samples and the difference of average boiling water shrinkage direction difference.

Table 8

^*Ratio of refraction is with respect to the rate of change of mean refractive index: utilize bigger in the difference of the maximin in the ratio of refraction and mean refractive index in all samples one to calculate rate of change.

Table 9

The film effect of embodiment

Shown in table 3～9, any is very little along volume single-piece longitudinal thickness inequality in the film rolling of embodiment 1～8, and elastomeric content is little, and the variation of rerum naturas such as tensile elasticity rate, boiling water shrinkage and ratio of refraction is little.And rerum naturas such as this elastomeric content is little, tensile elasticity rate, boiling water shrinkage and ratio of refraction change in the film rolling of little embodiment 1～8 any and the S type phenomenon of curling all do not occur, and lamination process is good.In addition, dashing of the film of formation embodiment 1～8 film rolling connects intensity (obdurability, anti-pin hole) well, the lamination strength height.And except anti-pin hole was very good, its variation was little, is suitable for washy packaging for foodstuff purposes such as liquid meat soup.

Relative therewith, the film rolling of comparative example 1～6 is big along volume single-piece longitudinal thickness inequality, elastomeric content, and the variation of rerum naturas such as tensile elasticity rate, boiling water shrinkage and ratio of refraction is big.Find the curling phenomenon of S type, and lamination process is bad.In addition, the anti-pin hole of the film rolling of comparative example 1～6 is bad, and it changes greatly, is not suitable for washy packaging for foodstuff purposes such as liquid meat soup.

Utilize possibility on the industry

Because polyamide resin film roll of the present invention is except having above-mentioned excellent processability Outside the energy, pinhole resistance is very good, and its variation is also little, can be applicable to well the boiling food Product processing purposes.

Claims (25)

1. polyamide resin film roll, its be by the hybrid resin by polyamide-based resin and thermoplastic elastomer is formed, width is below the above 3.0m of 0.2m, length is that film below the above 30000m of 300m batches the film rolling that forms, the 1st sample portion of cutting out is arranged on apart from coiling terminal 2m with interior position, the final sample portion of cutting out is arranged on apart from coiling starting point 2m with interior position, every about 100m a sample is set from described the 1st sample portion that cuts out and cuts out portion, it is characterized in that, satisfy following condition (1) and (2):

(1) each sample to cutting out from described each portion that cuts out, measure the content of thermoplastic elastomer composition, when the aviation value that calculates these content is average content, the rate of change of the thermoplastic elastomer component content of all samples with respect to average content ± 10% scope in

(2) thickness change on the whole length of volume length direction of being batched with respect to mean thickness ± 2%～± 10% scope in.

2. polyamide resin film roll, its be by the hybrid resin by polyamide-based resin and thermoplastic elastomer is formed, width is below the above 3.0m of 0.2m, length is that film below the above 30000m of 300m batches the film rolling that forms, the 1st sample portion of cutting out is arranged on apart from coiling terminal 2m with interior position, the final sample portion of cutting out is arranged on apart from coiling starting point 2m with interior position, every about 100m a sample is set from described the 1st sample portion that cuts out simultaneously and cuts out portion, it is characterized in that, satisfy following condition (3):

(3) each sample to cutting out from described each portion that cuts out, the tensile elasticity rate of MEASUREMENTS OF THIN take-up direction, the aviation value of these tensile elasticity rates is that average tensile elasticity rate is that 1.30Gpa is above and less than 2.50GPa, the rate of change of the tensile elasticity rate of all samples with respect to described average tensile elasticity rate ± 10% scope in.

3. polyamide resin film roll, its be by the hybrid resin by polyamide-based resin and thermoplastic elastomer is formed, width is below the above 3.0m of 0.2m, length is that film below the above 30000m of 300m batches the film rolling that forms, the 1st sample portion of cutting out is arranged on apart from coiling terminal 2m with interior position, the final sample portion of cutting out is arranged on apart from coiling starting point 2m with interior position, every about 100m a sample is set from described the 1st sample portion that cuts out simultaneously and cuts out portion, it is characterized in that, satisfy following condition (4):

(4) each sample to cutting out from described each portion that cuts out uses back-and-forth bending test machine, and the pin hole number when carrying out the crooked test in 3000 cycles continuously with the speed in 1 minute about 40 cycle is all less than 10.

4. as polyamide resin film roll as described in each in the claim 1～3, wherein, to each sample that cuts out from described each portion of cutting out, when the maxim in the boiling water shrinkage of measuring all directions is maximum boiling water shrinkage, the aviation value of these maximum boiling water shrinkages is that average boiling water shrinkage is 3%～6%, simultaneously, the rate of change of the maximum boiling water shrinkage of all samples with respect to described average boiling water shrinkage ± 2%～± 10% scope in.

5. as polyamide resin film roll as described in each in the claim 1～3, wherein, to each sample that cuts out from described each portion of cutting out, obtaining when being boiling water shrinkage direction difference with respect to the boiling water shrinkage of length direction+45 ° direction with respect to the absolute value of the difference of the boiling water shrinkage of length direction-45 ° direction, the aviation value of these boiling water shrinkage direction differences is that average boiling water shrinkage direction difference is below 1.5%, simultaneously, the rate of change of the sample boiling water shrinkage direction difference of all samples with respect to described average boiling water shrinkage direction difference ± 2%～± 10% scope in.

6. as polyamide resin film roll as described in each in the claim 1～3, wherein, to each sample that cuts out from described each portion of cutting out, when measuring the ratio of refraction of thickness direction, the aviation value of these ratio of refraction is that mean refractive index is more than 1.500 below 1.520, simultaneously the variations in refractive index rate of all samples with respect to described mean refractive index ± 2% scope in.

7. as polyamide resin film roll as described in each in the claim 1～3, wherein, the main component of polyamide-based resin is a nylon 6.

8. as polyamide resin film roll as described in each in the claim 1～3, wherein, the main component of thermoplastic elastomer is at least a in polyamide-based elastic body, the polyolefins elastic body.

9. as polyamide resin film roll as described in each in the claim 1～3, wherein, the polyamide resin film that is batched is the article with the polyolefin resin film laminating.

10. as polyamide resin film roll as described in each in the claim 1～3, wherein, from the T mould, the polyamide-based hybrid resin of fusion is extruded, it is contacted with metallic roll and cool off, will batch the polyamide resin film of thus obtained not directed sheet-like article after biaxial stretch-formed.

11. as polyamide resin film roll as described in each in the claim 1～3, wherein, the polyamide resin film after will being stretched by the tentering extension method batches.

12., wherein, will the polyamide resin film after twin shaft extends one by one be batched as polyamide resin film roll as described in each in the claim 1～3.

13., wherein, the polyamide resin film after longitudinally and laterally twin shaft extends is batched as polyamide resin film roll as described in each in the claim 1～3.

14. as polyamide resin film roll as described in each in the claim 1～3, wherein, under than the high temperature more than glass temperature+20 of the main component of described polyamide-based hybrid resin ℃, at least after with two stages the sheet-like article of being made up of unoriented in fact polyamide-based hybrid resin longitudinally being stretched with the multiplying power more than 3 times,, the polyamide resin film that experiences after the described stretching is batched along laterally stretching with the multiplying power more than 3 times.

15. as polyamide resin film roll as described in each in the claim 1～3, wherein, to implement after the final stretch processing and heat fixation polyamide resin film batch.

16., wherein, the polyamide resin film of having implemented relaxation processes behind the heat fixation is batched as polyamide resin film roll as described in each in the claim 1～3.

17. as polyamide resin film roll as described in each in the claim 1～3, wherein, in the polyamide resin film after batching, add at least a in lubricant, antiblocking agent, heat stabilizer, antioxidant, antistatic additive, photostabilizer, the Dent resistance modifier.

18., wherein, in the polyamide resin film after batching, add inorganic particle as polyamide resin film roll as described in each in the claim 1～3.

19. as polyamide resin film roll as described in each in the claim 1～3, wherein, inorganic particle is that mean grain size is the silica dioxide granule of 0.5～5.0 μ m.

20., wherein, in the polyamide resin film after batching, add higher fatty acid as polyamide resin film roll as described in each in the claim 1～3.

21. manufacture method that is used for making each described polyamide resin film roll of claim 1～3, comprise that filming operation, the not extension film that this filming operation is obtained longitudinally and laterally carry out the twin shaft extension process of twin shaft extension and the operation of the film after the twin shaft extension being batched volumeization, described filming operation is on one side to the thin slice is made up of polyamide-based resin with carry out melt extruded by the thin slice that thermoplastic elastomer is formed and also make film in one side, it is characterized in that, satisfy following condition (1) and (2):

(1) in described filming operation, to carrying out melt extruded after polyamide-based resin thin slice and the mixing of thermoplastic elastomer thin slice, the shape of each thin slice that uses is the oval column with the elliptic jet that comprises major diameter and minor axis, and, with the average major diameter of thermoplastic elastomer thin slice, average minor axis and average sheet length adjust to the average major diameter with respect to the polyamide-based resin thin slice, average minor axis and average sheet length ± 20% with interior scope

(2) in described filming operation,, simultaneously, add the sublimability segregation and prevent agent and carry out the mixing of polyamide-based resin thin slice and thermoplastic elastomer thin slice carrying out melt extruded after polyamide-based resin thin slice and the mixing of thermoplastic elastomer thin slice.

22. manufacture method as polyamide resin film roll as described in the claim 21, wherein, described twin shaft extension process is a kind of like this operation, it is back along cross directional stretch promptly longitudinally to carry out the stretching of two stages, in described two stages longitudinally stretched, the stretching ratio of F/s was than the stretching ratio height of subordinate phase.

23. manufacture method as polyamide resin film roll as described in the claim 21, wherein, described filming operation comprises using and is provided with the operation of carrying out melt extruded as the extrusion press of the infundibulate hopper of material web supply unit, the angle of inclination of described hopper is adjusted to more than 65 °, and, adjust to below the above 1000ppm of 800ppm supplying to the polyamide-based resin thin slice before the described hopper and the moisture rate of thermoplastic elastomer thin slice, adjust to more than 80 ℃ supplying to the polyamide-based resin thin slice before the described hopper and the temperature of thermoplastic elastomer thin slice.

24. manufacture method as polyamide resin film roll as described in the claim 21, wherein, described twin shaft extension process is included in the preheating procedure implemented before the described longitudinal stretching and the heat treatment step of enforcement described longitudinal stretching after, with the rangeability of the film surface temperature of at a point in described preheating procedure, heat treatment step and the longitudinal stretching operation adjust to along the mean temperature of the whole length of film ± 1 ℃ of scope in.

25. manufacture method as polyamide resin film roll as described in the claim 21, wherein, described filming operation comprises that the molten resin that will extrude is wound on the chill roll and the roller refrigerating work procedure that cools off from described extrusion press, in described roller refrigerating work procedure, molten resin is attracted along the direction opposite with described coiling direction by suction device on the whole width of molten resin with the chill roll surface contact portion.