CN1789090A - Polyamides mixing resin laminated film coil and method for preparing same - Google Patents

Polyamides mixing resin laminated film coil and method for preparing same Download PDF

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Publication number
CN1789090A
CN1789090A CN 200510128643 CN200510128643A CN1789090A CN 1789090 A CN1789090 A CN 1789090A CN 200510128643 CN200510128643 CN 200510128643 CN 200510128643 A CN200510128643 A CN 200510128643A CN 1789090 A CN1789090 A CN 1789090A
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China
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laminated film
resin laminated
film coil
mixing resin
fragment
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CN100532091C (en
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西忠嗣
宫口义纪
小田尚伸
野濑克彦
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Toyobo Co Ltd
Toyo Textile Co Ltd
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Toyo Textile Co Ltd
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Abstract

To provide a polyamide mixed resin laminated film roll that can smoothly conduct bag making by lamination at a high yield and can efficiently provide a package free from S-shaped curling. The polyamide mixed resin laminated film roll is a roll obtained by winding a polyamide mixed resin laminated film comprising a plurality of polyamide mixed rein sheets stacked on top of each other. A first sample taken-off part is provided within 2 m from the end of winding of the film, and a final sample taken-off part is provided within 2 m from the start of winding of the film. The roll is regulated so that, when sample taken-off parts are provided at intervals of about 100 m from the first sample taken-off part, for all samples taken off from the taken-off parts, the elastomer content, tensile modulus of elasticity, thickness unevenness in the longitudinal direct and other properties fall within a predetermined variation range.

Description

Polyamides mixing resin laminated film coil and manufacture method thereof
Technical field
The present invention relates to batch the uniform high quality thin film volume of rerum natura on long size that polyamides mixing resin laminated laminated film forms, detailed says, the present invention relates to and the polyolefin resin film laminating the good polyamides mixing resin laminated film coil of processability (the particularly processability under the high humidity) when being used to the packing of distilling food etc.
Background technology
With nylon is the Biaxially orientated polyamide-based resin film of main component, because its tough and gas barrier property, anti-pin hole, the transparency, printing etc. are good, therefore, be widely used as the packing of various food such as various aqueous food, food containing water, frozen food, distillation food, paste food, poultry meat aquatic food, particularly in recent years, be widely used in distilling the packing of food.This polyamide-based resin film for example with laminations such as polyolefin resin film such as polyethylene or polypropylene, parallel folding twice of streamwise, to cut after three limit thermal weldings then, constitute three limit sealing bags of open Kaifeng state on one side, fill after various food seal in inside, in boiling water, carry out pasteurization, supply market.
But when using Biaxially orientated polyamide-based resin film, after pasteurization was handled, warpage took place in the bight that is created in packaging bag, and four limits are curled into the phenomenon (below be called S word curl phenomenon) of S word shape, as the remarkable variation of outward appearance of package goods.Therefore, as the method that reduces this curling phenomenon, as described in patent documentation 1, disclosed the long-pending method that is adjusted into particular value of rate of change with the thin-film width direction of the boiling water shrinkage distortion rate of Biaxially orientated polyamide-based resin film and angle of molecular orientation, but in this method, because temperature when the dimensionally stable sexual needs during for the raising boiling water treating improve heat setting terrifically or the mitigation heat treatment after the enforcement stretching exceedingly, therefore, produce the obdurability of the film that obtains and the problem that anti-pin hole suffers damage.
Therefore, as described in patent documentation 2, applicant's invention has also disclosed: be adjusted in the specific number range by boiling water shrinkage or ratio of refraction (flexion rate) with film, do not make obdurability or anti-pin hole reduction, and the method for the Biaxially orientated polyamide based resin film of the curling phenomenon of S word is not taken place.
Patent documentation 1: the spy opens flat 4-103335 communique
Patent documentation 2: the spy opens flat 8-174663 communique
According to the method for above-mentioned patent documentation 2, can obtain the Biaxially orientated polyamide based resin film that tough and anti-pin hole is good, the curling phenomenon of S word does not take place.But, in the process of carrying out bag processing by lamination, conditions such as pressure during thermal welding and time, because the film rolling of each use is finely tuned, therefore, even the aviation value that is wound on physics values such as the boiling water shrinkage of the film on the film rolling and ratio of refraction is in the scope of patent documentation 2 time, in the variation of a volume film rolling when big, in bag processing, wrinkle enters between the film when also occurring in lamination easily, or fault such as yield rate variation.
The formation of another invention is, after being extruded, batches the various kinds of resin mixed melting in the manufacture method of biaxially oriented film volume of biaxially oriented film, method as the change that is used to reduce dynamic friction coefficient, the applicant has also proposed to make peace by the shape one that makes the raw material fragment, and to increase extruder raw material supplying portion be the angle of inclination of funnel-form hopper (hopper), the method (spy opens 2004-181777) that the segregation of raw material is diminished.But, even this method as the change (becoming Move) of rerum naturas such as boiling water shrinkage that is used to suppress to be wound in the film on the film rolling and ratio of refraction and the method for disperse (バ ラ Star キ), also may not be conclusive method.
Therefore, the applicant just is used to produce the production technology of highly uniform biaxially oriented film volume and studies repeatedly without single devotion, and the result has invented the polyamide resin film roll (special hope 2004-262922) that rerum natura height such as film thickness, boiling water shrinkage or ratio of refraction are even, can not produce wrinkle between the film when lamination, can carry out bag processing with good yield rate.
Summary of the invention
According to uniform polyamide resin film rolls of rerum natura height such as above-mentioned film thickness, boiling water shrinkage and ratio of refraction, be good obdurability and the anti-pin hole that does not damage polyamide-based resin film, the material of the excellent processability when the curling phenomenon of S word, lamination process do not take place.But, even the uniform polyamide resin film roll of rerum natura height as mentioned above, when carrying out lamination process under high humidity such as summer, polyamides mixing resin laminated film can not manifest good sliding sometimes on the roller of lamination process machine, may not necessarily obtain good processing characteristics.
And only the anti-pin hole of the film that is made of polyamide-based resin is limited, may not be suitable for the packing purposes that liquid soup etc. contains the food of large quantity of moisture.Means as the anti-pin hole that is used to improve polyamide-based resin film, known in as the polyamide-based resin of film raw material the method for filled elastomer, but in this hybrid resin film rolling, by only reducing the change of rerum naturas such as film thickness, boiling water shrinkage or ratio of refraction, when carrying out lamination process, can not obtain good processability, and, in each three limit sealing bag of lamination process, on anti-pin hole, produce discrete (バ ラ Star キ).
The inventor to be used to improve polyamide-based resin film under high humidity sliding and do not have the production technology of change, and being used to make the uniform production technology of biaxial stretch-formed hybrid resin film height that constitutes by polyamide-based resin and elastomeric hybrid resin to carry out research and development extensively and profoundly, the result has finished the present invention.Its purpose is, the problem that can eliminate existing polyamide resin film roll is provided, can in requiring the packing purposes of extra high anti-pin hole, use, even under the high humidity in summer, also can almost not have fault ground, carry out the processing of lamination bag swimmingly, can obtain not having the Biaxially orientated polyamide class mixing resin laminated film coil of the packing material that the S word batches effectively.In addition, be provided in the back processing of bag processing etc., can obtain the Biaxially orientated polyamide class mixing resin laminated film coil of processed goods with high yield rate.And, provide and can make this Biaxially orientated polyamide class mixing resin laminated film coil manufacture method effectively.
Among the present invention, first invention provides polyamides mixing resin laminated film coil, its following formation: the polyamides mixing resin laminated film coil that a plurality of polyamide-based resin sheets (sheet) lamination that will be made of the hybrid resin of polyamide-based resin and thermoplastic elastomer forms is got, making its width is 0.2m～3.0m, length is 300m～30000m, obtain polyamides mixing resin laminated film coil, with interior (Off イ Le system Juan き Final わ り か ら 2m is with interior To) first sample is set at the coiling termination 2m of distance film and cuts out portion, in addition, begin 2m at the coiling of distance film and the portion that finally cuts out is set with interior (the Off イ Le system volume I beginning, め か ら 2m was with interior To), simultaneously, cut out the every about 100m of portion (a kind order Try material cut り go out the every To of the か ら Approximately 100m of portion) apart from first sample when sample being set cutting out portion, satisfying following important document (1) and (2):
(1) at the content of each sample that cuts out from the described respectively portion of cutting out being measured the thermoplastic elastomer composition, when the aviation value of calculating these content is average content, all the fluctuation rate of the thermoplastic elastomer component content of samples with respect to average content in ± 10% scope;
The thickness variation rate of the length direction total length of the volume that (2) batches with respect to mean thickness in ± 2%～± 10% scope.
Second invention provides polyamides mixing resin laminated film coil, its following formation: the polyamides mixing resin laminated film coil that a plurality of polyamide-based resin sheet laminations that will be made of the hybrid resin of polyamide-based resin and thermoplastic elastomer form is got, making its width is 0.2m～3.0m, length is 300m～30000m, obtain polyamides mixing resin laminated film coil, coiling termination 2m at the distance film cuts out portion with interior first sample that is provided with, in addition, coiling at the distance film begins 2m with the interior portion that finally cuts out that is provided with, simultaneously, cutting out the every about 100m of portion apart from first sample when sample being set cutting out portion, satisfy following important document (3).
(3) when each sample that cuts out from the described respectively portion of cutting out is measured the tensile modulus of film take-up direction, the aviation value of these tensile moduluses is that average tensile modulus is 1.30GPa～less than 2.50GPa, simultaneously, all the fluctuation rate of the tensile modulus of samples with respect to described average tensile modulus in ± 10% scope.
The 3rd invention provides polyamides mixing resin laminated film coil, its following formation: the polyamides mixing resin laminated film coil that a plurality of polyamide-based resin sheet laminations that will be made of the hybrid resin of polyamide-based resin and thermoplastic elastomer form is got, making its width is 0.2m～3.0m, length is 300m～30000m, obtain polyamides mixing resin laminated film coil, coiling termination 2m at the distance film cuts out portion with interior first sample that is provided with, in addition, coiling at the distance film begins 2m with the interior portion that finally cuts out that is provided with, simultaneously, cutting out the every about 100m of portion apart from first sample when sample being set cutting out portion, satisfy following important document (4).
(4) for each sample that cuts out from the described respectively portion of cutting out, the number of pin hole all is no more than 10 when using Gelboflex experimental engine (ゲ Le ボ Off レ Star Network ス テ ス one) to carry out the bending test in 3000 cycles continuously with the speed in 40 cycles of each minute.
The formation of the 4th invention is, in first～the 3rd each invention, when each sample that cuts out from the described respectively portion of cutting out being measured maxim the omnidirectional boiling water shrinkage and is maximum boiling water shrinkage, the aviation value of these maximum boiling water shrinkages is that average boiling water shrinkage is 2%～6%, simultaneously, all the fluctuation rate of the maximum boiling water shrinkage of samples with respect to described average boiling water shrinkage in ± 2%～± 10% scope.
The formation of the 5th invention is, in first～the 3rd each invention, each sample that cuts out from the described respectively portion of cutting out is being obtained when being boiling water shrinkage direction difference for the boiling water shrinkage of+45 degree directions with respect to length direction for the absolute value of difference of the boiling water shrinkage of-45 degree directions with respect to length direction, the aviation value of these boiling water shrinkage direction differences is that average boiling water shrinkage direction difference is no more than 2.0%, simultaneously, all the fluctuation rate of the boiling water shrinkage direction difference of samples with respect to described average boiling water shrinkage direction difference in ± 2%～± 30% scope.
The formation of the 6th invention is that in first～the 3rd each invention, each sample that cuts out from the described respectively portion of cutting out satisfies following important document (5) and following important document (6).
(5) when measuring the three-dimensional surface roughness of take-up direction, the aviation value of these three-dimensional surface roughness is that average surface roughness is in the scope of 0.01～0.06 μ m, simultaneously, all the fluctuation rate of the three-dimensional surface roughness of samples with respect to described average surface roughness in ± 5%～± 20% scope;
(6) when measuring turbidity (haze, ヘ イ ズ), the aviation value of these turbidity be average turbidity in 1.0～4.0 scope, simultaneously, all the fluctuation rate of the turbidity of samples with respect to described average turbidity in ± 2% ± 15% scope.
The formation of the 7th invention is, in first～the 3rd each invention, when each sample of cutting out from the described respectively portion of cutting out is measured dynamic friction coefficient under 23 ℃, the atmosphere of 80RH, the aviation value of these dynamic friction coefficients is that mean coefficient of kinetic sliding friction is in 0.3～0.8 scope, simultaneously, all the fluctuation rate of the dynamic friction coefficient of samples with respect to described mean coefficient of kinetic sliding friction in ± 5%～± 30% scope.
The formation of the 8th invention is, in first～the 3rd each invention, when each sample that cuts out from the described respectively portion of cutting out is measured the content of inorganic particulate, the aviation value of these inorganic particulate content is that average content is in the scope of 0.01～0.5 weight %, simultaneously, all the fluctuation rate of the inorganic particulate content of samples with respect to described average content in ± 2%～± 10% scope.
The formation of the 9th invention is, in first～the 3rd each invention, when each sample that cuts out from the portion of cutting out is respectively measured the ratio of refraction of thickness direction, the aviation value of these ratio of refraction is that mean refractive index is 1.500～1.520, simultaneously, all the fluctuation rate of the ratio of refraction of samples with respect to described mean refractive index in ± 2% scope with interior (in ± 2%).
The formation of the tenth invention is, in first～the 3rd each invention, the mean grain size of the inorganic particulate of 1/3 part of through thickness near in the polyamides mixing resin laminated film that batches, each Biao Layer Inter of (Biao Li each top layer in the table) is littler than near the mean grain size of the inorganic particulate of the part in addition in these top layers.
The formation of the 11 invention is that in first～the 3rd each invention, the major component that constitutes the polyamide of polyamides mixing resin laminated film is a nylon 6.
The formation of the tenth binomial invention is that in first～the 3rd each invention, polyamides mixing resin laminated film coil is that the polyamides mixing resin laminated film coil that is formed by at least two kinds of different polyamide-based resin compounds is got the film rolling that forms.
The formation of the 13 invention is that in first～the 3rd each invention, polyamides mixing resin laminated film that batches and polyolefin resin film laminating form.
The formation of the 14 invention is, in first～the 3rd each invention, be to extrude the polyamide-based resin of fusion from T shape mould, it is contacted with metallic roll and cool off, carry out the non-oriented flap that obtains thus biaxial stretch-formed and obtain biaxial stretch-formed polyamides mixing resin laminated film, the biaxial stretch-formed polyamides mixing resin laminated film coil that obtains is got the polyamides mixing resin laminated film coil that forms.
The formation of the 15 invention is, in first～the 3rd each invention, is that the polyamides mixing resin laminated film coil that (the テ Application one extends) method that stretches by stenter stretches is got the polyamides mixing resin laminated film coil that forms.
The formation of the 16 invention is, in first～the 3rd each invention, is that the polyamides mixing resin laminated film coil of successively biaxial-oriented (Zhu Er Shaft extends) is got the polyamides mixing resin laminated film coil that forms.
The formation of the 17 invention is, in first～the 3rd each invention, is longitudinally to get the polyamides mixing resin laminated film coil that forms with horizontal biaxial stretch-formed polyamides mixing resin laminated film coil.
The formation of the 18 invention is, in first～the 3rd each invention, be the flap that will constitute by non-oriented in fact polyamide-based resin under glass transition temperature+20 ℃ high temperature than described polyamide-based resin (preceding note Port リ ア ミ De is that Trees fat ガ ラ ス translocation moves temperature+20 ℃ I り も high temperature In) with at least 3 times multiplying powers two-stage longitudinal stretching at least, then, with at least 3 times multiplying power cross directional stretch, the polyamides mixing resin laminated film coil that obtains is got the polyamides mixing resin laminated film coil that forms.
The formation of the 19 invention is, in first～the 3rd each invention, is to get the polyamides mixing resin laminated film coil that forms with having carried out after the final stretch processing polyamides mixing resin laminated film coil of heat setting.
The formation of the 20 invention is, in first～the 3rd each invention, is that the polyamides mixing resin laminated film coil that has carried out relaxation processes after the heat setting is got the polyamides mixing resin laminated film coil that forms.
The formation of the 21 invention is, in first～the 3rd each invention, in the polyamides mixing resin laminated film that batches, added lubricant, anti blocking agent (Block ロ Star キ Application グ prevents drug), heat stabilizer, antioxidant, antistatic additive (band Electricity prevents drug), photostabilizer (fast light drug), the Dent resistance modifier (attack of Nai Red property improvement drug) at least a.
The formation of the 20 binomial invention is in first～the 3rd each invention, to have added inorganic particulate in the polyamides mixing resin laminated film that batches.
The formation of the 23 invention is that in the invention of the 20 binomial, inorganic particulate is that mean grain size is the silica particle of 0.5～5.0 μ m.
The formation of the 24 invention is in first～the 3rd each invention, to have added higher fatty acid in the polyamides mixing resin laminated film that batches.
The formation of the 25 invention is, be used to make the manufacture method of the polyamides mixing resin laminated film coil of first invention, comprise: melt extrude the hybrid resin that constitutes by polyamide-based resin and thermoplastic elastomer by adopting coetrusion from a plurality of extruders, form the filming operation of the polyamides mixing resin laminated sheet material that does not stretch; Longitudinally reach with the mixing resin laminated sheet material of not drawing polyamide class that will obtain in this filming operation and laterally to carry out biaxial stretch-formed biaxial stretch-formed operation, satisfy following important document (a)～(f).
(a) described filming operation is: melt extrude after with polyamide-based resin fragment (chip) and the mixing of thermoplastic elastomer fragment, simultaneously, add the mixing that sublimable segregation prevents agent and carries out this polyamide-based resin fragment and thermoplastic elastomer fragment;
(b) described filming operation is: polyamide-based resin fragment and themoplasticity synthetic resin fragment are mixed, and lamination has added the polyamide-based hybrid resin sheet of 0.1～2.0 weight % inorganic particulate on top layer;
(c) described biaxial stretch-formed operation is: stretch the back along cross directional stretch in 2 stages longitudinally, simultaneously, make the stretching ratio height of the stretching ratio of the F/s that described 2 stages longitudinally stretch than subordinate phase;
(d) described filming operation is: after with polyamide-based resin fragment and the mixing of thermoplastic elastomer fragment, melt extrude from each extruder, simultaneously, each fragment that uses be shaped as oval column with the oval section that comprises major diameter and minor axis, and themoplasticity synthetic resin fragment is adjusted to average major diameter with respect to the polyamide-based resin sheet, average minor axis and average chip length, have to be included in separately ± 25% with the average major diameter in the interior scope, average minor axis and average chip length;
(e) described filming operation is: comprise using to have the operation that the funnel-form hopper melt extrudes as a plurality of extruders of raw material fragment supply unit, simultaneously, the leaning angle of described funnel-form hopper all is adjusted into and is not less than 65 degree, and the water ratio that supplies to the polyamide-based resin fragment before the described funnel-form hopper is adjusted into 800ppm～1000ppm, and the temperature that supplies to the polyamide-based resin fragment before the described funnel-form hopper is adjusted into and is not less than 80 ℃;
(f) described filming operation is: comprise and will batch the operation of cooling off on the chill roll from the polyamides mixing resin laminated sheet material that described a plurality of extruders melt extrude by coetrusion, simultaneously, in this refrigerating work procedure, the contact portion on polyamides mixing resin laminated sheet material and chill roll surface, on the whole width of polyamides mixing resin laminated sheet material, on the direction opposite, attract with take-up direction by suction device;
The formation of the 26 invention is in the 25 invention, in described filming operation, by using high concentration raw material fragment, to go up the top layer (ス キ Application Layer) that lamination has added 0.05～2.0 weight % inorganic particulate at sandwich layer (core layer).
The formation of the 27 invention is, in the 25 invention, the high concentration raw material fragment that uses in described filming operation is to have added 5 weight %～the be lower than polyamide-based resin fragment of 20 weight % inorganic particulates.
The formation of the 28 invention is, in the 25 invention, in described filming operation, the porosity volume (Fine Kong Rong Plot) of the inorganic particulate that adds in the polyamide-based resin sheet material that is laminated to top layer is 0.5～2.0ml/g, and mean grain size is 1.0～5.0 μ m.
The formation of the 29 invention is, in the 25 invention, be included in the heat treatment step that preheats operation and carry out after the longitudinal stretching operation that carries out before the longitudinal stretching operation, these longitudinal stretching operations, the mobility scale (becoming the Move width of cloth) that preheats the film surface temperature of at a point in operation and the heat treatment step are adjusted on the total length of film in the scope of mean temperature ± 1 ℃.
According to polyamides mixing resin laminated film coil of the present invention, even that carries out the highly anti-pin hole of requirement under the high humidity in summer is used for packing liquid soup (liquid ス one プ, liquid soup) under the situation of the bag operation of etc. three limit sealing bags, can almost not have fault ground yet, carry out the processing of lamination bag swimmingly, can obtain the packing material that does not have the S word to curl effectively.In addition, in the back processing of bag processing etc., can obtain processed goods with high yield rate.And if use polyamides mixing resin laminated film coil of the present invention, then the used for packing foods bag after the processing of lamination bag has high anti-pin hole, and, the discrete minimizing of the anti-pin hole of each bag.
In addition, according to the manufacture method of polyamides mixing resin laminated film coil of the present invention, can be cheap and obtain having high anti-pin hole and the good polyamide resin film roll of lamination process under the high humidity very efficiently.
The specific embodiment
Polyamides mixing resin laminated film coil of the present invention, cutting out (cut り and go out) sample by the following method, each sample that respectively cuts out is measured the content of thermoplastic elastomer composition, when the aviation value of calculating these content was average content, all the fluctuation rate of the content of the thermoplastic elastomer composition of samples need be in ± 10% scope (the 1st) with respect to average content.
Cutting out of sample of the present invention at first, cuts out portion at the coiling termination 2m of distance film with interior first sample that is provided with, in addition, coiling at the distance film begins 2m with the interior portion that finally cuts out that is provided with, and simultaneously, sample is set cuts out portion cutting out the every about 100m of portion apart from first sample.In addition, " every about 100m " is meant, also can cuts out sample in the position about 100m ± 1m.
When cutting out of said sample is described more specifically, for example the time with the polyamide-based winding film rolling of length 498m, the coiling from film stop to 2m to cut out initial sample (1) between interior.In addition, cutting out for convenience of sample and be cut into rectangle (tiltedly not cutting), make its have along the limit of film length direction and along with the limit of the direction of length direction quadrature.Then, beginning the position that side is left 100m to reeling, cut second sample (2) from the part that cuts.Equally, cut the 3rd sample (3), cut the 4th sample (4), cut the 5th sample (5) in position from 400m to the beginning side of reeling that leave in position from 300m to the beginning side of reeling that leave in position from 200m to the beginning side of reeling that leave.Like this, when cutting out sample, because the remaining 100m that is shorter than, so the sample (6) of the 6th (finally) is to cut from the coiling of distance film to begin 2m with interior arbitrary part.
And, as mentioned above, at the content to the sample quantitative analysis thermoplastic elastomer composition that cuts, when the aviation value of calculating these content was average content, all the fluctuation rate of the content of the thermoplastic elastomer composition of samples need be in ± 10% scope with respect to average content.At this, all the fluctuation rate of the content of the thermoplastic elastomer composition of sample is meant, minimum and maximum in the content (measured value) of the thermoplastic elastomer composition of obtaining whole samples, and when obtaining the difference of big side of these differences with average content in minimum and maximum and average content, this differs from the ratio with respect to average content.In addition, as described later, the content of thermoplastic elastomer composition can be measured by the following method, promptly, with respect to Surface Vertical ground cutting film, form ultrathin section, with specific material the elastic body composition is dyeed, calculate the method that accounts for coloured portions single-piece area ratio, also can wait the following method of other method to measure by infrared analysis or the NMR analysis of paying close attention to the distinctive peak of elastic body.
In addition, polyamides mixing resin laminated film coil of the present invention, the fluctuation rate of the elastic body component content of the whole samples that preferably cut out average content ± 9% with interior scope, more preferably ± 8% with interior scope, particularly preferably in ± 7% with interior scope.
And, polyamides mixing resin laminated film coil of the present invention, the fluctuation rate of the elastic body component content of the whole samples that preferably cut out is the smaller the better, but when considering to measure precision, the lower limit of this fluctuation rate exceeds with about 2%.
In addition, polyamides mixing resin laminated film coil of the present invention, when each sample that cuts out from the portion of cutting out was respectively measured tensile modulus, the aviation value that needs these tensile moduluses was that average tensile modulus is 1.30GPa (1300N/mm 2)～less than 2.50GPa (2500N/mm 2), simultaneously, all the fluctuation rate of the tensile modulus of samples with respect to above-mentioned average tensile modulus be adjusted into ± 10% scope in (the 2nd invention).At this, all the fluctuation rate of the tensile modulus of sample is meant, maximum in obtaining the tensile modulus of whole samples, minimum, and when obtaining the difference of big side of these maximums, the difference with average tensile modulus in minimum and average tensile modulus, this differs from the ratio with respect to average tensile modulus.
In addition, the tensile modulus that constitutes the film of polyamides mixing resin laminated film coil is being important aspect the obdurability that improves film itself, the anti-pin hole, in tensile modulus during less than 1.30GPa, obdurability, anti-pin hole are insufficient, on the contrary, when surpassing 2.5GPa, when making three limit sealing bags, tearing property (drawing fragility) degenerates, so not preferred.Aspect the tearing property when improving obdurability, anti-pin hole and form three limit sealing bags, more preferably the scope of tensile modulus is 1.50GPa～2.30GPa.
In addition, polyamides mixing resin laminated film coil of the present invention, the fluctuation rate of the tensile modulus of the whole samples that preferably cut out average tensile modulus ± 9% with interior scope, more preferably ± 8% with interior scope, preferred ± 7% is with interior scope especially.
And, polyamides mixing resin laminated film coil of the present invention, the fluctuation rate of the tensile modulus of the whole samples that preferably cut out is the smaller the better, but when considering to measure precision, the lower limit of this fluctuation rate exceeds with about ± 2%.
In addition, polyamides mixing resin laminated film coil of the present invention, for each sample that cuts out from the portion of cutting out respectively, need by the following method, use the Gelboflex experimental engine to adjust, make that the number of the pin hole when carrying out 3000 on-cycle bending tests continuously with per minute 40 on-cycle speed all is to be no more than 10 (the 3rd inventions).
The measuring method of anti-pin hole
Will with laminations such as polyolefin film, and cut into the prescribed level (film of 20.3cm * 27.9cm), after conditioning (conditioning) at the appointed time under the temperature of stipulating, the humidity, reel and set up (volume frame) rectangularity test film, and make the cylindric of specified length.Then, the two ends of this cylindrical thin-film are individually fixed in the periphery of discoid fixed head of Gelboflex experimental engine and the periphery of discoid moving head, make the axle at moving head parallel (parallel To subtend) two relatively in the direction upper edge of fixed head, during only near specified length (7.6cm), rotate predetermined angular (440 °), then, be not rotated, after the craspedodrome specified length (6.4cm), be reversed these actions, make moving head return original position, this makes the speed only continuous circulation of repeatedly stipulating (3000 circulation) of this 1 on-cycle bending test with specified speed (per minute 40 circulations) as an on-cycle bending test.Then, counting is at the specialized range (497cm that removes the fixed head and the part on the moving head periphery that are fixed in testing film 2) the pinhole number that produces of part.
In addition, polyamides mixing resin laminated film coil of the present invention, when cutting out sample by above-mentioned method, when the method below utilizing was measured maxim in the omnidirectional boiling water shrinkage and is maximum boiling water shrinkage whole samples, preferably the aviation value with these maximum boiling water shrinkages was that average boiling water shrinkage is adjusted into 2%～6%.
In addition, polyamides mixing resin laminated film coil of the present invention, when cutting out sample by said method, by following method whole samples being obtained when being boiling water shrinkage direction difference for the boiling water shrinkage of+45 degree directions with respect to length direction for the absolute value of difference of the boiling water shrinkage of-45 degree directions with respect to length direction, preferably is that average boiling water shrinkage direction difference is adjusted into and is no more than 2.0% with the aviation value of these boiling water shrinkage direction differences.
[measuring method of boiling water shrinkage (BS), maximum boiling water shrinkage (BSx), average boiling water shrinkage (BSax), boiling water shrinkage direction poor (BSd), average boiling water shrinkage direction poor (BSad)]
The film that will cut out from the respectively portion of cutting out of polyamides mixing resin laminated film coil is cut into square shape, places at least 2 hours under 23 ℃, the atmosphere of 65%RH.Draw with the central authorities of this sample is the circle (about the about 20cm of diameter) at center, with vertical (film is drawn direction) is 0 °, draw by the straight line at circle center in 0～165 ° of direction by cw with 15 ° of intervals, measure the diameter of all directions, as the length before handling.Then, at the sample that will cut out furnace run after 30 minutes in boiling water, with its taking-up, wipe the moisture that is attached to the surface, carry out air-dry, then, in 23 ℃, the atmosphere of 65RH, placed at least 2 hours, as mentioned above, be determined at the length of the straight line that draws on each diametric(al), 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) with following formula 1～5.
Length after length-processing before BS=[(handles)/the preceding length of processing] * 100 (%) ... 1
The shrinkage percentage (%) of maximum during BSx=measures on 0～165 ° of direction with 15 ° of intervals ... 2
The summation of the BSx of the whole samples of BSax=/sample number ... 3
BSd=| (BS of 45 ° of directions)-(BS of 135 ° of directions) | ... 4
The summation of the BSd of the whole samples of BSad=/sample number ... 5
In addition, the value of the BSx of the film of formation polyamides mixing resin laminated film coil, guarantee with film shaped for the resistance to effect of heat (lamination strength or anti-lamination strength) of bag shape when carrying out hot water treatment in, be important aspect the obdurability that improves film itself, the anti-pin hole.Because less than 2% o'clock, obdurability, anti-pin hole were insufficient in the value of BSx, on the other hand, when surpassing 6%, it is bad lamination to take place, or the heat-resisting lamination strength during hot water treatment is insufficient, therefore not preferred.Aspect raising obdurability, anti-pin hole and plyability or heat-resisting lamination strength, more preferably the scope of BSx is 3.5～5.0%.
In addition, the curling phenomenon that the value of BSd of film that constitutes polyamides mixing resin laminated film coil produces during to boiling water treating is brought big influence, the value of BSd is big more, bag easy more warpage (anti-り returns り), curl obviously, if BSd is suppressed at is no more than 2%, preferably be no more than 1.5%, more preferably no more than 1.2%, the warpage of the bag in the time of then can suppressing boiling water treating can prevent the curl generation of phenomenon of S word.
In addition, polyamides mixing resin laminated film coil of the present invention, the fluctuation rate of the maximum boiling water shrinkage (BSx) of the whole samples that preferably cut out are adjusted in the scope of average boiling water shrinkage (BSax) ± 2%～± 10% (more than ± 2% ± below 10%).At this, so-called all fluctuation rates of the maximum boiling water shrinkage (BSx) of sample are meant: maximum, minimum in obtaining the maximum boiling water shrinkage (BSx) of whole samples, and when obtaining the difference of big side of these maximums, the difference with average boiling water shrinkage in minimum and average boiling water shrinkage, this differs from the ratio with respect to average boiling water shrinkage.
Promptly, in polyamides mixing resin laminated film coil of the present invention, when the boiling water shrinkage of establishing sample (1)～(6) is Xn (n=1～6), the maxim Xmax of preferred Xn and average boiling water shrinkage (BSax) poor, and the difference of minimum value Xmin and average boiling water shrinkage (BSax) all in ± 10%.In other words, preferred | BSax-Xn| (‖ represents absolute value) is no more than 10%.
In addition, polyamides mixing resin laminated film coil of the present invention, the fluctuation rate of the maximum boiling water shrinkage (BSx) of the whole samples that preferably cut out is controlled at average boiling water shrinkage (BSa) ± 9% with interior scope, more preferably be controlled at ± 8% with interior scope, especially preferably be controlled at ± 7% with interior scope.
And, polyamides mixing resin laminated film coil of the present invention, the fluctuation rate of the maximum boiling water shrinkage (BSx) of the whole samples that preferably cut out is the smaller the better, but when considering to measure precision, the lower limit of this fluctuation rate is considered to exceed with about 2%.
In addition, polyamides mixing resin laminated film coil of the present invention, the fluctuation rate of the boiling water shrinkage direction poor (BSd) of the whole samples that preferably cut out are adjusted in the scope of average boiling water shrinkage direction poor (BSad) ± 2%～± 30% (more than 2% ± below 30%).At this, so-called all fluctuation rates of the boiling water shrinkage direction poor (BSd) of sample are meant: maximum, minimum in the boiling water shrinkage direction of obtaining whole samples poor (BSd), and when obtaining the difference of big side of these maximums, the difference with average boiling water shrinkage direction difference in minimum and average boiling water shrinkage direction difference, this differs from the ratio with respect to average boiling water shrinkage direction difference.
That is, in polyamides mixing resin laminated film coil of the present invention, when the boiling water shrinkage direction difference of establishing sample (1)～(6) is Yn (n=1～6), the maxim Ymax of preferred Yn and average boiling water shrinkage direction poor (BSad) poor, and the difference of minimum value Ymin and average boiling water shrinkage direction poor (BSad) all in ± 30%.In other words, preferred | BSad-Yn| (‖ represents absolute value) is no more than 30%.
In addition, polyamides mixing resin laminated film coil of the present invention, the fluctuation rate of the boiling water shrinkage direction poor (BSd) of the whole samples that preferably cut out is controlled at average boiling water shrinkage direction poor (BSad) ± 20% with interior scope, more preferably be controlled at ± 15% with interior scope, especially preferably be controlled at ± 10% with interior scope, especially preferably be controlled at ± 8% with interior scope.
And, polyamides mixing resin laminated film coil of the present invention, the fluctuation rate of the maximum boiling water shrinkage direction poor (BSd) of the whole samples that preferably cut out is the smaller the better, but when considering to measure precision, the lower limit of this fluctuation rate is considered to exceed with about 2%.
In addition, polyamides mixing resin laminated film coil of the present invention, the aviation value of the three-dimensional surface roughness of the whole samples that preferably cut out (SRa) is the scope of average surface roughness (SRaa) at 0.01～0.06 μ m, more preferably in the scope (in addition, one of measuring method of three-dimensional surface roughness example illustrates in an embodiment) of 0.02～0.05 μ m.Because it is not, can not obtain the good sliding under the high humidity, so preferred when average surface roughness during less than 0.01 μ m, on the contrary, because it is not when average surface roughness surpasses 0.06 μ m, with the gleyness reduction of film such as polyolefin, so preferred when carrying out lamination process.
Polyamides mixing resin laminated film coil of the present invention, the fluctuation rate of the three-dimensional surface roughness of the whole samples that preferably cut out (SRa) are adjusted in the scope of mean roughness (SRaa) ± 5%～± 20% (more than ± 5% ± below 20%).At this, so-called all fluctuation rates of the three-dimensional surface roughness (SRa) of sample are meant: maximum, minimum in obtaining the three-dimensional surface roughness of whole samples (SRa), and when obtaining the difference of big side of these maximums, the difference with average surface roughness in minimum and average surface roughness, this difference is with respect to ratio of average surface roughness.
Promptly, in polyamides mixing resin laminated film coil of the present invention, when the three-dimensional surface roughness of establishing said sample (1)～(6) is SRn (n=1～6), the maxim SRmax of preferred SRn and average surface roughness (SRaa) poor, and the difference of minimum value SRmin and average surface roughness all in ± 20%.In other words, | SRaa-SRn| (‖ represents absolute value) is no more than 20%.
In addition, polyamides mixing resin laminated film coil of the present invention, the fluctuation rate of the three-dimensional surface roughness of the whole samples that preferably cut out (SRa) is controlled at average surface roughness (SRaa) ± 15% with interior scope, more preferably be controlled at ± 10% with interior scope, especially preferably be controlled at ± 8% with interior scope.And, polyamides mixing resin laminated film coil of the present invention, the fluctuation rate of the three-dimensional surface roughness of the whole samples that preferably cut out (SRa) is the smaller the better, but when considering to measure precision, considers that the lower limit of this fluctuation rate exceeds with about 5%.
In addition, polyamides mixing resin laminated film coil of the present invention, the aviation value of the turbidity of the whole samples that preferably cut out are that average turbidity is controlled at 1.0～4.0 scope, more preferably 1.5～3.0 scope.Because it is not when average turbidity surpasses 4.0,, therefore preferred carrying out the outward appearance deterioration that bag adds the bag that forms man-hour.In addition, average turbidity is the smaller the better, but when considering to measure precision, considers that the lower limit of this average turbidity exceeds with about 1.0.
In addition, polyamides mixing resin laminated film coil of the present invention, the fluctuation rate of the turbidity of the whole samples that preferably cut out are adjusted in the scope of average turbidity ± 2%～± 15% (more than ± 2% ± below 15%).At this, so-called all fluctuation rates of the turbidity of sample are meant: the maximum in obtaining the turbidity of whole samples, minimum, and when obtaining the difference of big side of these maximums, the difference with average turbidity in minimum and average turbidity, this difference is with respect to ratio of average turbidity.
Promptly, in polyamides mixing resin laminated film coil of the present invention, when the turbidity of establishing said sample (1)～(6) is Hn (n=1～6), the maxim Hmax of preferred Hn and average turbidity poor, and the difference of minimum value Hmin and average turbidity (Han) all in ± 15%.In other words, | Han-Hn| (‖ represents absolute value) is no more than 15%.
In addition, polyamides mixing resin laminated film coil of the present invention, the fluctuation rate of the turbidity of the whole samples that preferably cut out is controlled at average turbidity ± 10% with interior scope, more preferably be controlled at ± 8% with interior scope, and, polyamides mixing resin laminated film coil of the present invention, the fluctuation rate of the turbidity of the whole samples that preferably cut out is the smaller the better, but when considering to measure precision, consider that the lower limit of this fluctuation rate exceeds with about 2%.
In addition, polyamides mixing resin laminated film coil of the present invention, preferably will be adjusted at respect to mean thickness at the fluctuation rate of the thickness on the length direction total length ± scope of 2%～± 10% (more than ± 2% ± below 10%) in.At this, what is called is meant at the fluctuation rate of the thickness of length direction total length: obtaining maximum, minimum in the thickness on the length direction total length, and when obtaining the difference of big side of these maximums, the difference with mean thickness in minimum and mean thickness, this difference is with respect to ratio of mean thickness.
Promptly, in polyamides mixing resin laminated film coil of the present invention, need make the maximum of T max of the thickness on the length direction total length and mean thickness (at the mean thickness Ta of length direction total length) poor, and the difference of minimum value Tmin and mean thickness (Ta) all in ± 10%.
In addition, polyamides mixing resin laminated film coil of the present invention, preferably the fluctuation rate of the thickness on the length direction total length be controlled at mean thickness (Ta) ± 8% with interior scope, more preferably ± 6% with interior scope.
And, polyamides mixing resin laminated film coil of the present invention, preferably the fluctuation rate of the thickness on the length direction total length is the smaller the better, but considers the performance of film forming apparatus, considers that the lower limit of this fluctuation rate exceeds with about 2%.
On the other hand, in the polyamides mixing resin laminated film coil of the present invention, the aviation value of the dynamic friction coefficient of 23 ℃ * 80%RH of the whole samples that preferably cut out (μ d) is the scope of mean coefficient of kinetic sliding friction (μ da) 0.3～0.8, more preferably in 0.4～0.6 scope.Because if the mean coefficient of kinetic sliding friction of 23 ℃ * 80%RH is lower than 0.3, add man-hour at bag, on cylinder, produce the skew (ズ レ) of film, processability is reduced, therefore not preferred, on the contrary, because when mean coefficient of kinetic sliding friction surpasses 0.8, under high humidity, can not obtain good sliding, therefore not preferred.
In addition, in the polyamides mixing resin laminated film coil of the present invention, the fluctuation rate of the dynamic friction coefficient of the whole samples that preferably cut out (μ d) be adjusted at mean coefficient of kinetic sliding friction ± scope of 5%～± 30% (more than ± 5% ± below 30%) in.At this, so-called all fluctuation rates of the dynamic friction coefficient (μ d) of sample are meant: maximum, minimum in obtaining the dynamic friction coefficient of whole samples (μ d), and when obtaining the difference of big side of these maximums, the difference with mean coefficient of kinetic sliding friction in minimum and mean coefficient of kinetic sliding friction, this difference is with respect to ratio of mean coefficient of kinetic sliding friction.
Promptly, in polyamides mixing resin laminated film coil of the present invention, when the dynamic friction coefficient of establishing said sample (1)～(6) is μ n (n=1～6), the maxim μ max of preferred μ n and mean coefficient of kinetic sliding friction (μ da) poor, and the difference of minimum value μ min and mean coefficient of kinetic sliding friction all in ± 30%.In other words, | μ da-μ n| (‖ represents absolute value) is no more than 30%.
In addition, polyamides mixing resin laminated film coil of the present invention, the fluctuation rate of the dynamic friction coefficient of the whole samples that preferably cut out (μ d) is controlled at the scope of mean coefficient of kinetic sliding friction ± 20%, and more preferably ± 15% with interior scope, further preferred ± 10% is with interior scope.And, polyamides mixing resin laminated film coil of the present invention, the fluctuation rate of the dynamic friction coefficient of the whole samples that preferably cut out (μ d) is the smaller the better, but when considering to measure precision, considers that the lower limit of this fluctuation rate exceeds with about 5%.
On the other hand, polyamides mixing resin laminated film coil of the present invention, the aviation value of the content of the inorganic particulate of the whole samples that preferably cut out is the scope of average content at 0.01～0.5 weight %, the more preferably scope of 0.05～0.3 weight % (in an embodiment one of inorganic particulate Determination on content method example being described in addition).Since when average content is lower than 0.01 weight %, under high humidity, can not obtain good sliding, therefore not preferred, on the contrary, because it is not when average content surpassed 0.5 weight %, the amilan that is difficult to remove in the Fabrication procedure carried out recycling, therefore preferred.
In addition, polyamides mixing resin laminated film coil of the present invention, the fluctuation rate of the inorganic particulate content of the whole samples that preferably cut out are adjusted in the scope of average content ± 2%～± 10% (more than ± 2% ± below 10%).At this, so-called all fluctuation rates of the inorganic particulate content of sample are meant: maximum, minimum in obtaining the inorganic particulate content of whole samples, and when obtaining the difference of big side of these maximums, the difference with average content in minimum and average content, this difference is with respect to ratio of average content.
Promptly, in polyamides mixing resin laminated film coil of the present invention, when the content of the inorganic particulate of establishing said sample (1)～(6) is Cn (n=1～6), the maxim Cmax of preferred Cn and average content (Ca) poor, and the difference of minimum value Cmin and average content all in ± 10%.In other words, preferred | Ca-Cn| (‖ represents absolute value) is no more than 10%.
In addition, in the polyamides mixing resin laminated film coil of the present invention, the fluctuation rate of the inorganic particulate content of the whole samples that preferably cut out be controlled at average content ± 8% with interior scope, more preferably ± 6% with interior scope.And, polyamides mixing resin laminated film coil of the present invention, the fluctuation rate of the inorganic particulate content of the whole samples that preferably cut out is the smaller the better, but when considering to measure precision, considers that the lower limit of this fluctuation rate exceeds with about 2%.
In addition, polyamides mixing resin laminated film coil of the present invention, when utilizing said method to cut out sample, when whole samples being obtained the ratio of refraction (Nz) of thickness direction, preferably the aviation value with these ratio of refraction is that mean refractive index (Nza) is adjusted into 1.500～1.520.In addition, mean refractive index is calculated with following formula 6.
Nz summation/sample the number of the whole samples of Nza=... 6
In addition, the Nz value that constitutes the biaxially oriented film of polyamides mixing resin laminated film coil is brought big influence to lamination strength and thickness spot membrane qualities such as (thick body spots).Therefore, mean refractive index is 1.500～1.520 such important documents conditions that necessitate when using after with biaxially oriented film and polyolefin resin film laminating.And,, insufficient at Nz with the lamination strength of polyolefin resin film etc. less than 1.500 o'clock, in the boiling water treating behind bag etc. and laminate substrate between peel off easily.On the other hand, this Nz reduces in the process that non-stretched film is biaxial stretch-formed in turn.In other words, can consider also with Nz that the big expression of Nz stretches insufficient, surpasses at 1.520 o'clock at Nz,, can not obtain satisfied membrane quality because biaxial stretch-formed deficiency significantly manifests thickness spot etc. as one of stretching index.Consider lamination strength and membrane quality two aspects, the scope of preferred especially Nz is 1.507～1.516 scope.
In addition, polyamides mixing resin laminated film coil of the present invention, preferably the fluctuation rate of the ratio of refraction of whole samples that will cut out (Nz) with respect to the aviation value of these ratio of refraction (below be called mean refractive index) be adjusted into ± 2% with interior scope.At this, so-called all ratio of refraction (Nz) fluctuation rates of sample are meant: maximum, minimum in obtaining the ratio of refraction of whole samples (Nz), and when obtaining the difference of big side of these maximums, the difference with mean refractive index in minimum and mean refractive index, this difference is with respect to ratio of mean refractive index.
Promptly, in polyamides mixing resin laminated film coil of the present invention, when the ratio of refraction of establishing sample (1)～(6) is Nz1～Nz6, the maxim Nmax of preferred Nz1～Nz6 and mean refractive index poor, and the difference of the minimum value Nmin of Nz1～Nz6 and mean refractive index all in ± 2%.In other words, preferred | mean refractive index-Nz1|～| mean refractive index-Nz6| is no more than 2%.In addition, polyamides mixing resin laminated film coil of the present invention, the fluctuation rate of the ratio of refraction of the whole samples that more preferably cut out (Nz) with respect to mean refractive index ± 1% with interior scope.
And, polyamides mixing resin laminated film coil of the present invention, the fluctuation rate of the ratio of refraction of the whole samples that preferably cut out (Nz) is the smaller the better, but considers to measure precision or mechanical precision, considers that the lower limit of this fluctuation rate exceeds with about 0.1%.
As mentioned above, the rerum naturas such as tensile modulus of the thermoplastic elastomer in the one volume polyamides mixing resin laminated film coil are adjusted into the value of specialized range, simultaneously, reduce the change of rerum naturas such as the content of thermoplastic elastomer or tensile modulus, thus, can prevent the deterioration of the outward appearance in bag processing or the lamination process, even under high humidity, also can process the anti-pin hole of each bag after the bag processing high and not discrete (バ ラ Star キ) with good yield rate swimmingly.
As the amilan that uses among the present invention, for example can enumerate with the epsilon-caprolactams is the nylon 6 of primary raw material.In addition, as other amilan, can enumerate the amilan that obtains by with polycondensations such as three-membered ring or the lactams more than it, omega-amino acid, dibasic acid and diamines.Specifically, as lactams, except the epsilon-caprolactams that the front illustration is crossed, for example can enumerate: oenantholcatam (エ Na Application ト ラ Network system, oenantholactam), spicy inner formyl amine, lauric lactam, omega-amino acid for example can be enumerated: 6-aminocaprolc acid, 7-aminoheptylic acid, 9 aminononanoic acid, the amino undecanoic acid of 11-.In addition, dibasic acid for example can be enumerated: adipic acid, glutaric acid, heptandioic acid, suberic acid, azelaic acid, decanedioic acid, hendecane diacid (acid of ウ Application デ カ Application ジ オ Application), 12 carbon docosandioic acids (acid of De デ カ ジ オ Application), hexadecane diacid (acid of ヘ キ サ デ カ ジ オ Application), icosane diacid (acid of エ イ コ サ Application ジ オ Application), 20 carbon, two enedioic acids (acid of エ イ コ サ ジ エ Application ジ オ Application), 2,2, the 4-trimethyladipic acid, terephthalic acid, isophthalic acid, 2, the 6-naphthalene dicarboxylic acids, Xlylene dicarboxylic acid (acid of キ シ リ レ Application ジ カ Le ボ Application).Diamines for example can be enumerated: ethylene diamine, propane diamine, butanediamine, hexamethylenediamine, pentanediamine, hendecane diamines, 2,2,4 (or 2,4,4)-trimethyl hexamethylenediamine, cyclohexanediamine, two (4,4 '-aminocyclohexyl) methane, m-xylylenediamine (メ キ シ リ レ Application ジ ア ミ Application) etc.And, can use poly-mer or copolymer that these polycondensations are obtained, for example: nylon 6,7,11,12,6.6,6.9,6.11,6.12,6T, 6I, MXD6 (m xylylene adipamide 6), 6/6.6,6/12,6/6T, 6/6I, 6/MXD6 etc.And, when making polyamides mixing resin laminated film coil of the present invention, above-mentioned polyamide-based resin can be used or mixes at least two kinds of uses separately.
In addition, in above-mentioned polyamide-based resin, particularly preferably be relative viscosity among the present invention and be those of 2.0～3.5 scopes.The relative viscosity of polyamide-based resin can exert an influence to the obdurability of the biaxially oriented film that obtains and ductility etc., if relative viscosity is lower than 2.0, then its strength under shock becomes not enough, on the contrary, if relative viscosity surpasses 3.5, then there is the tendency that causes successively biaxial-oriented property (Zhu Er Shaft extensibility) variation by the drawing stress maximum.In addition, the so-called relative viscosity among the present invention is poly-mer 0.5g to be dissolved among the 97.5% sulfuric acid 50ml obtain solution, uses this solution to survey timer-operated value at 25 ℃.
As the thermoplastic elastomer that uses in the present invention, for example preferably use the ionomer etc. of olefine kind resins such as polyolefins elastic bodys such as copolymer, vinyl ionomer of copolymer, styrene or butadidenne of polyamide-based elastic body, ethylene methacrylic acid copolymer, ethene and the butylene of the block of polyamide-based resin such as nylon 6 or nylon 12 and PTMG (polytetramethylene glycol) or PEG (carbowax) etc. or random copolymers etc.
In addition, the amount of the thermoplastic elastomer that adds in polyamide-based resin is not particularly limited, but the lower limit of addition preferably is not less than 1 weight %, more preferably is not less than 2 weight %, especially preferably is not less than 3 weight %.On the other hand, the upper limit of addition preferably is no more than 15 weight %, more preferably no more than 10 weight %, especially preferably is no more than 6 weight %.When the addition of thermoplastic elastomer is lower than 1 weight %, can not obtain good anti-pin hole, so not preferred, on the contrary, when the addition of thermoplastic elastomer surpassed 15 weight %, so the obdurability of infringement film was not preferred.
The following manufacturing of polyamides mixing resin laminated film coil of the present invention: will melt extrude as the amilan fragment (chip) and the thermoplastic elastomer fragment of raw material, obtain non-stretched film (laminated film does not stretch), longitudinally (length direction) and laterally (Width) with this non-stretched film biaxial stretch-formed after, coil into web-like.
Polyamides mixing resin laminated film need have the structure of A/B (two kinds two-layer) or A/B/A (two kinds three layers) or A/B/C (three kinds three layers).Consider preferred symmetrical layers structure A/B/A from the aspect of curling.In addition, in the following description, the thick-layer when constituting the non-layer (being the B layer of A/B/A or A/B/C layer structure) that is positioned at outermost central part and two kinds of double-layer structures in each layer of laminated film (the B layer during the A/B layer structure of thin A layer and thick B layer) is called sandwich layer.In addition, be positioned at outermost layer (A when being A/B layer structure, B layer; A, C layer when A/B/A or A/B/C layer structure) and the thin layer during two kinds of double-layer structures (the A layer during the A/B layer structure of thin A layer and thick B layer) be called the top layer.
The preferred A layer of thickness ratio of each of polyamides mixing resin laminated film layer or A layer and C layer are 5～50%, more preferably 10～20%, preferred especially 12～18%.Under the situation of two kinds three layers A/B/A structures, the thickness ratio of the top layer A layer of aforementioned record is meant the thickness ratio sum on two top layers, under the situation of three kinds three layers A/B/C structures, the top layer A layer of aforementioned record and the thickness ratio of C layer are meant the thickness ratio sum on two top layers.Since when the thickness ratio of A layer or A layer and C layer less than 5% the time, thickness spot (thick body spot) causes the fluctuation rate increase of turbidity, thereby not preferred.On the other hand, because when the thickness ratio of A layer or A layer and C layer surpassed 30%, bending fatigue resistance worsened, when pinhole number increases, transparency deterioration, thereby not preferred.
In addition, in order to make aforesaid laminated film, when the non-oriented in fact polyamide-based hybrid resin sheet material of the layer structure of making aforementioned A/B, aforementioned A/B/A or aforementioned A/B/C, can suitably adopt the poly-mer that will constitute each layer to use and divide other extruder fusion, coextrusion, be poured on the swing roller from nozzle (mouthful gold), make its rapid cooling curing, obtain the method (so-called coetrusion) of non-oriented in fact polyamide sheet material thus.
Secondly, the manufacture method that is used to obtain polyamides mixing resin laminated film coil of the present invention is described.The present inventor is to the change or discrete research of rerum naturas such as the spot of thickness longitudinally (the thickness spot on the total length of film rolling) of film rolling, boiling water shrinkage, found that, the change of described spot of thickness longitudinally and rerum natura and discrete mainly is to be subjected to resin with fusion to form the influence of the various major causes in the cast operation of non-stretched film.Promptly, when the water ratio of the resin of the low or feeding hopper of the temperature of the resin when supplying with the funnel-form hopper that directly links with extruder (below be called hopper) was high, the spot of thickness longitudinally of non-stretched film increased or the change and discrete increase of biaxially oriented film rerum natura.In addition, in the time will being wound on the metallic roll from the resin that T shape mould is extruded, when the contact point confusion of resin and metallic roll, the spot of thickness longitudinally of non-stretched film also can become greatly, and change of the rerum natura of biaxially oriented film or discrete also change are big.And, when the stretching condition in the biaxial stretch-formed operation is not suitable for, the spot of the thickness longitudinally broadening of non-stretched film, the change of rerum natura or discrete also increase.
And the present inventor has carried out without single devotion research based on the above-mentioned fact, found that, when making film rolling, by using following means, even can obtain the change of rerum natura also can keep good sliding less under high humidity film rolling.
(1) uniformization of the shape of polyamide-based resin fragment and elastic body fragment
Water ratio when (2) resin chips is dry descends
(3) temperature when hopper is supplied with resin keeps
(4) suitableization of hopper shape
(5) segregation during mixed with resin prevents the interpolation of agent
(6) segregation prevents dysgenic the removing that the interpolation of agent causes
(7) suitableization of stretching condition
(8) use of high concentration raw material fragment
(9) adjustment of inorganic particulate proterties
(10) adjustment of film laminating form
Below, order illustrates above-mentioned each means.
(1) uniformization of the shape of polyamide-based resin sheet and elastomeric sheets
In the manufacturing of polyamides mixing resin laminated film coil of the present invention, after in hopper, will mixing as the amilan fragment of raw material and elastic body fragment, in a plurality of extruders (being used to form the extruder of each layer of laminated film) with its melting mixing, melt extrude, make film (so-called blending method) thus.Promptly, in dividing other hopper, supply with polyamide-based resin fragment and elastic body fragment continuously or off and on, as required by the buffering hopper, finally before each extruder (before) or just going up in the hopper (below be called final hopper) of (just going up), limit mixed polyamide resin chips and elastic body fragment, these raw material fragments are supplied with to extruder quantitatively according to extrusion capacity in the limit, form film.
But, capacity or shape according to final hopper, under the few situation of situation that amount of debris in final hopper is many and the fragment residual volume in the final hopper, the raw material segregation phenomena can take place, promptly the fragment of supplying with to each extruder from final hopper is formed different phenomenons.In addition, this segregation phenomena is unobvious especially simultaneously at the shape or the proportion of fragment.And, making long (Long chi な) during film, this segregation phenomena can cause that tensile modulus, anti-pin hole, maximum boiling water shrinkage, boiling water shrinkage direction are poor, the ratio of refraction change of film thickness, thickness direction.
Promptly, when the varying in size of the size of polyamide-based resin fragment and elastic body fragment, when the compound of fragment falls in final hopper, because little fragment falls earlier easily, therefore, fragment residual volume in final hopper after a little while, the ratio of big fragment increases, this is the reason that causes the raw material segregation.Therefore, in order to obtain the few film rolling of rerum natura change, need suppress the phenomenon of the raw material segregation in the final hopper according to the shape of amilan fragment and elastic body fragment.
The raw material fragment of polyamide normally takes out with line (strand) shape from polyplant with molten condition after polymerization, forms with line material cutter (strand cutter) cutting after the direct water-cooling.Therefore, the polyamide fragment is that section is oval oval column.On the other hand, elastic body raw material fragment multiform becomes to have the discoid of oval-shaped profile, the shape of polyamide fragment and elastic body fragment and the relation of raw material segregation are studied, found that, by with the average major diameter (mm) of the section ellipse of elastomeric raw material fragment, average minor axis (mm), average chip length (mm) with respect to the average major diameter (mm) of the section ellipse of the raw material fragment of polyamide-based resin, average minor axis (mm), average chip length (mm) be adjusted at respectively ± scope in 25% in, can reduce the above-mentioned raw materials segregation.In addition, since when with the average major diameter of the section ellipse of elastic body fragment, average minor axis, average chip length with respect to the average major diameter of the section ellipse of polyamide-based resin fragment, average minor axis, on average chip length be adjusted at respectively ± scope in 20% in the time, anti-segregation effect is extremely remarkable, therefore more preferably.
(2) water ratio during the dry resin fragment reduces
The fragment of supplying with in each hopper makes it reduce moisture usually by the heating of batch mixer devices such as (blender).When carrying out such fragment dry, when making mylar volume or polypropylene film volume, consider usually when drying, to reduce water ratio, can suppress to extrude the hydrolysis in the operation, obtain the good film volume.But, the result of present inventor's research is, when making polyamides mixing resin laminated film coil, only reduce water ratio when dry, be difficult to stretch, can not obtain the uniform film rolling of rerum natura, by water ratio is controlled in the specialized range, guarantee moisture to a certain degree, can hydrolysis in extruding operation, suitably carry out plasticized, can obtain the uniform film rolling of rerum natura.That is,, the water ratio of amilan fragment and thermoplastic elastomer fragment need be controlled at 800ppm～1000ppm for obtaining film rolling of the present invention.When the water ratio of fragment surpasses 1000ppm, when carrying out fusion, encouraged hydrolysis, make the longitudinal thickness spot variation of non-stretched film, the longitudinal thickness spot of biaxially oriented film is increased, cause the change of rerum natura or discrete.On the contrary, when the water ratio of fragment was lower than 800ppm, viscosity was too high during fusion, and system film (stretching easiness) worsens.The optimum moisture content of the fragment of supplying with in hopper in addition, is 850ppm～950ppm.
(3) temperature when each hopper is supplied with resin keeps
As mentioned above, even when the water ratio with fragment is adjusted into 800ppm～1000ppm,, can not obtain the uniform film rolling of rerum natura placing when supplying to each hopper fragment behind the heat drying drops to normal temperature (room temperature) to temperature after.That is, for obtaining film rolling of the present invention, need keep under the hi-heat situation, supply with to each hopper that is communicated with each extruder at the fragment that will use heat drying such as batch mixer.Specifically, need keep by the fragment of batch mixer heat drying supplying with each hopper under at least 80 ℃ the situation, more preferably keep under 90 ℃ the situation directly each hopper of supply at least.When the temperature of the fragment of supplying with each hopper during less than 80 ℃, the (Yao み Write body of nipping of resin) variation, become thickness spot or the change of rerum natura and discrete reason longitudinally, can not get film rolling of the present invention.In addition, when utilizing the dry fragment of device such as batch mixer, baking temperature need be adjusted into and be no more than 150 ℃.When baking temperature surpasses 150 ℃, hydrolysis might take place during owing to drying, therefore not preferred.In addition, with the temperature of the fragment of batch mixer heat drying during less than 80 ℃, need heat once more makes it to keep being not less than 80 ℃ and feeding hoppers.
(4) suitableization of hopper shape
By using the funnel-form hopper as the final hopper that is communicated with each extruder, and its leaning angle is controlled at is not less than 70 °, big fragment is also fallen equally easily with little fragment, the upper end of control content thing is while keeping horizontal surface to descend, therefore, can effectively reduce the raw material segregation.More preferably its leaning angle is for being not less than 75 °.In addition, the leaning angle of so-called hopper is meant the angle between funnelform hypotenuse and the horizontal line section.Also can use a plurality of hoppers, at this moment, in the expectation bucket in office, also all need its leaning angle is controlled to be and be not less than 70 °, more preferably be not less than 75 ° in the upstream of final hopper.
In addition, in order to suppress the change of boiling water shrinkage, preferably the cutting by the raw material fragment that uses etc. reduces the ratio of the powder body that produces.Because powder body encourages the generation of raw material segregation, therefore preferably remove the powder body that produces at in-process, reduce the ratio of the powder body that comprises in each hopper.The ratio of the micropowder that contains is entering in the full operation of extruder to the raw material fragment, preferably is controlled in the 1 weight %, more preferably is controlled in the 0.5 weight %.As the concrete grammar that is used to reduce the powder body ratio, for example when forming fragment, sieve or remove powder body by cyclone air filter during at air transferring raw material fragment with line material cutter.
(5) segregation during hybrid resin prevents the interpolation of agent
In addition, as the means that reduce the raw material segregation in each hopper, preferably in polyamide-based resin in each hopper and the elastomeric mixing, add sublimable segregation and prevent agent.Prevent agent as this sublimable segregation, can use the glycol that reduces boiling point, wherein preferably use polyoxyethylene polyoxy dipropylene glycol (polyoxyethylenepolyoxypropylene glycol).In addition, the sublimable segregation of adding in the raw material fragment of polyamide-based resin or the elastomeric raw material fragment amount that prevents agent is with respect to polyamide-based resin and elastomeric total weight meter preferably in the scope 0.02%～2.00%.When less than 0.02% the time, can not obtain enough anti-segregation effects, therefore not preferred, on the contrary, and when greater than 2.00% the time, not exclusively distillation, therefore not preferred.
And, as the means that reduce the raw material segregation in each hopper, also preferably the capacity of the hopper that uses is suitably changed.At this, the suitable capacity of each hopper with respect to extruder discharge rate hourly (discharge-amount) in the scope of 15～120 weight %, more preferably with respect to extruder discharge rate hourly in the scope of 20～100 weight %.
In addition, as the method for resinoid raw material fragment of mixed polyamide and elastic body raw material fragment, also can supply with in final hopper and each extruder with middle hopper (buffering hopper) by mixing.
In addition, can enumerate respectively as polyamide-based resin or elastic body, when mixing plurality of raw materials, the method of in each hopper, mixing in the weight feed plurality of raw materials at device from continuous and quantitative base feed fragment, or use batch mixer or paddle dryer (paddle dryer) etc. in the method for mixing before etc., but when using the latter, preferably reduce the size of raw material fragment, make can when discharging compound, not produce the raw material segregation.
(6) add the elimination (attraction of molten resin when metallic roll contacts) that segregation prevents the adverse effect that agent causes
Melt extruding fragment, when obtaining non-stretched film, utilize coetrusion,, carry out lamination by the temperature fusion fragment of each extruder with 200 ℃～300 ℃, extrude from T shape mould, thus, being shaped to film like (lamination sheet) (promptly casts, casting), then, the utilization method that will be wound on the chill rolls such as metallic roll that are cooled to set point of temperature is cooled off rapidly.In addition, from thickness spot, rerum natura change or the aspect that disperses consider that the preferred molten extrusion temperature is 240 ℃～290 ℃ longitudinally.For obtaining film rolling of the present invention, when the resin with fusion is wound up on the metallic roll, the air gap distance of the vertical direction that exports to the chill roll surface of T shape film (promptly from) is adjusted into 20～60mm, simultaneously, the vacuum tank suction devices such as (vacuum chambers) that utilization has a wide attraction mouth of width attracts the contact portion on molten resin and chill roll surface on direction opposite with take-up direction on the full duration of molten resin, thus, forcibly molten resin is close to (adherence) on metallic roll.
And, at this moment, for preventing that above-mentioned sublimable segregation from preventing that agent from hindering the situation of being close to (adherence) of molten resin to chill roll, need will attract the attraction wind speed of the part of mouth to be adjusted into 2.0～7.0m/sec, in addition, vacuum tank also can have a succession of sucking hole, but is easily to adjust the attraction wind speed that attracts mouth, with attracting mouth to be distinguished into the part of specified quantity in the horizontal, can on each part, attract the adjustment of wind speed.In addition, when increasing the speed of cast (casting), follow the rotation generation of metallic roll to follow stream, hindered be close to (adherence) of molten resin to metallic roll, therefore, more effectively adopt the attraction of suction device, for improving the be close to degree of molten resin to metallic roll, preferably will be arranged on by the wide shield that poly tetrafluoroethylene soft materials such as (registered trade mark (RTM)s) forms the upstream side adjacent with suction device (with respect to suction device with the opposite side of hand of rotation of metallic roll), cover and follow stream.In addition, for obtaining film rolling of the present invention, discrete (the バ ラ Star キ) of the attraction wind speed of vacuum tank must be suppressed in the average attraction wind speed (setting value) ± 20%, more preferably be suppressed at ± 10% in.And, filter preferably is set in vacuum tank, not produce because the change of the attraction wind speed of the vacuum tank that oligomer dust etc. causes, simultaneously, by feeding back the pressure reduction before and after this filtrations, adjusting attractive force.
In addition, for obtaining film rolling of the present invention, when the resin with fusion is wound up on the chill roll, need utilize needle electrode that the resin sheet (sheet) of fusion is applied the direct current negative charge (direct current Negative Electricity lotus) of 2～15kv, 90～105mA, on metallic roll, be close to continuously when making glow discharge (グ ロ one is put Electricity) and cooling rapidly.At this moment, when the direct current negative charge that will apply is adjusted into the scope of 7～14kv, because the thickness spot of longitudinal direction, rerum natura change or discrete decline, thereby preferred.In addition,, the discrete of direct current negative charge that applies need be suppressed in the average negative charge (setting value) ± 20% for obtaining film rolling of the present invention, more preferably be suppressed at ± 10% in.
(7) suitableization of stretching condition
As non-stretched film is carried out biaxial stretch-formed method, need to adopt non-stretched film longitudinally stretched with the roll-type stretcher and with stenter (tenter) formula stretcher behind cross directional stretch, carry out the longitudinal and transverse drawing process of heat-set treatment and mitigation processing.In addition, for obtaining film rolling of the present invention,, need to adopt so-called indulging-vertical-cross directional stretch method as biaxial stretch-formed method.So-called indulging-vertical-cross directional stretch method, be meant: when polyamide film longitudinal stretching that will be non-oriented in fact, carry out the stretching of F/s, and be not cooled to Tg or below it, then carry out the stretching of subordinate phase, to be not less than 3.0 times, preferably to be not less than 3.5 times ratio and to carry out cross directional stretch, further carry out the method for heat setting then.And, for obtaining film rolling of the present invention, carry out above-mentioned vertical-vertical-during cross directional stretch, need to set the longitudinal stretching multiplying power height of F/s longitudinal stretching multiplying power than subordinate phase.That is, the longitudinal stretching multiplying power by setting F/s is than the longitudinal stretching multiplying power height of subordinate phase, not only can make rerum natura such as boiling water shrinkage good, can also obtain discrete few film rolling of these rerum naturas.In addition, indulging-indulge-during cross directional stretch, usually the longitudinal stretching multiplying power of setting F/s is lower than the longitudinal stretching multiplying power of subordinate phase, the adhesion of pair roller when stretching, F/s can not take place, and can easily stretch, but by using poly tetrafluoroethylene (registered trade mark (RTM)) to make special rollers such as roller, even set the longitudinal stretching multiplying power height of the longitudinal stretching multiplying power of F/s than subordinate phase, also can not cause the adhesion of pair roller, and can easily stretch.
As mentioned above, indulging-indulge-during cross directional stretch, preferably the longitudinal stretching of F/s is being controlled under 80～90 ℃ the temperature and carries out about 2.0～about 2.4 times of stretchings.When the stretching ratio of F/s is higher than above-mentioned scope,, therefore not preferred because the thickness spot becomes big longitudinally.And, preferably the longitudinal stretching of subordinate phase is controlled under 65～75 ℃ the temperature and carries out about 1.3～about 1.7 times of stretchings.Because when the subordinate phase stretching ratio is lower than above-mentioned scope, boiling distortion (the askew body of ボ イ Le) increases, there is not practicality, therefore not preferred, on the contrary, because when the stretching ratio of subordinate phase was higher than above-mentioned scope, intensity (intensity during 5% elongation etc.) reduced longitudinally, there is not practicality, therefore not preferred.
In addition, as mentioned above, indulging-indulge-when horizontal,, can adopt hot-rolling stretching, infrared radiation stretching etc. as the longitudinal stretching method.In addition, adopt this vertical-vertical-when the cross directional stretch method is made film rolling of the present invention, not only change of thickness spot, rerum natura longitudinally or discrete diminishing, but also can reduce horizontal rerum natura change or discrete.In addition, vertical-vertical-during cross directional stretch, be 3.0～4.5 times preferably with total longitudinal stretching condition enactment.
In addition, indulging-indulge-during cross directional stretch, preferably cross directional stretch is set at and under 120～140 ℃ temperature, carries out about 4.0～5.5 times of stretchings.Because when the multiplying power of cross directional stretch was lower than above-mentioned scope, horizontal intensity (intensity during 5% elongation etc.) step-down did not have practicality, therefore not preferred, on the contrary, because when the multiplying power of cross directional stretch is higher than above-mentioned scope, horizontal percent thermal shrinkage increases, and is therefore not preferred.On the other hand, because when the temperature of cross directional stretch was lower than above-mentioned scope, the boiling distortion became big, does not have practicality, therefore not preferred, on the contrary, because when the temperature of cross directional stretch is higher than above-mentioned scope, horizontal intensity (intensity during 5% elongation etc.) reduces, and does not have practicality, and is therefore not preferred.
In addition, for obtaining film rolling of the present invention, preferably indulging under 180～230 ℃ the temperature-indulging-heat-set treatment behind the cross directional stretch.Since when the temperature of heat-set treatment is lower than above-mentioned scope, vertically reaches horizontal percent thermal shrinkage and increase, therefore not preferred, on the contrary,, therefore not preferred because when the temperature of heat-set treatment was higher than above-mentioned scope, the strength under shock of biaxially oriented film reduced.
And, for obtaining film rolling of the present invention, preferably make mitigation after the heat setting handle to be set at and relax 2～10%.Since when the ratio that relaxes processing is lower than above-mentioned scope, vertically reaches horizontal percent thermal shrinkage and become big, therefore not preferred, on the contrary, owing to when the ratio that relaxes processing is higher than above-mentioned scope, vertically reaches horizontal intensity (intensity during 5% elongation etc.) and reduce, there is not practicality, therefore not preferred.
In addition, the width of film rolling is not particularly limited, but considers that from the processing ease aspect width lower limit of film rolling preferably is not less than 0.35m, more preferably is not less than 0.5m.On the other hand, the width upper limit of film rolling preferably is no more than 2.5m, more preferably no more than 2.0m, further preferably is no more than 1.5m.And the volume length of film rolling is not particularly limited, but from being easy to batch or the easy operating aspect considers that the volume length lower limit of film rolling preferably is not less than 500m, more preferably is not less than 1000m.On the other hand, the long upper limit of the volume of film rolling preferably is no more than 25000m, more preferably no more than 20000m, further preferably is no more than 15000m.In addition, when film thickness is the 15 μ m left and right sides, especially preferably be no more than 12000m.In addition, batch core and can use 3 inches, 6 inches, 8 inches etc. paper, plastic core or metal coremaking usually.
On the other hand, the thickness that constitutes the film of film rolling of the present invention is not particularly limited, but for example as the packaging polyamides mixing resin laminated film, is preferably 8～50 μ m, more preferably 10～30 μ m.
And, in the polyamides mixing resin laminated film that constitutes film rolling of the present invention, in the scope that does not encumber characteristic, also can contain various additives such as lubricant (sliding drug), anti blocking agent, heat stabilizer, antioxidant, antistatic additive, photostabilizer, Dent resistance modifier.Particularly, preferably contain various inorganic particulates for the sliding that makes biaxially oriented film is good.In addition, when interpolation has the organic lubricants such as the two stearic acid of ethylene of the effect that reduces surface energy, because the sliding of the film of formation film rolling is good, thereby preferred.
In addition, in the polyamides mixing resin laminated film that constitutes film rolling of the present invention,, can heat-treat or the damping processing in order to make dimensional stability good according to purposes.And, for the gleyness that makes film surface is good, can carry out also that corona treatment (corona treatment), coating are handled and flame treatment (fire is scorching to be handled) etc., or print, processing such as evaporation.
(8) use of high concentration raw material fragment
As mentioned above, contain various inorganic particulates in the polyamide-based resin to adjust the roughness of surface of film, at this moment in order to improve the sliding of biaxially oriented film under high humidity, preferably to make, by adding inorganic particulate, can show the good sliding under the high humidity with specific adding method.That is, when in polyamide-based resin, adding inorganic particulate, be not inorganic particulate with powder be added into carry out in the extruder mixing, but preferred employing the: in polyamide-based resin, add the high concentration inorganic particulate in advance and make masterbatch material (master batch) polymer fragment, with the method for this masterbatch material fragment (high concentration raw material fragment) with the polyamide-based resin blend dilution that does not contain inorganic particulate.By adopting this means, (メ Le ト ラ イ Application meltline) is gone up phase mutual friction (こ The れ closes う) between the inorganic particulate, improves the dispersiveness of inorganic particulate, the influence that the result brings the sliding under the high humidity at molten thread.
In addition, when making high concentration raw material fragment, preferably the addition with inorganic particulate in the polyamide-based resin is set at 5～20 weight %, more preferably 10～15 weight %.Because when the addition of inorganic particulate surpassed 20 weight %, the dispersiveness of inorganic particulate reduced, and might form foreign matter in film, and is therefore not preferred.On the contrary, because when the addition of inorganic particulate surpassed 5 weight %, economic benefit worsened, therefore not preferred.And, when making this high concentration raw material fragment, because when by carrying out when mixing with inorganic particulate after method such as in advance amilan being pulverized to become the powder corpuscle under the state of cooling, the dispersiveness of inorganic particulate in resin improves, thereby preferably.
(9) adjustment of inorganic particulate proterties
When in polyamide-based resin, adding inorganic particulate,, can show the good sliding under the high humidity by making an addition to the proterties specialization of the inorganic particulate in the amilan that constitutes the top layer.That is, as the inorganic particulate that adds, the inorganic particulate that preferably has 0.5～5.0 μ m mean grain size (being mean grain size), special preferred silica particle.Because when mean grain size is lower than 0.5 μ m, can not obtain good sliding, on the contrary, when mean grain size surpassed 5.0 μ m, the transparency was bad, and so-called " (order け comes off) " takes place during printing, so not preferred.In addition, the mensuration of mean grain size, can adopt by Coulter-counter (Coulter counter) particle size distribution that obtains and calculate the method for weight mean diameter, also can measure, the particle that polyamides mixing resin laminated film is separated out with the acid dissolving can also be measured by the particle before in polyamide-based resin, adding.In addition, the porosity volume of inorganic particulate (porevolume) is preferably 0.5～2.0ml/g, more preferably 0.8～1.5ml/g.Since when porosity volume is lower than 0.5ml/g, the transparency deterioration of film, therefore not preferred, because it is not when porosity volume was higher than 2.0ml/g, the sliding of film worsened, therefore preferred.And, owing to not only in the amilan that constitutes the top layer, add inorganic particulate, when also adding a spot of inorganic particulate of 0.001～0.005 weight % in the amilan that is constituting sandwich layer, sliding under the high humidity greatly improves, therefore preferably, more preferably add the inorganic particulate of 0.002～0.004 weight %.In addition, because the particle diameter of inorganic particulate when making an addition to sandwich layer in is increased to the thickness on top layer or its when above, the sliding under the high humidity is more stable, so preferably.In addition, the sliding causes for stable under high humidity is still indeterminate like this, but considers it is because fluctuating (undulation) effect of the film surface that the inorganic particulate in the sandwich layer also comes brings the cause of good influence to the sliding under the high humidity.
(10) adjustment of film laminating form
As mentioned above,, form concavo-convexly at film surface, can show sliding by in polyamide-based resin, adding inorganic particulate, but this moment by adjusting the laminate form of film, thereby even under high humidity, also can show good sliding.Promptly, in the manufacture method of film rolling of the present invention, as mentioned above, by using coetrusion to melt extrude from a plurality of extruders, can form laminated film (laminate) with a plurality of layers of structure, but this moment, the preferred discharge rate of adjusting the resin that melt extrudes as the top layer, so that the thickness on the final top layer after stretching is 0.5～4.0 μ m, more preferably be adjusted into 1.0～3.0 μ m.
In addition, by using the means of (6), (7) in the stretching process that when formation does not stretch laminated film, uses the means of above-mentioned (1)～(5) and (8)～(10), the laminated film that do not stretching, the thickness spot of each layer that constitutes laminated film can be reduced, and then laminated film single-piece thickness spot can be reduced.And, because this, can reduce the rerum natura change of film rolling very effectively.In addition, the only any limited means in the means of above-mentioned (1)～(10) can be effectively reduces the rerum natura change of film rolling not make contributions, and is used in combination by the means with (1)～(10), and rerum natura that can very effective reduction film rolling changes.
Embodiment
Below, the present invention is described in detail by embodiment, but the present invention is not subjected to any qualification of the form of such embodiment, and in the scope that does not break away from main idea of the present invention, change can suit.At the film forming condition of the film rolling of composition, embodiment and the comparative example of the proterties of the raw material fragment A～I that uses in embodiment and the comparative example, raw material fragment A～I respectively shown in table 1～4.In addition, fragment A is made of nylon 6 (relative viscosity=2.8, Tg=41 ℃) 99.85 weight %, ethylene bis stearamide 0.15 weight %, fragment B, C are to be that 2.0 μ m, porosity volume are that the silica particle 15.0 weight % of 0.8ml/g constitute by nylon 6 (with the same rerum natura of fragment A) 85.00 weight %, mean grain size, and, the shape of fragment A～C all is an elliptical cylinder-shape, and the section major diameter of fragment A, B, section minor axis, chip length are all identical.In addition, fragment D, I are copolymer (relative viscosity=2.0) formations by nylon 12 and PTMG (polytetramethylene glycol), fragment E is made of the copolymer (relative viscosity=2.4) of nylon 6 and PEG (carbowax), fragment F is by ethylene methacrylic acid copolymer (190 ℃ MFR (melt flow rate, MeltFlow Rate)=and 2.4g/10 minute) constitute, fragment G is made of ethylene-butylene copolymer (MFR=2.0g/10 minute), and fragment H is made of vinyl ionomer (MFR=2.4g/10 minute).And the shape of fragment D～I all is oval column, and the section major diameter of fragment D～H, section minor axis, chip length are all identical.
Table 1
The composition of resin etc. Lubricant Shape (aviation value; Mm)
Nylon 6 (weight %) Ethylene bis stearamide (weight %) Mean grain size (μ m) Porosity volume (ml/g) Addition (weight %) The section major diameter The section minor axis Chip length
Fragment A 99.85 0.15 - - - 2.4 2.2 2.1
Fragment B 85.00 - 2.0 0.8 15.0 2.4 2.2 2.1
Fragment C 85.00 - 2.0 0.8 15.0 4.5 2.2 4.8
Table 2
The composition of resin etc. The trade name of resin Shape (aviation value; Mm) Relative viscosity MFR (190 ℃) (g/10 branch)
The section major diameter The section minor axis Chip length
Fragment D Nylon 12/PTMG copolymer The system DA330 of Japan weaving society 2.5 2.2 2.2 2.0 -
Fragment E Nylon 6/PEG copolymer The system ペ バ of ア Le ケ マ society Star Network ス MH1657 2.5 2.2 2.2 2.4 -
Fragment F Ethylene methacrylic acid copolymer The system ニ ユ of Mitsui デ ユ Port Application society Network レ Le NO502 2.5 2.2 2.2 - 2.4
Fragment G Ethylene-butylene copolymer The system of Mitsui Chemicals society Off マ one A4085 2.5 2.2 2.2 - 2.0
Fragment H The vinyl ionomer The system Ha イ ミ ラ of Mitsui デ ユ Port Application society Application 1605 2.5 2.2 2.2 - 2.4
Fragment I Nylon 12/PTMG copolymer The system ペ バ of ア Le ケ マ society Star Network ス 4033 4.5 2.2 2.8 2.0 -
Table 3
Laminate form Film forming condition (extruding～cool off)
Ground floor (skin) extruder condition The second layer (interlayer) extruder condition The 3rd layer of (internal layer) extruder condition The attraction wind speed of vacuum tank (m/ branch)
Layer structure Bed thickness is than (skin/interlayer/internal layer) (μ m) The mixture ratio of resin (weight %) Segregation prevents agent addition (ppm) The leaning angle of hopper (degree) The water ratio of fragment (ppm) Fragment temperature when hopper is supplied with (℃) The mixture ratio of resin (weight %) Segregation prevents agent addition (ppm) The leaning angle of hopper (degree) The water ratio of fragment (ppm) Fragment temperature when hopper is supplied with (℃) The mixture ratio of resin (weight %) Segregation prevents agent addition (ppm) The leaning angle of hopper (degree) The water ratio of fragment (ppm) Fragment temperature when hopper is supplied with (℃)
Embodiment 1 2 kinds 3 layers 2/11/2 A/B/D＝96.5/0.5/3 1000 70 800 91 A/B/D＝96.97/0.03/3 1000 70 800 91 A/B/D＝96.5/0.5/3 1000 70 800 91 5.0±0.5
Embodiment 2 2 kinds 3 layers 2/11/2 A/B/D＝96/1/3 1000 70 800 91 A/B/D＝96.94/0.06/3 1000 70 800 91 A/B/D＝96/1/3 1000 70 800 91 5.0±0.5
Embodiment 3 2 kinds 3 layers 1/13/1 A/B/D＝96.5/0.5/3 1000 70 800 91 A/B/D＝96.97/0.03/3 1000 70 800 91 A/B/D＝96.5/0.5/3 1000 70 800 91 5.0±0.5
Embodiment 4 2 kinds 3 layers 2/11/2 A/B/D＝96.5/0.5/3 1000 70 800 91 A/B/D＝96.97/0.03/3 1000 70 800 91 A/B/D＝96.5/0.5/35 1000 70 800 91 5.0±0.5
Embodiment 5 2 kinds 3 layers 2/11/2 A/B/D＝96.5/0.5/3 1000 70 800 91 A/B/D＝96.97/0.03/3 1000 70 800 91 A/B/D＝96.5/0.5/3 1000 70 800 91 5.0±0.5
Embodiment 6 2 kinds 3 layers 2/11/2 A/B/D＝96.5/0.5/3 1000 65 800 91 A/B/D＝96.97/0.03/3 1000 65 800 91 A/B/D＝96.5/0.5/3 1000 65 800 91 5.0±0.5
Embodiment 7 2 kinds 3 layers 2/11/2 A/B/D＝89.5/0.5/10 1000 70 800 91 A/B/D＝89.97/0.03/10 1000 70 800 91 A/B/D＝89.5/0.5/10 1000 70 800 91 5.0±0.5
Embodiment 8 2 kinds 3 layers 2/11/2 A/B/E＝94.5/0.5/5 1000 70 800 91 A/B/E＝94.97/0.03/5 1000 70 800 91 A/B/E＝94.5/0.5/5 1000 70 800 91 5.0±0.5
Embodiment 9 2 kinds 3 layers 2/11/2 A/B/F＝94.5/0.5/5 1000 70 800 91 A/B/F＝94.97/0.03/5 1000 70 800 91 A/B/F＝94.5/0.5/5 1000 70 800 91 5.0±0.5
Embodiment 10 2 kinds 3 layers 2/11/2 A/B/G＝94.5/0.5/5 1000 70 800 91 A/B/G＝94.97/0.03/5 1000 70 800 91 A/B/G＝94.5/0.5/5 1000 70 800 91 5.0±0.5
Embodiment 11 2 kind 3 2/11/2 A/B/H＝94.5/0.5/5 1000 70 800 91 A/B/H＝94.97/0.03/5 1000 70 800 91 A/B/H＝94.5/0.5/5 1000 70 800 91 5.0±0.5
Layer
Comparative example 1 1 kind 1 layer -/15/- - - - - - A/B/D＝96.5/0.5/3 1000 70 800 91 - - - - - 5.0±0.5
Comparative example 2 2 kinds 3 layers 2/11/2 A/C/D＝96.5/0.5/3 1000 70 800 91 A/C/D＝96.97/0.03/3 1000 70 800 91 A/C/D＝96.5/0.5/3 1000 70 800 91 5.0±0.5
Comparative example 3 2 kinds 3 layers 2/11/2 A/B/I＝96.5/0.5/3 1000 70 800 91 A/B/I＝96.97/0.03/3 1000 70 800 91 A/B/I＝96.5/0.5/3 1000 70 800 91 5.0±0.5
Comparative example 4 2 kinds 3 layers 2/11/2 A/B/D＝96.5/0.5/3 1000 45 800 91 A/B/D＝96.97/0.03/3 1000 45 800 91 A/B/D＝96.5/0.5/3 1000 45 800 91 5.0±0.5
Comparative example 5 2 kinds 3 layers 2/11/2 A/B/D＝96.5/0.5/3 1000 70 800 30 A/B/D＝96.97/0.03/3 1000 70 800 30 A/B/D＝96.5/0.5/3 1000 70 800 30 5.0±0.5
Comparative example 6 2 kinds 3 layers 2/11/2 A/B/D＝96.5/0.5/3 1000 70 1500 85 A/B/D＝96.97/0.03/3 1000 70 1500 85 A/B/D＝96.5/0.5/3 1000 70 1500 85 5.0±0.5
Comparative example 7 2 kinds 3 layers 2/11/2 A/B/D＝96.5/0.5/3 0 70 800 91 A/B/D＝96.97/0.03/3 0 70 800 91 A/B/D＝96.5/0.5/3 0 70 800 91 5.0±0.5
Comparative example 8 2 kinds 3 layers 2/11/2 A/B/D＝96.5/0.5/3 1000 70 800 91 A/B/D＝96.97/0.03/3 1000 70 800 91 A/B/D＝96.5/0.5/3 1000 70 800 91 5.0±0.5
Table 4
Film forming condition (stretching～heat treatment)
First longitudinal stretching Second longitudinal stretching Cross directional stretch Heat setting (℃) Relaxation processes (%)
Temperature (℃) Multiplying power Temperature (℃) Multiplying power Temperature (℃) Multiplying power
Embodiment 1 85 2.1 70 1.6 130 4.0 210 5.0
Embodiment 2 85 2.1 70 1.6 130 4.0 210 5.0
Embodiment 3 85 2.1 70 1.6 130 4.0 210 5.0
Embodiment 4 90 2.2 70 1.5 130 4.0 210 5.0
Embodiment 5 85 2.1 70 1.6 130 3.6 215 3.0
Embodiment 6 85 2.1 70 1.6 130 4.0 210 5.0
Embodiment 7 85 2.1 70 1.6 130 4.0 210 5.0
Embodiment 8 85 2.1 70 1.6 130 4.0 210 5.0
Embodiment 9 85 2.1 70 1.6 130 4.0 210 5.0
Embodiment 10 85 2.1 70 1.6 130 4.0 210 5.0
Embodiment 11 85 2.1 70 1.6 130 4.0 210 5.0
Comparative example 1 85 2.1 70 1.6 130 4.0 210 5.0
Comparative example 2 85 2.1 70 1.6 130 4.0 210 5.0
Comparative example 3 85 2.1 70 1.6 130 4.0 210 5.0
Comparative example 4 85 2.1 70 1.6 130 4.0 210 5.0
Comparative example 5 85 2.1 70 1.6 130 4.0 210 5.0
Comparative example 6 85 2.1 70 1.6 130 4.0 210 5.0
Comparative example 7 85 2.1 70 1.6 130 4.0 210 5.0
Comparative example 8 90 1.5 70 2.2 130 4.0 210 5.0
[embodiment 1]
By utilizing coetrusion that polyamide-based hybrid resin is melt extruded (in mould lamination and extrude) from three extruders (first～the 3rd extruder), and batch on the metallic roll of the rotation that is cooled to 17 ℃, make its rapid cooling, obtain the non-stretched film (polyamides mixing resin laminated) of two kinds of three-deckers of thickness 257 μ m thus.The formation method (to the operation that melt extrudes) of each of non-stretched film layer is as described below.In addition, in the following description, sequentially be called ground floor, the second layer, the 3rd layer (promptly the 3rd layer surface is the contact surface of metallic roll) from polyamides mixing resin laminated top layer.
The formation of ground floor (skin)
Use the mixing device (Block レ Application ダ one device) of 15kl in about 8.0 hours above-mentioned fragment A, B, D to be warmed to about 120 ℃ in the limit respectively, the limit is carried out predrying.Take each fragment of specified amount in the batch mixer, measure water ratio, the water ratio of fragment A, B, D all is 800ppm.In addition, the mensuration of water ratio is used karl Fischer moisture meter (the system MKC-210 of KYOTO Electronics society), carries out under the condition of 230 ℃ of sample weight 1g, sample heating-up temperature.
Then, each fragment in each batch mixer after predrying is supplied with in mixing and blending machine (mixing ミ キ サ one) respectively continuously by quantitative feed screw.In addition, the delivery volume of fragment A is set at 96.5 weight %, the delivery volume of fragment B is set at 0.5 weight %, the delivery volume of fragment C is set at 3.0 weight %.In addition, add polyoxyethylene polyoxy dipropylene glycol (polyoxyethylenepolyoxypropylene glycol) (the system ニ ユ of Sanyo chemistry society one Port one Le PE-64) and prevent agent as sublimable segregation in the hopper of having supplied with fragment A and fragment B, making its total weight with respect to fragment A, B, D is 1000ppm.
Then, as mentioned above, fragment A, the B that will mix in mixing and blending machine, the mixed material of D supply to respectively in the hopper directly over the extruder (first extruder) continuously by quantitative feed screw.The capacity of hopper is to put into 150kg raw material fragment.In addition, the leaning angle of hopper is adjusted to 70 °.
In addition, when in hopper, supplying with fragment A, B, D,, supply with to hopper at short notice, so that the temperature of the fragment in each batch mixer can be not low excessively from drying by mixing and blending machine.Fragment A, the B of (before), the temperature of D all are about 91 ℃ before hopper is supplied with.Then, fragment A, B, D (finishing mixing) with supplying with melt extrude it under 270 ℃ with single-screw first extruder from T shape mould.
The formation of the second layer (interlayer)
As mentioned above, in mixing and blending machine, supply with fragment A, B, D in dried each batch mixer continuously respectively with quantitative feed screw.In addition, the delivery volume of fragment A is set at 96.97 weight %, the delivery volume of fragment B is set at 0.03 weight %, the delivery volume of fragment D is set at 3.0 weight %.In addition, add polyoxyethylene polyoxy dipropylene glycol (the system ニ ユ of Sanyo chemistry society one Port one Le PE-64) and prevent agent as sublimable segregation in the hopper of having supplied with fragment A and fragment B, making its total weight with respect to fragment A, B, D is 1000ppm.
Then, as mentioned above, fragment A, the B that will mix in mixing and blending machine, the mixed material of D deliver to respectively in the hopper directly over the extruder (second extruder) continuously by quantitative feed screw.The capacity of hopper is to put into 150kg raw material fragment.In addition, the leaning angle of hopper is adjusted to 70 °.
In addition, when in hopper, supplying with fragment A, B, D,, supply with to hopper at short notice, so that the temperature of the fragment in each batch mixer can be not low excessively from drying by mixing and blending machine.Fragment A, B before hopper is supplied with, the temperature of D all are about 91 ℃.Then, fragment A, B, D (finishing mixing) with supplying with melt extrude it under 270 ℃ with single-screw second extruder from T shape mould.
The formation of the 3rd layer (internal layer)
As mentioned above, in mixing and blending machine, supply with fragment A, B, D in dried each batch mixer continuously respectively with quantitative feed screw.In addition, the delivery volume of fragment A is set at 96.5 weight %, the delivery volume of fragment B is set at 0.5 weight %, the delivery volume of fragment D is set at 3.0 weight %.In addition, add polyoxyethylene polyoxy dipropylene glycol (the system ニ ユ of Sanyo chemistry society one Port one Le PE-64) and prevent agent as sublimable segregation in the hopper of having supplied with fragment A and fragment B, making its total weight with respect to fragment A, B, D is 1000ppm.
Then, as mentioned above, fragment A, the B that will mix in mixing and blending machine, the mixed material of D deliver to respectively in the hopper directly over the extruder (the 3rd extruder) continuously by quantitative feed screw.The capacity of hopper is to put into 150kg raw material fragment.In addition, the leaning angle of hopper is adjusted to 70 °.
In addition, when in hopper, supplying with fragment A, B, D,, supply with to hopper at short notice, so that the temperature of the fragment in each batch mixer can be not low excessively from drying by mixing and blending machine.Fragment A, B before hopper is supplied with, the temperature of D all are about 91 ℃.Then, fragment A, B, D (finishing mixing) with supplying with melt extrude it under 270 ℃ with single-screw the 3rd extruder from T shape mould.
In addition, in each extruder of embodiment 1, the mean length of thermoplastic elastomer (fragment D), average minor axis, average chip length be with respect to the mean length of each polyamide-based resin fragment (fragment A, B), average minor axis, average chip length, be included in respectively ± 20% with in the interior scope.In addition, adjust the discharge rate of first～three extruder of non-stretched film in forming, making ground floor/second layer/3'sth layer thickness ratio is 2/11/2.
In addition, air gap when being wound on molten resin on the metallic roll (air gap) is adjusted into 40mm, by needle electrode, the film of fusion is applied the direct current negative charge of 11 ± 1.1kv, 100mA, and carry out glow discharge, the resin static of fusion is close on the metallic roll.In addition, when being wound on molten resin on the metallic roll, the part that contacts with metallic roll by the resin with fusion utilizes vacuum tank to attract in the opposite direction to the side of batching with resin on the whole width of molten resin, promotes molten resin being close to metallic roll.In addition, the attraction wind speed of vacuum tank is adjusted into 5.0 ± 0.5m/ second on the whole width (being the full duration of molten resin) that attracts mouth.
Then, utilize poly tetrafluoroethylene (registered trade mark (RTM)) system roller with the about 85 ℃ of longitudinal stretchings of draft temperature about 2.1 times (first longitudinal stretching) non-stretched film that obtains after, utilize the ceramic roller with about 1.6 times of 70 ℃ of longitudinal stretchings of draft temperature (second longitudinal stretching).Further the sheet material with longitudinal stretching imports in the stenter continuously, 4.0 times of about 130 ℃ of cross directional stretchs, carry out heat setting at about 210 ℃, and carry out 5.0% transverse relaxation handle after with its cooling, and two edges portion is removed in cutting, thus the biaxially oriented film of about 15 μ m is made film 2000m continuously or more than it, made former film rolling (ミ Le ロ one Le).With obtain biaxial stretch-formed after laminated film cut thinly along thickness direction, under electron microscope, observe, ground floor, the second layer, the 3rd layer thickness are respectively about 2 μ m, about 11 μ m, about 2 μ m.
In addition, the mobility scale scope of the film surface temperature when making the 2000m film continuously is mean temperature ± 0.8 ℃ at preheating procedure, is mean temperature ± 0.6 ℃ at stretching process, in heat treatment step is the scope of mean temperature ± 0.5 ℃.In addition, the former film rolling (ミ Le ロ one Le) that obtains is cut into width 400mm, length 2000mm, batches on 3 inches the paper tube, obtain two volume polyamides mixing resin laminated film coils (cutting volume, ス リ Star ト ロ one Le).Then, use the two volume cutting volumes (i.e. the volume that obtains by same former film rolling (ミ Le ロ one Le)) that obtain to utilize following method to carry out evaluating characteristics.In addition, in the mensuration of following BS (boiling water shrinkage), BSx (maximum boiling water shrinkage), BSd (the boiling water shrinkage direction is poor), ratio of refraction, coiling termination 2m at the distance film cuts out portion with interior first sample that is provided with, cutting out the every about 100m of portion from first sample is provided with the 2nd～20th sample and cuts out portion, begin 2m at the coiling of distance film and the 21st sample is set cuts out portion, cut out the sample film from these each sample portions of cutting out of the 1st to the 21st with interior.Evaluation result is shown in table 5～9.In expression during evaluation result, relevant strength under shock, lamination strength are shown as the mobility scale of the numerical value of the aviation value of each the specimen sample numerical value after the mensuration and each specimen sample.In addition, curl, be shown as number and whole comprehensive evaluation levels of specimen sample of the specimen sample of each evaluation level about the S word.
[boiling water shrinkage]
The biaxially oriented film (sample film) that will cut out from the respectively portion of cutting out of single cutting volume (slit roll) cuts into the square of 21cm on one side, places at least 2 hours under 23 ℃, the atmosphere of 65%RH.The central authorities of drawing with this sample are the circle of the diameter 20cm at center, are 0 ° with vertically (film is drawn direction), draw by the straight line at circle center in 0～165 ° of direction by cw with 15 ° of intervals, measure the diameter of all directions, as the length before handling.Then, at the sample that will cut out furnace run after 30 minutes in boiling water, with its taking-up, wipe the moisture that is attached to the surface, carry out air-dry, then, in 23 ℃, the atmosphere of 65RH, placed at least 2 hours, as mentioned above, be determined at the length of the straight line that draws on each diametric(al), 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) according to following formula 1～5.
Then, by maximum, the minimum in the maximum boiling water shrinkage (BSx) of obtaining whole samples, calculate and big side of these maximums, difference in minimum and average boiling water shrinkage poor with average boiling water shrinkage (BSax), calculate the ratio (%) of this difference, obtain the fluctuation rate of maximum boiling water shrinkage (BSx) thus with respect to average boiling water shrinkage (BSax) with respect to average boiling water shrinkage (BSax).In addition, by maximum, the minimum in the boiling water shrinkage direction of obtaining whole samples poor (BSd), calculate and big side of these maximums, difference in minimum and average boiling water shrinkage direction poor (BSad) poor with average boiling water shrinkage direction poor (BSad), calculate the ratio (%) of this difference, obtain the fluctuation rate of boiling water shrinkage direction poor (BSd) thus with respect to average boiling water shrinkage direction poor (BSad) with respect to average boiling water shrinkage direction poor (BSad).
[three-dimensional surface roughness]
The surface of the biaxially oriented film (sample film) that the respectively portion of cutting out from single cutting volume is cut out, use contact pin type three-dimensional surface roughness meter (the little slope institute system of Co., Ltd., SE-3AK), radius 2 μ m at pin, load 30mg, under the condition of the speed 0.1mm/s of pin, with cut-out (cutoff) value at the length direction of film is 0.25mm, 1mm measures in measured length, be divided into 500 points at interval with 2 μ m, in addition, Width along film, measuring at measured length 0.3mm, be divided into 150 points with the interval of 2 μ m with above-mentioned same condition.Use three-dimensional roughness analytical equipment (the little Ban Yanjiusuoshe system of Co., Ltd., TDA-21) that the height of the three-dimensional of the cut-point each point that obtains is analyzed, obtain three-dimensional average surface roughness (nm).
[the dynamic friction coefficient μ d under the high humidity]
The biaxially oriented film that the respectively portion of cutting out that use is rolled up from cutting cuts out is according to JIS-C2151, by the dynamic friction coefficient between the following condition evaluating skin.
Measure atmosphere: 23 ℃, 80%RH
Test piece: wide 130mm, long 250mm
Test speed: 150mm/ branch
[turbidity]
Each biaxially oriented film that cuts out for the respectively portion of cutting out from cutting volume according to JIS-K7136, uses nephelometer (Japanese electric look Industrial Co., Ltd system, 300A) to measure.In addition, measure and carry out secondary, obtain its aviation value.
[content of inorganic particulate]
Obtain the weight of the residue of biaxially oriented film when 800 ℃ of burnings that will cut out from the respectively portion of cutting out of cutting volume, the ratio (percentage) of calculating this residue weight film weight preceding with respect to burning is as inorganic particulate (silica) content.In addition, when measuring inorganic particulate content, also can adopt the weight of the residue when obtaining the biaxially oriented film that to cut out from the portion of cutting out respectively and being dissolved in the sulfuric acid equal solvent, calculate the method for the weight of this residue with respect to the ratio (percentage) of initial film weight.
[longitudinal thickness spot]
Cutting being twisted on the overall length of length direction cutting makes the thickness spot and measures with the cutting volume into about the 3cm width.Then, use the thickness spot determinator (wide region high sensitivity electronic gauge K-313A) of ア Application リ Star society system to obtain mean thickness, maximum ga(u)ge, minimum thickness on the length direction total length.Then, calculate the poor of big side of in these maximum ga(u)ges, the minimum thickness and difference mean thickness and mean thickness, calculate the ratio (%) of this difference, thus, calculate the fluctuation rate of the thickness on the length direction total length with respect to mean thickness by following formula 7.
The fluctuation rate of thickness=| maximum ga(u)ge or minimum thickness-mean thickness |/mean thickness ... 7
[ratio of refraction]
Use [the Abbe refractometer 4T type] of ア go society system, each sample film that will cut out from each sample portion of cutting out is placed at least 2 hours 23 ℃, the atmosphere of 65%RH after, measure the ratio of refraction (Nz) of thickness direction.In addition, calculate the average mean refractive index of whole sample films,, calculate in the full sample the poor of maximum or minimum Nz and mean refractive index as table 6, simultaneously, calculate this difference with respect to the ratio of mean refractive index as fluctuation rate.
[strength under shock]
Each sample film that will cut out from the portion of cutting out is respectively placed at least 2 hours 23 ℃, the atmosphere of 65%RH after, use the smart mechanism of Japan to make [the film shock test machine TSS formula] of society's system, utilize the semisphere impactor of diameter 12.7mm to measure disruption characteristic, as strength under shock.In addition, also calculate the average strength under shock of whole sample films.
[content of elastic body composition]
Each sample film that will cut out from the portion of cutting out respectively vertically cuts off with respect to Surface Vertical and with respect to take-up direction, makes ultra-thin section, utilizes ultrathin sectioning, by phosphotungstic acid (acid of リ Application Application グ ス テ Application) and ruthenium-oxide dyeing, modulation sample.Then, use society of NEC system transmission electron microscope (JEM2010), observe for 10000 times with multiplying power, according to taking the photograph electron micrograph (the about 220mm of the about 160mm * take-up direction of thickness direction).Then, use the imaged processing equipment of society of NEC (analySIS), the area of calculating the elastomer portion that is dyeed by phosphotungstic acid and ruthenium-oxide accounts for the single-piece ratio, as the content of elastic body composition.
[tensile modulus]
Each sample Film sampling length 150mm, the width 15mm that will cut out from the portion of cutting out respectively, 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, use the system オ of Shimadzu Corporation one ト グ ラ Off AG-100E type, the film of damping is sandwiched in the middle of the fragment that separates the 100mm distance, stretch with draw speed 200mm/ branch, calculate the interior drawing stress of stretch ratio limit and the ratio of distortion cooresponding, as tensile modulus with it.
[lamination process]
Use the boiling water shrinkage above-mentioned with mensuration, the longitudinal thickness spot, ratio of refraction, the different cutting volume (obtaining) of cutting volume of strength under shock by same former film rolling (ミ Le ロ one Le), to the biaxially oriented film coating polyurethanes cementation coating agent (ウ レ Application is the AC drug) (the system EL443 of Japan モ one ト Application society) that constitutes this cutting volume, then, on it, use the single test laminater (シ Application グ Le テ ス ト ラ ミ ネ one one) of モ ダ Application マ シ Na リ one society's system, at 315 ℃ of LDPE (low density polyethylene (LDPE)) films of extruding thickness 15 μ m, further LLDPE (straight-chain low density polyethylene) film of continuous laminating thickness 40 μ m thereon obtains three laminate rolls of laminated structure layer by layer that are made of polyamide-based hybrid resin/LDPE/LLDPE.Processability when in addition, estimating the manufacturing laminate roll by following three stages.In addition, the temperature when estimating lamination process is about 25 ℃, and humidity is about 75%RH.
Zero: do not produce wrinkle on the volume, do not need to carry out the condition adjustment
△: the wrinkle of eliminating volume by regularization condition
*: no matter carry out the adjustment of any condition, all can on volume, produce wrinkle.
[lamination strength]
In addition, to be cut into width 15mm, length 200mm from the laminated film that this laminate roll cuts out, as test piece, use the テ Application シ ロ Application UMT-II-500 type of Japan ボ one Le De ウ イ Application society system, under the condition of 23 ℃ of temperature, relative humidity 65%, measure the peel strength of polyamides mixing resin laminated film layer and LDPE interlayer.In addition, draw speed is the 10cm/ branch, and peel angle is 180 degree, released part is added water measure.In addition, the mensuration of lamination strength is meant: the coiling at the distance laminate roll stops in the 2m, cut out first test piece, cut out the 2nd～the 20th test piece apart from the every about 100m of the portion that cuts out of first test piece, coiling at the distance film begins in the 2m, cut out the 21st test piece, these the 1st～the 21st each test pieces are measured.In addition, also calculate the aviation value of these measured values.
[S word curl phenomenon]
As mentioned above, use the Sealing tester (テ ス ト シ one ラ one) of western mechanical society system, to be parallel to as the laminated film that laminate roll batches and batch folded lengthwise twice, simultaneously, longitudinally the every 20mm in each two ends seals 150 ℃ of Continuous Heat, and vertically seal 10mm intermittently with the interval of 150mm thereon, obtain the half-blank of width 200mm.Along with its length direction cutting two edges portion of batching, make hermetic unit be 10mm after, be that the boundary cuts off with the hermetic unit along perpendicular direction, make three limit sealing bag (sealed widths: 10mm).From these three limits sealing bags, select coiling by the distance laminate roll to stop three limit sealing bags that 2m makes with interior part as first sample, will by about 100,200 from the making part of this first sample ... 1800, the three limit sealing bags made of the part of 1900m select respectively as the 2nd～20th sample, will select as the 21st sample by the distance laminate roll three limit sealing bags that beginning 2m makes with interior part of reeling.And, with the heat treatment after 30 minutes in boiling water of these 21 three limit sealing bags, under 23 ℃, the atmosphere of 65%RH, keep diel, further that these 21 three limit sealing bags are overlapping, from the last load that applies 1kg towards the whole face of bag, after keeping diel, remove load, the following degree of estimating the warpage (the S word curls) of bag.
◎: do not have warpage fully
Zero: see warpage slightly
*: obviously see warpage
* *: warpage is remarkable
[anti-pin hole]
To cut into the size of 20.3cm (8 inches) * 27.9cm (11 inches) from the laminated film that above-mentioned laminate roll cuts out, oblong test film (laminated film) after this cut-out was placed 24 hours under the condition of 23 ℃ of temperature, relative humidity 50% at least, nursed one's health.Then, this rectangular test film of volume frame (volume frame) makes the cylindric of length 20.32cm (8 inches).Then, with one section periphery that is fixed on the discoid fixed head of Gelboflex experimental engine (industrial society of science system, NO.901 type) (according to the MIL-B-131C standard) of this cylindrical thin-film, the other end of cylindrical thin-film is fixed on the periphery that separates the discoid moving head of the relative experimental engine of 17.8cm (7 inches) with fixed head.Then, make moving head on the fixed head direction, along 440 ° of the rotations during only near 7.6cm (3.5 inches) of the axle at parallel relative two, then, do not make its rotation, behind the 6.4cm that advances (2.5 inches), its action reversed is carried out, make moving head return original position, a such on-cycle bending test is carried out 3000 circulations continuously repeatedly with per minute 40 on-cycle speed.Then, count except that the part that is fixed in fixed head and moving head periphery of test film pinhole number (that is every 497cm, that the part in 17.8cm (7 inches) * 27.9cm (11 inches) produces 2The pinhole number of (77 sq in)).
[embodiment 2]
When forming ground floor and the 3rd layer, with the fragment A in each batch mixer, B, when D supplies with by the hopper of mixing and blending machine directly over first extruder and the 3rd extruder, the delivery volume of fragment A is set at 96.0 weight %, the delivery volume of fragment B is set at 1.0 weight %, the delivery volume of fragment D is set at 3.0 weight %, simultaneously, when forming the second layer, with the fragment A in each batch mixer, B, when D supplies with hopper directly over second extruder by mixing and blending machine, the delivery volume of fragment A is set at 96.94 weight %, the delivery volume of fragment B is set at 0.06 weight %, the delivery volume of fragment D is set at 3.0 weight %.In addition, operate similarly to Example 1, obtain polyamides mixing resin laminated film coil.Then, utilize the characteristic of the film rolling that method evaluation similarly to Example 1 obtains.Evaluation result is shown in table 5～9.
[embodiment 3]
Melt extruding the raw material fragment from first～the 3rd extruder, when forming not the tensile layer laminated sheet, adjust the discharge rate of first～the 3rd extruder, making ground floor/second layer/3'sth layer thickness ratio is 1/13/1, in addition, operate similarly to Example 1, obtain polyamine class mixing resin laminated film coil.With obtain biaxial stretch-formed after laminated film cut thinly along thickness direction, utilize electron microscope to observe, ground floor, the second layer, the 3rd layer thickness are respectively about 1 μ m, about 13 μ m, about 1 μ m.Then, utilize the characteristic of the film rolling that method evaluation similarly to Example 1 obtains.Evaluation result is shown in table 5～9.
[embodiment 4]
Utilizing poly tetrafluoroethylene (registered trade mark (RTM)) system roller behind about 2.2 times of the about 90 ℃ of longitudinal stretchings of draft temperature (first longitudinal stretching) non-stretched film that obtains of operation similarly to Example 1, utilize the ceramic roller with draft temperature about 70 ℃ with about 1.5 times of its longitudinal stretching (second longitudinal stretching).Further the sheet material with longitudinal stretching imports in the stenter similarly to Example 1 continuously, 4.0 times of about 130 ℃ of cross directional stretchs, carry out heat setting at about 213 ℃, and at the transverse relaxation processing after cooling that carries out 5.0%, two edges portion is removed in cutting, thus, the biaxially oriented film of about 15 μ m is made film 2000m continuously or more than it.The mobility scale of the film surface temperature when in addition, making film continuously similarly to Example 1.Cut similarly to Example 1 and batch by the biaxially oriented film that will obtain, obtain polyamides mixing resin laminated film coil.Then, utilize the characteristic of the film rolling that method evaluation similarly to Example 1 obtains.Evaluation result is shown in table 5～9.
[embodiment 5]
To operate the non-stretched film that obtains similarly to Example 1, carry out the two-stage longitudinal stretching similarly to Example 1.Then, import the sheet material of longitudinal stretching in the stenter continuously, 3.6 times of about 130 ℃ of cross directional stretchs, carry out heat setting at about 215 ℃, and at the transverse relaxation processing after cooling that carries out 3.0%, two edges portion is removed in cutting, thus, the biaxially oriented film of about 15 μ m is made film 2000m continuously or more than it.The mobility scale of the film surface temperature when in addition, making film continuously similarly to Example 1.Cut similarly to Example 1 and batch by the biaxially oriented film that will obtain, obtain polyamides mixing resin laminated film coil.Then, utilize the characteristic of the film rolling that method evaluation similarly to Example 1 obtains.Evaluation result is shown in table 5～9.
[embodiment 6]
During hopper directly over the raw material fragment in the batch mixer being supplied with each extruder (first～the 3rd extruder), the leaning angle of each hopper is changed to 65 °, in addition, operate similarly to Example 1, obtain polyamide-based resin mixing laminate roll.Then, utilize the characteristic of the film rolling that method evaluation similarly to Example 1 obtains.Evaluation result is shown in table 5～9.
[embodiment 7]
When forming ground floor and the 3rd layer, with the fragment A in each batch mixer, B, when D supplies with by the hopper of mixing and blending machine directly over first extruder and the 3rd extruder, the delivery volume of fragment A is set at 89.5 weight %, the delivery volume of fragment B is set at 0.5 weight %, the delivery volume of fragment D is set at 10.0 weight %, simultaneously, when forming the second layer, with the fragment A in each batch mixer, B, when D supplies with hopper directly over second extruder by mixing and blending machine, the delivery volume of fragment A is set at 89.97 weight %, the delivery volume of fragment B is set at 0.03 weight %, the delivery volume of fragment D is set at 10.0 weight %, in addition, the delivery volume with fragment D is set at 10.0 weight %.In addition, operate similarly to Example 1, obtain polyamides mixing resin laminated film coil.Then, utilize the characteristic of the film rolling that method evaluation similarly to Example 1 obtains.Evaluation result is shown in table 5～9.
[embodiment 8]
When forming ground floor and the 3rd layer, use raw material fragment E to replace raw material fragment D.In addition, when forming ground floor and the 3rd layer, with the fragment A in each batch mixer, B, when E supplies with by the hopper of mixing and blending machine directly over first extruder and the 3rd extruder, the delivery volume of fragment A is set at 94.5 weight %, the delivery volume of fragment B is set at 0.5 weight %, the delivery volume of fragment E is set at 5.0 weight %, simultaneously, when forming the second layer, with the fragment A in each batch mixer, B, when E supplies with hopper directly over second extruder by mixing and blending machine, the delivery volume of fragment A is set at 94.97 weight %, the delivery volume of fragment B is set at 0.03 weight %, the delivery volume of fragment D is set at 5.0 weight %.In addition, operate similarly to Example 1, obtain polyamides mixing resin laminated film coil.In addition, in implementing each extruder of 8, the average major diameter of thermoplastic elastomer fragment (fragment E), average minor axis, average chip length with respect to the average major diameter of each polyamide-based resin fragment (fragment A, B), average minor axis, average chip length be included in respectively ± 20% with interior scope.Then, utilize the characteristic of the film rolling that method evaluation similarly to Example 1 obtains.Evaluation result is shown in table 5～9.
[embodiment 9]
Except that using raw material fragment F replacement raw material fragment E, identical with embodiment 8, obtain polyamides mixing resin laminated film coil.In addition, in each extruder of embodiment 9, the average major diameter of thermoplastic elastomer fragment (fragment F), average minor axis, average chip length with respect to the average major diameter of each polyamide-based resin fragment (fragment A, B), average minor axis, average chip length be included in respectively ± 20% with interior scope.Then, utilize the characteristic of the film rolling that method evaluation similarly to Example 1 obtains.Evaluation result is shown in table 5～9.
[embodiment 10]
Except that using raw material fragment G replacement raw material fragment E, identical with embodiment 8, obtain polyamides mixing resin laminated film coil.In addition, in each extruder of embodiment 10, the average major diameter of thermoplastic elastomer fragment (fragment G), average minor axis, average chip length with respect to the average major diameter of each polyamide-based resin fragment (fragment A, B), average minor axis, average chip length be included in respectively ± 20% with interior scope.Then, utilize the characteristic of the film rolling that method evaluation similarly to Example 1 obtains.Evaluation result is shown in table 5～9.
[embodiment 11]
Except that using raw material fragment H replacement raw material fragment E, identical with embodiment 8, obtain polyamides mixing resin laminated film coil.In addition, in each extruder of embodiment 11, the average major diameter of thermoplastic elastomer fragment (fragment H), average minor axis, average chip length with respect to the average major diameter of each polyamide-based resin fragment (fragment A, B), average minor axis, average chip length be included in respectively ± 20% with interior scope.Then, utilize the characteristic of the film rolling that method evaluation similarly to Example 1 obtains.Evaluation result is shown in table 5～9.
[comparative example 1]
When forming not the stretching resin sheet material, do not form ground floor and the 3rd layer, and form single layer structure; When forming the second layer, during hopper fragment A, B in each batch mixer, D are supplied with second extruder by mixing and blending machine directly over, the delivery volume of fragment A is set at 96.5 weight %, the delivery volume of fragment B is set at 0.5 weight %, the delivery volume of fragment D is set at 3.0 weight %.In addition, identical with embodiment 1, obtain polyamides mixing resin laminated film coil.Then, utilize the characteristic of the film rolling that method evaluation similarly to Example 1 obtains.Evaluation result is shown in table 5～9.
[comparative example 2]
Except that using raw material fragment C to replace the raw material fragment B, all the other are operated similarly to Example 1, obtain polyamides mixing resin laminated film coil.In addition, in comparative example 2, the average major diameter of thermoplastic elastomer fragment (fragment D), average chip length with respect to the average major diameter of single polyamide-based resin fragment (fragment C), average chip length be not included in respectively ± 20% with in the interior scope.Then, utilize the characteristic of the film rolling that method evaluation similarly to Example 1 obtains.Evaluation result is shown in table 5～9.
[comparative example 3]
Except that using raw material fragment I replacement raw material fragment D, all the other are identical with embodiment 1, obtain polyamides mixing resin laminated film coil.In addition, in comparative example 3, the average major diameter of thermoplastic elastomer fragment (fragment I), average chip length with respect to the average major diameter of each polyamide-based resin sheet (fragment A, B), average chip length be not included in respectively ± 20% with interior scope.Then, utilize the characteristic of the film rolling that method evaluation similarly to Example 1 obtains.Evaluation result is shown in table 5～9.
[comparative example 4]
During except that the hopper directly over the raw material fragment in the batch mixer being supplied with each extruder (first～the 3rd extruder) leaning angle of hopper is changed into 45 °, identical with embodiment 1, obtain polyamides mixing resin laminated film coil.Then, utilize the characteristic of the film rolling that 1 identical method evaluation obtains with embodiment, evaluation result is shown in table 5～9.
[comparative example 5]
After raw material fragment A, B, D is predrying, supply with before each hopper directly over each extruder by mixing and blending machine, it was placed in each batch mixer about 5 hours, in addition, operate similarly to Example 1, obtain polyamides mixing resin laminated film coil.In addition, supply to fragment A, the B before each hopper, the water ratio of D be 800ppm all, supply to before fragment A, B of each hopper, the temperature of D all is about 30 ℃.Then, utilize the characteristic of the film rolling that method evaluation similarly to Example 1 obtains.Evaluation result is shown in table 5～9.
[comparative example 6]
Be warmed to about 100 ℃ method except that the predrying condition with raw material fragment A, B, D changes at about 4.0 hours, operate similarly to Example 1, obtain polyamides mixing resin laminated film coil.In addition, after predrying, take each fragment of specified amount in each batch mixer, measure water ratio, the water ratio of fragment A, B, D all is 1500ppm, by mixing and blending machine supply with fragment A, the B before the hopper directly over each extruder, the temperature of D all is about 85 ℃.Then, utilize the characteristic of the film rolling that method evaluation similarly to Example 1 obtains.Evaluation result is shown in table 5～9.
[comparative example 7]
Remove when raw material fragment A, B, D are supplied with by the hopper of mixing and blending machine directly over each extruder, in each hopper, do not add segregation and prevent beyond the agent, identical with embodiment 1, obtain polyamides mixing resin laminated film coil.Then, utilize the characteristic of the film rolling that method evaluation similarly to Example 1 obtains.Evaluation result is shown in table 5～9.
[comparative example 8]
Utilizing poly tetrafluoroethylene (registered trade mark (RTM)) system roller behind about 1.5 times of the about 90 ℃ of longitudinal stretchings of draft temperature (first longitudinal stretching) non-stretched film that obtains of operation similarly to Example 1, utilize the ceramic roller with draft temperature about 70 ℃ with about 2.2 times of its longitudinal stretching (second longitudinal stretching).Further the sheet material with longitudinal stretching imports in the stenter continuously, carries out cross directional stretch similarly to Example 1, carries out heat setting, and carrying out transverse relaxation processing after cooling, two edges portion is removed in cutting, thus, the biaxially oriented film of about 15 μ m is made film 2000m continuously or more than it.The mobility scale of the film surface temperature when in addition, making film continuously similarly to Example 1.Then, by the film that will obtain and embodiment 1 identical operations is cut and curl, obtain polyamides mixing resin laminated film coil.Then, utilize the characteristic of the film rolling that method evaluation similarly to Example 1 obtains.Evaluation result is shown in table 5～9.
Table 5
The characteristic of polyamide-based resin mixing laminate roll
Dynamic friction coefficient Turbidity The surface thickness
Mean coefficient of kinetic sliding friction Maximum, minimum in the dynamic friction coefficient of whole samples Dynamic friction coefficient is with respect to the fluctuation rate of mean coefficient of kinetic sliding friction *(％) Average turbidity (%) Maximum, the minimum (%) of the turbidity of whole samples Turbidity is with respect to the fluctuation rate of average turbidity *(％) Average surface roughness (μ m) Maximum, the minimum (μ m) of the roughness of surface of whole samples The surperficial relative average surface of rugosity roughly is the fluctuation rate of rugosity roughly *(％)
Embodiment 1 0.62 0.77 24.2 2.7 2.4 11.1 0.042 0.046 9.5
Embodiment 2 0.43 0.51 18.6 3.8 3.5 7.9 0.050 0.055 10.0
Embodiment 3 0.64 0.80 25.0 2.2 2.4 9.1 0.040 0.047 17.5
Embodiment 4 0.57 0.72 26.3 2.6 2.3 11.5 0.041 0.046 12.2
Embodiment 5 0.53 0.62 17.0 3.2 2.9 9.4 0.045 0.048 6.7
Embodiment 6 0.67 0.58 13.4 2.8 2.5 10.7 0.043 0.050 16.3
Embodiment 7 0.66 0.78 18.2 3.6 3.9 8.3 0.044 0.049 11.4
Embodiment 8 0.58 0.51 12.1 2.4 2.2 8.3 0.040 0.046 15.0
Embodiment 9 0.62 0.72 16.1 3.6 3.3 8.3 0.043 0.039 9.3
Embodiment 10 0.57 0.69 21.1 3.8 3.5 7.9 0.044 0.049 11.4
Embodiment 11 0.58 0.50 13.8 2.4 2.6 8.3 0.040 0.046 15.0
Comparative example 1 0.45 0.51 13.3 30.1 34.7 15.3 0.064 0.069 7.8
Comparative example 2 0.62 0.86 38.7 2.6 2.1 19.2 0.039 0.049 25.6
Comparative example 3 0.75 1.05 40.0 2.9 2.3 20.7 0.043 0.051 18.6
Comparative example 4 0.67 0.89 32.8 2.7 3.2 18.5 0.041 0.051 24.4
Comparative example 5 0.68 0.55 19.1 2.6 3.1 19.2 0.040 0.048 20.0
Comparative example 6 0.67 0.83 23.9 2.7 2.9 7.4 0.042 0.046 9.5
Comparative example 7 0.77 1.15 49.4 3.0 3.5 16.7 0.044 0.055 25.0
Comparative example 8 0.68 0.83 22.1 2.7 3.1 14.8 0.037 0.046 24.3
*Dynamic friction coefficient is with respect to the fluctuation rate of mean coefficient of kinetic sliding friction: by the big side calculating fluctuation rate of the difference with mean coefficient of kinetic sliding friction in maximum in the dynamic friction coefficient of whole samples, minimum.
*Turbidity is with respect to the fluctuation rate of average turbidity: the maximum of the turbidity by whole samples, the big side calculating fluctuation rate of the difference with average turbidity in minimum.
*Roughness of surface is with respect to the fluctuation rate of average surface roughness: the maximum of the roughness of surface by whole samples, the big side calculating fluctuation rate of the difference with average surface roughness in minimum.
Table 6
The characteristic of polyamide-based resin mixing laminate roll
Silica content Boiling water shrinkage The boiling water shrinkage direction is poor
Average silica content (%) Maximum, minimum (%) in the silica content of whole samples Silica content is with respect to the fluctuation rate of average silica content *(％) Average boiling water shrinkage (BSax:%) Maximum, minimum (%) in the maximum boiling water shrinkage of whole samples Maximum boiling water shrinkage is with respect to the fluctuation rate of average boiling water shrinkage *(％) Average boiling water shrinkage direction poor (BSad:%) Maximum, the minimum (%) of the boiling water shrinkage direction difference of whole samples Boiling water shrinkage direction difference is with respect to the fluctuation rate of average boiling water shrinkage direction difference *(％)
Embodiment 1 0.022 0.023 4.5 3.3 3.5 6.1 1.4 1.5 7.1
Embodiment 2 0.045 0.042 6.7 3.5 3.7 5.7 1.6 1.4 12.5
Embodiment 3 0.013 0.012 7.7 3.2 3.1 3.1 1.6 1.4 12.5
Embodiment 4 0.022 0.020 9.1 3.0 3.2 6.7 1.6 1.7 6.3
Embodiment 5 0.022 0.021 4.5 2.8 2.7 3.6 1.6 1.8 12.5
Embodiment 6 0.021 0.020 4.8 3.1 2.9 6.5 1.5 1.6 6.7
Embodiment 7 0.022 0.021 4.5 3.0 3.2 6.7 1.4 1.3 7.1
Embodiment 8 0.022 0.021 4.5 3.3 3.2 3.0 1.0 1.1 10.0
Embodiment 9 0.021 0.022 4.8 3.8 4.0 5.3 1.3 1.5 15.4
Embodiment 10 0.022 0.020 9.1 4.1 4.4 7.3 1.5 1.3 13.3
Embodiment 11 0.021 0.020 4.8 3.6 3.9 8.3 1.6 1.7 6.3
Comparative example 1 0.066 0.072 9.1 4.2 4.5 7.1 1.4 1.6 14.3
Comparative example 2 0.022 0.018 18.2 5.2 4.6 11.5 1.5 1.7 13.3
Comparative example 3 0.021 0.019 9.5 4.3 4.9 14.0 2.1 2.5 19.0
Comparative example 4 0.022 0.025 13.6 4.8 5.2 8.3 1.6 1.7 6.3
Comparative example 5 0.022 0.020 9.1 5.0 4.5 10.0 1.7 1.9 11.8
Comparative example 6 0.023 0.021 8.7 6.1 6.8 11.5 2.4 1.9 20.8
Comparative example 7 0.022 0.021 4.5 4.7 4.2 10.6 1.8 2.4 33.3
Comparative example 8 0.021 0.017 19.0 3.9 3.6 7.7 1.9 1.7 10.5
*Silicone content is with respect to the fluctuation rate of average silicone content: by the maximum in the silica content of whole samples, minimum in the side calculating fluctuation rate big with the difference of average silica content.
*Maximum boiling water shrinkage is with respect to the fluctuation rate of average boiling water shrinkage; Calculate fluctuation rate by the maximum in the maximum boiling water shrinkage of whole samples, the big side of minimum difference interior and average boiling water shrinkage.
*Boiling water shrinkage direction difference is with respect to the fluctuation rate of average boiling water shrinkage direction difference; Calculate fluctuation rate by the maximum in the boiling water shrinkage direction difference of whole samples, the big side of minimum difference interior and average boiling water shrinkage direction difference.
Table 7
The characteristic of polyamides mixing resin laminated film coil
Thickness Ratio of refraction
Mean thickness (μ m) The maximum of thickness, minimum (μ m) on total length Thickness is with respect to the fluctuation rate of mean thickness *(％) Mean refractive index (Nz) Maximum, minimum in the ratio of refraction of whole samples Ratio of refraction is with respect to the fluctuation rate of mean refractive index *(％)
Embodiment 1 15.05 15.92 5.8 1.507 1.515 0.5
Embodiment 2 15.07 15.94 5.8 1.508 1.503 0.3
Embodiment 3 15.05 15.87 5.4 1.511 1.506 0.3
Embodiment 4 15.07 15.94 5.8 1.509 1.502 0.5
Embodiment 5 15.05 15.87 5.4 1.511 1.505 0.4
Embodiment 6 15.10 16.30 7.9 1.509 1.516 0.5
Embodiment 7 15.03 14.13 6.0 1.514 1.508 0.4
Embodiment 8 14.96 15.49 3.5 1.510 1.517 0.5
Embodiment 9 15.01 15.92 6.1 1.510 1.519 0.6
Embodiment 10 15.03 14.01 6.8 1.512 1.507 0.3
Embodiment 11 15.02 16.10 7.2 1.510 1.516 0.4
Comparative example 1 15.08 16.01 6.2 1.508 1.499 0.6
Comparative example 2 15.08 16.02 6.2 1.507 1.512 0.3
Comparative example 3 15.03 12.96 13.8 1.502 1.518 1.1
Comparative example 4 15.11 14.25 5.7 1.507 1.500 0.5
Comparative example 5 15.08 13.53 10.3 1.509 1.516 0.5
Comparative example 6 15.05 13.76 8.6 1.505 1.514 0.6
Comparative example 7 14.99 12.88 14.1 1.502 1.514 0.8
Comparative example 8 15.07 17.35 15.1 1.510 1.498 0.8
*Thickness is with respect to the fluctuation rate of mean thickness; By the maximum of the thickness of total length, minimum in the side calculating fluctuation rate big with the difference of mean thickness.
*Ratio of refraction is with respect to the fluctuation rate of mean refractive index; Calculate fluctuation rate by the maximum in the ratio of refraction of whole samples, the big side of minimum difference interior and mean refractive index.
Table 8
The characteristic of polyamides mixing resin laminated film coil
Elastomer content Tensile modulus
Elastomeric average content (%) Maximum, minimum (%) in the elastomer content of whole samples Content is with respect to the fluctuation rate of average content *(％) Average tensile modulus (GPa) Maximum, minimum (GPa) in the tensile modulus of whole samples Tensile modulus is with respect to the fluctuation rate of average tensile modulus *(％)
Embodiment 1 2.9 2.7 6.9 1.90 2.05 7.9
Embodiment 2 2.9 2.7 6.9 1.92 2.00 4.2
Embodiment 3 2.9 3.0 3.4 1.92 2.05 6.8
Embodiment 4 2.9 2.7 6.9 1.95 2.10 7.7
Embodiment 5 2.9 2.7 6.9 1.85 2.00 8.1
Embodiment 6 3.1 2.8 9.7 1.90 2.00 5.3
Embodiment 7 10.1 9.5 5.9 1.55 1.65 6.5
Embodiment 8 5.0 5.2 4.0 2.10 2.00 4.8
Embodiment 9 4.8 4.5 6.3 1.75 1.60 8.6
Embodiment 10 5.0 4.7 6.0 1.75 1.60 8.6
Embodiment 11 4.9 5.2 6.1 2.10 1.95 7.1
Comparative example 1 3.0 2.9 3.3 1.90 1.75 7.9
Comparative example 2 2.8 2.6 7.1 2.05 1.95 4.9
Comparative example 3 3.0 1.8 40.0 1.70 1.95 14.7
Comparative example 4 2.9 3.2 10.3 1.83 2.15 17.5
Comparative example 5 2.9 2.8 3.4 1.95 1.85 5.1
Comparative example 6 3.0 3.1 3.3 1.90 2.05 7.9
Comparative example 7 2.9 2.0 31.0 1.75 1.50 14.3
Comparative example 8 3.0 2.9 3.3 2.15 2.00 7.0
*Average content is with respect to the fluctuation rate of average content; Calculate fluctuation rate by the maximum in the elastomer content of whole samples, the big side of minimum difference interior and average content.
*Tensile modulus is with respect to the fluctuation rate of average tensile modulus; Calculate fluctuation rate by the maximum in the tensile modulus of whole samples, the big side of minimum difference interior and average tensile modulus.
Table 9
Evaluation result
The bending of S word Strength under shock (kg/cm) Lamination strength (g/15mm) Lamination process Anti-pin hole is (individual/497cm 2)
Comprehensively ◎, zero, * each sample number On average Mobility scale On average Mobility scale Aviation value min.～max
Embodiment 1 ◎ ◎··18，○··3 13.8 13.0～14.1 200 190～210 ○ 3 1～5
Embodiment 2 ◎ ◎··14，○··7 13.1 12.5～13.4 210 200～220 ○ 2 0～3
Embodiment 3 ◎ ◎··16，○··5 14.1 13.4～14.5 210 190～220 ○ 3 2～5
Embodiment 4 ○ ◎··9，○··12 13.3 13.0～13.5 200 190～210 ○ 3 l～4
Embodiment 5 ○ ◎··8，○··13 14.5 13.8～14.9 240 220～250 ○ 3 0～5
Embodiment 6 ◎ ◎··18，○··3 13.5 13.1～13.9 200 190～210 ○ 3 1～5
Embodiment 7 ◎ ◎··18，○··3 12.3 12.0～13.0 170 150～180 ○ 0 0
Embodiment 8 ◎ ◎··21 12.5 12.1～12.9 230 230～250 ○ 5 3～7
Embodiment 9 ◎ ◎··19，○··2 13.9 12.6～14.3 190 180～200 ○ 3 1～5
Embodiment 10 ◎ ◎··18，○··3 13.5 13.0～14.1 170 150～180 ○ 2 1～4
Embodiment 11 ◎ ◎··16，○··5 12.0 11.5～12.3 250 220～250 ○ 5 3～7
Comparative example 1 ○ ◎··9，○··12 14.0 13.3～14.3 220 200～240 ○ 3 1～4
Comparative example 2 ○ ◎··6，○··15 13.4 12.6～13.8 200 170～250 △ 3 1～5
Comparative example 3 × ○··5，×··16 12.3 10.6～13.0 130 120～170 × 12 0～25
Comparative example 4 ○ ◎··9，○··12 13.3 12.9～13.7 210 200～230 △ 7 4～11
Comparative example 5 ○～× ◎··1，○··8，×··12 13.7 12.8～14.1 230 170～260 △ 7 2～13
Comparative example 6 ○～× ○··5，×··16 12.9 11.9～13.6 210 170～240 × 7 3～12
Comparative example 7 ○～× ○··9，×··12 12.2 10.8～13.2 150 130～170 △ 9 2～16
Comparative example 8 ○～× ◎··2，○··6，×··13 13.9 12.7～14.7 200 150～220 × 8 4～15
[effect of the film of embodiment]
According to table 5～9 as can be known, the film rolling of embodiment, roller longitudinal thickness spot on the whole is all very little, and the change of the rerum naturas such as dynamic friction coefficient under elastomeric content, tensile modulus, boiling water shrinkage, ratio of refraction, the high humidity is all little.Like this, the film rolling of the equable embodiment of rerum naturas such as elastomeric content, tensile modulus can not cause the phenomenon of S word bending, even under high humidity (75%RH), lamination process is also good, and dispersing of anti-pin hole is also little.In addition, the anti-pin hole of film of film rolling that constitutes embodiment is high, and strength under shock (obdurability), lamination strength are also high.Relative therewith, the film rolling of comparative example, roller on the whole the spot of thickness longitudinally or elastomeric content, tensile modulus, boiling water shrinkage, ratio of refraction, high humidity under the change of rerum natura such as dynamic friction coefficient all big, or anti-pin hole is discrete big, or see S word buckling phenomenon, or lamination process is bad.

Claims (29)

1. polyamides mixing resin laminated film coil, be that the polyamides mixing resin laminated film coil that a plurality of polyamide-based resin sheet laminations that will be made of the hybrid resin of polyamide-based resin and thermoplastic elastomer form is got, making its width is 0.2m～3.0m, length is 300m～30000m, and the polyamides mixing resin laminated film coil that obtains, it is characterized in that
Coiling termination 2m at the distance film cuts out portion with interior first sample that is provided with, in addition, the coiling at the distance film begins 2m with the interior portion that finally cuts out that is provided with, simultaneously, cut out the every about 100m of portion apart from first sample when sample being set cutting out portion, satisfying following important document (1) and (2):
(1) at the content of each sample that cuts out from the described respectively portion of cutting out being measured the thermoplastic elastomer composition, when the aviation value of calculating these content is average content, all the fluctuation rate of the thermoplastic elastomer component content of samples with respect to average content in ± 10% scope;
The thickness variation rate of the length direction total length of the volume that (2) batches with respect to mean thickness in ± 2%～± 10% scope.
2. polyamides mixing resin laminated film coil, be that the polyamides mixing resin laminated film coil that a plurality of polyamide-based resin sheet laminations that will be made of the hybrid resin of polyamide-based resin and thermoplastic elastomer form is got, making its width is 0.2m～3.0m, length is 300m～30000m, and the polyamides mixing resin laminated film coil that obtains, it is characterized in that
Stop 2m at the coiling of distance film and cut out portion, in addition, begin 2m with the interior portion that finally cuts out that is provided with, simultaneously, cutting out the every about 100m of portion apart from first sample when sample being set cutting out portion, satisfy following important document (3) at the coiling of distance film with interior first sample that is provided with:
(3) when each sample that cuts out from the described respectively portion of cutting out is measured the tensile modulus of film take-up direction, the aviation value of these tensile moduluses is that average tensile modulus is 1.30GPa～less than 2.50GPa, simultaneously, all the fluctuation rate of the tensile modulus of samples with respect to described average tensile modulus in ± 10% scope.
3. polyamides mixing resin laminated film coil, be that the polyamides mixing resin laminated film coil that a plurality of polyamide-based resin sheet laminations that will be made of the hybrid resin of polyamide-based resin and thermoplastic elastomer form is got, making its width is 0.2m～3.0m, length is 300m～30000m, and the polyamides mixing resin laminated film coil that obtains, it is characterized in that
Stop 2m at the coiling of distance film and cut out portion, in addition, begin 2m with the interior portion that finally cuts out that is provided with, simultaneously, cutting out the every about 100m of portion apart from first sample when sample being set cutting out portion, satisfy following important document (4) at the coiling of distance film with interior first sample that is provided with:
(4) for each sample that cuts out from the described respectively portion of cutting out, the number of pin hole all is no more than 10 when using the Gelboflex experimental engine to carry out the bending test in 3000 cycles continuously with the speed in 40 cycles of each minute.
4. as each described polyamides mixing resin laminated film coil in the claim 1～3, it is characterized in that, when each sample that cuts out from the described respectively portion of cutting out being measured maxim the omnidirectional boiling water shrinkage and is maximum boiling water shrinkage, the aviation value of these maximum boiling water shrinkages is that average boiling water shrinkage is 2%～6%, simultaneously, all the fluctuation rate of the maximum boiling water shrinkage of samples with respect to described average boiling water shrinkage in ± 2%～± 10% scope.
5. as each described polyamides mixing resin laminated film coil in the claim 1～3, it is characterized in that, each sample that cuts out from the described respectively portion of cutting out is being obtained when being boiling water shrinkage direction difference for the boiling water shrinkage of+45 degree directions with respect to length direction for the absolute value of difference of the boiling water shrinkage of-45 degree directions with respect to length direction, the aviation value of these boiling water shrinkage direction differences is that average boiling water shrinkage direction difference is no more than 2.0%, simultaneously, all the fluctuation rate of the boiling water shrinkage direction difference of samples with respect to described average boiling water shrinkage direction difference in ± 2%～± 30% scope.
6. as each described polyamides mixing resin laminated film coil in the claim 1～3, it is characterized in that each sample that cuts out from the described respectively portion of cutting out satisfies following important document (5) and following important document (6):
(5) when measuring the three-dimensional surface roughness of take-up direction, the aviation value of these three-dimensional surface roughness is that average surface roughness is in the scope of 0.01～0.06 μ m, simultaneously, all the fluctuation rate of the three-dimensional surface roughness of samples with respect to described average surface roughness in ± 5%～± 20% scope;
(6) when measuring turbidity, the aviation value of these turbidity be average turbidity in 1.0～4.0 scope, simultaneously, all the fluctuation rate of the turbidity of samples with respect to described average turbidity in ± 2% ± 15% scope.
7. as each described polyamides mixing resin laminated film coil in the claim 1～3, it is characterized in that, when each sample of cutting out from the described respectively portion of cutting out is measured dynamic friction coefficient under 23 ℃, the atmosphere of 80RH, the aviation value of these dynamic friction coefficients is that mean coefficient of kinetic sliding friction is in 0.3～0.8 scope, simultaneously, all the fluctuation rate of the dynamic friction coefficient of samples with respect to described mean coefficient of kinetic sliding friction in ± 5%～± 30% scope.
8. as each described polyamides mixing resin laminated film coil in the claim 1～3, it is characterized in that, when each sample that cuts out from the described respectively portion of cutting out is measured the content of inorganic particulate, the aviation value of these inorganic particulate content is that average content is in the scope of 0.01～0.5 weight %, simultaneously, all the fluctuation rate of the inorganic particulate content of samples with respect to described average content in ± 2%～± 10% scope.
9. as each described polyamides mixing resin laminated film coil in the claim 1～3, it is characterized in that, when each sample that cuts out from the portion of cutting out is respectively measured the ratio of refraction of thickness direction, the aviation value of these ratio of refraction is that mean refractive index is 1.500～1.520, simultaneously, all the fluctuation rate of the ratio of refraction of samples with respect to described mean refractive index ± 2% with interior scope.
10. as each described polyamides mixing resin laminated film coil in the claim 1～3, it is characterized in that, in the polyamides mixing resin laminated film that batches, near the mean grain size of the inorganic particulate of 1/3 part of the through thickness in the table each top layer is littler than near the mean grain size of the inorganic particulate of the part in addition in these top layers.
11., it is characterized in that the major component that constitutes the polyamide of polyamides mixing resin laminated film is a nylon 6 as each described polyamides mixing resin laminated film coil in the claim 1～3.
12. as each described polyamides mixing resin laminated film coil in the claim 1～3, it is characterized in that, be that the polyamides mixing resin laminated film coil that is formed by at least two kinds of different polyamide-based resin compounds is got the polyamides mixing resin laminated film coil that forms.
13., it is characterized in that polyamides mixing resin laminated film that batches and polyolefin resin film laminating form as each described polyamides mixing resin laminated film coil in the claim 1～3.
14. as each described polyamides mixing resin laminated film coil in the claim 1～3, it is characterized in that, be to extrude the polyamide-based resin of fusion from T shape mould, it is contacted with metallic roll and cool off, carry out the non-oriented flap that obtains thus biaxial stretch-formed and obtain biaxial stretch-formed polyamides mixing resin laminated film, the biaxial stretch-formed polyamides mixing resin laminated film coil that obtains is got the polyamides mixing resin laminated film coil that forms.
15., it is characterized in that, be that the polyamides mixing resin laminated film coil that stretches by the stenter pulling method is got the polyamides mixing resin laminated film coil that forms as each described polyamides mixing resin laminated film coil in the claim 1～3.
16., it is characterized in that, be that successively biaxial-oriented polyamides mixing resin laminated film coil is got the polyamides mixing resin laminated film coil that forms as each described polyamides mixing resin laminated film coil in the claim 1～3.
17., it is characterized in that, be longitudinally to get the polyamides mixing resin laminated film coil that forms with horizontal biaxial stretch-formed polyamides mixing resin laminated film coil as each described polyamides mixing resin laminated film coil in the claim 1～3.
18. as each described polyamides mixing resin laminated film coil in the claim 1～3, it is characterized in that, be the flap that will constitute under with at least 3 times multiplying power two-stage longitudinal stretching at least than the glass transition temperature+20 ℃ high temperature of described polyamide-based resin by non-oriented in fact polyamide-based resin, then, with at least 3 times multiplying power cross directional stretch, the polyamides mixing resin laminated film coil that obtains is got the polyamides mixing resin laminated film coil that forms.
19. as each described polyamides mixing resin laminated film coil in the claim 1～3, it is characterized in that, be to get the polyamides mixing resin laminated film coil that forms with having carried out after the final stretch processing polyamides mixing resin laminated film coil of heat setting.
20., it is characterized in that, be that the polyamides mixing resin laminated film coil that has carried out relaxation processes after the heat setting is got the polyamides mixing resin laminated film coil that forms as each described polyamides mixing resin laminated film coil in the claim 1～3.
21. as each described polyamides mixing resin laminated film coil in the claim 1～3, it is characterized in that, in the polyamides mixing resin laminated film that batches, added at least a in lubricant, anti blocking agent, heat stabilizer, antioxidant, antistatic additive, photostabilizer, the Dent resistance modifier.
22. as each described polyamides mixing resin laminated film coil in the claim 1～3, it is characterized in that, in the polyamides mixing resin laminated film that batches, added inorganic particulate.
23. polyamides mixing resin laminated film coil as claimed in claim 22 is characterized in that, inorganic particulate is that mean grain size is the silica particle of 0.5～5.0 μ m.
24. as each described polyamides mixing resin laminated film coil in the claim 1～3, it is characterized in that, in the polyamides mixing resin laminated film that batches, added higher fatty acid.
25. the manufacture method of the described polyamides mixing resin laminated film coil of claim 1 is characterized in that,
Comprise: melt extrude the hybrid resin that constitutes by polyamide-based resin and thermoplastic elastomer by coetrusion from a plurality of extruders, form the filming operation of the polyamides mixing resin laminated sheet material that does not stretch thus;
Longitudinally reach with the mixing resin laminated sheet material of not drawing polyamide class that will obtain in this filming operation and laterally to carry out biaxial stretch-formed biaxial stretch-formed operation,
And satisfy following important document (a)～(f):
(a) described filming operation is: melt extrude after with polyamide-based resin fragment and the mixing of thermoplastic elastomer fragment, simultaneously, add the mixing that sublimable segregation prevents agent and carries out this polyamide-based resin fragment and thermoplastic elastomer fragment;
(b) described filming operation is: polyamide-based resin fragment and themoplasticity synthetic resin fragment are mixed, and lamination has added the polyamide-based hybrid resin sheet material of 0.1～2.0 weight % inorganic particulate on top layer;
(c) described biaxial stretch-formed operation is: stretch the back along cross directional stretch in 2 stages longitudinally, simultaneously, make the stretching ratio height of the stretching ratio of the F/s that described 2 stages longitudinally stretch than subordinate phase;
(d) described filming operation is: after with polyamide-based resin fragment and the mixing of thermoplastic elastomer fragment, melt extrude from each extruder, simultaneously, each fragment that uses be shaped as oval column with the oval section that comprises major diameter and minor axis, and themoplasticity synthetic resin fragment is adjusted to average major diameter with respect to the polyamide-based resin sheet, average minor axis and average chip length, have to be included in separately ± 25% with the average major diameter in the interior scope, average minor axis and average chip length;
(e) described filming operation is: comprise using to have the operation that the funnel-form hopper melt extrudes as a plurality of extruders of raw material fragment supply unit, simultaneously, the leaning angle of described funnel-form hopper all is adjusted into and is not less than 65 degree, and the water ratio that supplies to the polyamide-based resin fragment before the described funnel-form hopper is adjusted into 800ppm～1000ppm, and the temperature that supplies to the polyamide-based resin fragment before the described funnel-form hopper is adjusted into and is not less than 80 ℃;
(f) described filming operation is: comprise and will batch the operation of cooling off on the chill roll from the polyamides mixing resin laminated sheet material that described a plurality of extruders melt extrude by coetrusion, simultaneously, in this refrigerating work procedure, the contact portion on polyamides mixing resin laminated sheet material and chill roll surface, on the whole width of polyamides mixing resin laminated sheet material, on the direction opposite, attract with take-up direction by suction device.
26. the manufacture method of polyamides mixing resin laminated film coil as claimed in claim 25, it is characterized in that, in described filming operation, by using high concentration raw material fragment, lamination has added the top layer of 0.05～2.0 weight % inorganic particulate on sandwich layer.
27. the manufacture method of polyamides mixing resin laminated film coil as claimed in claim 25, it is characterized in that the high concentration raw material fragment that uses is to have added 5 weight %～the be lower than polyamide-based resin fragment of 20 weight % inorganic particulates in described filming operation.
28. the manufacture method of polyamides mixing resin laminated film coil as claimed in claim 25, it is characterized in that, the inorganic particulate that in the polyamide-based resin sheet material that is laminated to top layer, adds, its porosity volume is 0.5～2.0ml/g, mean grain size is 1.0～5.0 μ m.
29. the manufacture method of polyamides mixing resin laminated film coil as claimed in claim 25 is characterized in that, is included in the heat treatment step that preheats operation and carry out after the longitudinal stretching operation that carries out before the longitudinal stretching operation,
These longitudinal stretching operations, the mobility scale that preheats the film surface temperature of at a point in operation and the heat treatment step are adjusted on the total length of film in the scope of mean temperature ± 1 ℃.
CNB2005101286435A 2005-06-22 2005-11-23 Polyamides mixing resin laminated film coil and method for preparing same Active CN100532091C (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102076498A (en) * 2008-04-30 2011-05-25 东洋纺织株式会社 Substrate film with modified adhesiveness and hard coat film
CN107200856A (en) * 2010-11-17 2017-09-26 尤尼吉可株式会社 Semiaromatic polyamide composition film and its manufacture method

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102076498A (en) * 2008-04-30 2011-05-25 东洋纺织株式会社 Substrate film with modified adhesiveness and hard coat film
CN102076498B (en) * 2008-04-30 2014-12-17 东洋纺织株式会社 Substrate film with modified adhesiveness and hard coat film
CN107200856A (en) * 2010-11-17 2017-09-26 尤尼吉可株式会社 Semiaromatic polyamide composition film and its manufacture method

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