CN101327646B - Manufacturing method of biaxially stretched polyamide resin - Google Patents
Manufacturing method of biaxially stretched polyamide resin Download PDFInfo
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Abstract
The invention provides a manufacturing method for biaxial extension polyamide resin. When processing the biaxial extension for the sheets which are not extended via the expander-type biaxial stretch-forming machine, the surface crystallization index measured by the full-reflection FT-IR method for the sheets which are not extended before being provided to the expander is below 1-0; the sheets which are not extended is formed by the fusing polyamide resin via a squeezer; in order to achieve the purpose, the fusing polyamide resin by the squeezer is pressed on a cooling drum at 15-30 centigrade to obtain the sheets which are not extended; the fusing polyamide resin is dipped in warm water at 30-49 centigrade for more than 5 second and dipped in warm water at 50-65 centigrade for 60-150 seconds to make the water absorbing rate as 3.0-7.0 quality%; then the method processes the simultaneous biaxial extension in the expander-type biaxial stretch-forming machine.
Description
Technical field
The present invention relates to the manufacture method of Biaxially oriented polyamide resin film.
Background technology
Use the mechanical properties excellences such as hot strength, puncture intensity, pin hole intensity, impact strength of the Biaxially oriented polyamide resin film of nylon 6 grades, and gas barrier property, excellent heat resistance, therefore be widely used as food and other packaging material film.The manufacture method of biaxially-stretched film has the periosteum pulling method and uses the planar stretch method of expander, carries out the biaxial stretch-formed one by one method of horizontal stretching (or opposite) when the planar stretch method has stretching simultaneously in length and breadth of pair film after biaxial stretch-formed method and vertical the stretching.
In above-mentioned manufacture method, biaxial stretch-formed method of plane formula while is carried out biaxial stretch-formed method as the polyamide that crystallinity is high and is fit to.
Yet the fracture of film perhaps can take place owing to compare the mechanism complexity with pulling method one by one in plane formula simultaneously biaxial stretch-formed method sometimes in stretching process, the infringement operability, and have problems.
As the method for the operability that improves polyamide resin, propose in the TOHKEMY 2001-030352 communique: with all even the cooling fully of drum cooler is important, for this rotary speed to the follow-up guide roller that is connected in drum cooler is regulated.
Disclose in the TOHKEMY 2000-326402 communique: the temperature that will draw the drum cooler of the polyamides resin that is melt extruded is controlled to be alap temperature (15 ℃), obtain non-oriented in fact not stretched polyamide film, and come resin is plastified by the damping of in 20～80 ℃ warm water tank, carrying out below 10 minutes, when stretching, the stretching ratio of anchor clamps retained part is controlled simultaneously, thereby the film fracture is suppressed at 1 time/week can be with operation the time.
In TOHKEMY 2000-254966 communique and the TOHKEMY 2001-047508 communique, as the rise method of the generation that causes tension failure of the temperature that suppresses film end when stretching, the method that the temperature at the position that utilizes expander clamping film is controlled is proposed.
All methods of putting down in writing in the above-mentioned Japan special permission communique all are after the temperature that reduces drum cooler as much as possible obtains not drawing sheet, the two ends of clamping film, under than the high slightly temperature of the glass transition temperature of polyamide, in expander, carry out the method that vertical and horizontal stretch simultaneously.
Summary of the invention
But, wish the raising of operability more and more strongly from the needs of the aspect that reduces cost, it is not much of that tension failure reaches the level in 1 time/week, requires to reach than a week tension failure taking place still in long 1 day.But the number of times that the stretching inequality of end is controlled for minimizing tension failure during as mentioned above only to stretching is limited.That is, for method in the past, in a week (promptly 7 days, just 168 hours) this power lifetime unit, the fracture frequency when further reducing stretch processing is difficult.
The present invention will solve problem as described above exactly, provides can make when stretching to reach manufacture method more than the week, Biaxially oriented polyamide resin film the power lifetime till the film fracture takes place.
In order to address this is that, the inventor furthers investigate, found that: when the surface crystallization index that will obtain with the total reflection FT-IR method of passing through of the not drawing sheet before the anchor clamps clamping of biaxial stretch-formed machine of expander formula while is controlled to be specific value, breaks in the stretching process just reduce, thereby have finished the present invention.
That is to say that main points of the present invention are as follows.
(1) manufacture method of Biaxially oriented polyamide resin film, it is characterized in that, biaxial stretch-formed when obtaining biaxially-stretched film by using the biaxial stretch-formed machine of expander formula that drawing sheet is not carried out the while, making the total reflection FT-IR method of passing through that is provided to expander not drawing sheet before measure the surface crystallization index that obtains is below 1.0, and described not drawing sheet is to be formed by the polyamide through the extruder heating and melting.
(2) as the manufacture method of the Biaxially oriented polyamide resin film of (1), it is characterized in that, to be squeezed in through the polyamide of extruder heating and melting on 15～30 ℃ the drum cooler and the not drawing sheet that obtains, be immersed in 30～49 ℃ the warm water more than 5 seconds, being immersed in 50～65 ℃ the warm water 60～150 seconds again and making water absorption rate is 3.0～7.0 quality %, and being provided to the expander formula then, to carry out the while simultaneously in the biaxial stretch-formed machine biaxial stretch-formed.
As the manufacture method of the Biaxially oriented polyamide resin film of (1), it is characterized in that (3) it is 0.4～1.0 that the total reflection FT-IR method of passing through that is provided to the not drawing sheet before the expander is measured the surface crystallization index that obtains.
As the manufacture method of the Biaxially oriented polyamide resin film of (1), it is characterized in that (4) polyamide contains the above nylon 6 of 95 quality %.
(5) as the manufacture method of the Biaxially oriented polyamide resin film of (1), it is characterized in that the thickness of resulting polyamide resin is 10～30 μ m.
According to the present invention, can avoid in the stretching process when can be provided in Biaxially oriented polyamide resin film and making breakage problem generation, make and reach a week above steady production power lifetime and become the manufacture method of possible biaxial stretching polyamide film, can be used as up to now very effectively solution of fracture often take place when stretching.
The specific embodiment
Below, the present invention is described in detail.
Polyamide of the present invention is meant to have amido link (thermoplastic high molecular compound CONH-) in the molecule.For example, can enumerate nylon 6, nylon 66, NYLON610, nylon 612, nylon 11, nylon 12, nylon 46, nylon 1010, poly-hexamethylene terephthalamide (nylon 6T), poly-6I hexamethylene isoterephalamide (nylon 6I) etc.In addition,, comprise also that the reactant that makes hexamethylene diamine and adipic acid or M-phthalic acid carries out copolymerization and the copolyamide that forms as other composition, and the poly hexamethylene adipamide m-xylene diamine that forms by m-xylene diamine (metaxylenediamine) and adipic acid.In addition, also can be their mixture etc.In these materials, consider from productivity ratio, film properties and cost performance aspect, preferred nylon 6, special preferred polyamide resin contains the above nylon 6 of 95 quality %.
Generate monomer when suppressing fusion, more preferably these polyamides contain monocarboxylic acids such as organic ethylene oxidic ester, dicarboxylic anhydride, benzoic acid, diamines etc. as end-capping reagent.
The relative viscosity of above-mentioned polyamide has no particular limits, but the relative viscosity of preferably measuring under the condition of sulfuric acid as solvent, 25 ℃ of temperature, concentration 1g/dl of use 96% is 1.5～5.0.More preferably 2.5～4.5, more preferably 3.0～4.0.During this relative viscosity less than 1.5, the mechanical characteristic of film obviously reduces easily.In addition, surpass at 5.0 o'clock, the system film to film impacts easily.
As required, film properties is not being caused in the dysgenic scope, can in these polyamides, add one or more various additives such as pigment, antioxidant, ultra-violet absorber, anticorrisive agent, antistatic additive, inorganic particles.
In addition, in order to improve the resistance to blocking of film, also can cooperate one or more various mineral-type lubricants or organic series lubricant agent.As these lubricants, can enumerate clay, talcum, mica, calcium carbonate, zinc carbonate, wollastonite, silica, aluminium oxide, magnesia, calcium silicates, sodium aluminate, calcium aluminate, Almasilate, hollow glass bead (glass balloon), zinc oxide, antimony trioxide, zeolite, kaolin, hydrotalcite, phyllosilicate, stearmide, Shan Yu acid amides, sinapic acid acid amides, ethylenebisstearamide, phenolic resins, melmac, plexiglass etc.
In the present invention, biaxial stretching polyamide film can be made by the following method.
Put it briefly, for example with extruder with Amilan polyamide resin composition heating and melting under the temperature more than the fusing point, be extruded into sheet by slit-shaped mouth moulds such as T type mouth moulds.Then, by air knife casting method, air nozzle method, add known casting method such as static casting method, making its surface temperature that sticks to rotation is to carry out cooling curing on 15～25 ℃ the drum cooler surface, thus drawing sheet system film not.Again with the stretching-machine of expander formula to this not drawing sheet carry out stretch processing, thereby obtain biaxial stretching polyamide film.
In the manufacture method of biaxial stretching polyamide film of the present invention, reach power lifetime more than the week in order to make, promptly do not produce because of film fracture institute causes the steady production of problem to become possibility in order to make, must make the surface crystallization index of measuring when being provided to before not drawing sheet of expander by total reflection FT-IR method is below 1.0 on the whole width of roll.Surpass 1.0 part if produce this surface crystallization index, the frequency gets higher that then ruptures, the possibility that fracture takes place in the power lifetime unit in a week becomes high.If surpass 1.5, then for example can rupture more than 4 times in one day.If surpass 2.0, then fracture is frequent takes place, the productivity ratio extreme difference that becomes.
Total reflection FT-IR method is meant from film side-irradiation infrared ray, the forming and the method for crystalline state etc. of the absorption spectromtry film that obtains by the total reflection light by the film surface.According to this method, by obtaining not drawing sheet at 1199cm
-1Neighbouring peak crystallization and 1169cm
-1Near the ratio at noncrystalline peak, can obtain the crystallization index on film surface.This numerical value is high more, represents high more crystalline state.
If the surface crystallization index when measuring by total reflection FT-IR method is below 1.0, mean that then unstretching film becomes the low state of crystallinity, have the biaxial stretch-formed performance of being fit to.Therefore, be week situation above, that be difficult for taking place fracture power lifetime in the time of can being implemented in stretch processing.
If the surface crystallization index when measuring by total reflection FT-IR method surpasses 1.0, then become the high state of crystallinity, if produce such part, the position of fracture easily appears in width or length direction at film during then biaxial stretch-formed the processing, and the result just is easy to generate the film fracture.
Surface crystallization index when measuring the sheet be provided to before the expander in order to make by total reflection FT-IR method reaches below 1.0, for example must carry out following such processing.
Make the sheet that melt extrudes stick to the drum cooler surface when carrying out cooling curing, the surface temperature that makes drum cooler is 15～30 ℃, implement suction two stages then and handle, thus can obtain unstretching film on whole width surface crystallization characteristic underflow 1.0, crystallinity drawing sheet not uniformly.
If the surface temperature of drum cooler surpasses 30 ℃, then the surface crystallization index of drawing sheet can not surpass 1.0, so the uneven thickness of film can become greatly certainly, ruptures easily when stretching with expander.On the other hand, during 15 ℃ of less thaies, at the surface attachment dew of drum cooler, apparent low quality appears in the film generation part albefaction after the stretching, or because of the uneven uneven thickness that produces of partially crystallizable of drawing sheet not.
Then, must apply the suction in two stages to the not drawing sheet with drum cooler cooling, curing handles.For the not drawing sheet that is provided to before the stretching-machine, be applied in 30～49 ℃ the warm water phase I suction of dipping more than 5 seconds and handle, be applied to the second stage suction treatment process of flooding in 50～65 ℃ the warm water 60～150 seconds again.Utilize this method, can obtain whole width upper surface crystallization indexes be 1.0 below, the crystallinity sheet of drawing sheet before not uniformly as stretching.In addition, according to this method, the surface crystallization index that can make drawing sheet not usually is more than 0.4.
It is to be used for the processing of crystallization controlization successfully that the suction of phase I is handled.Owing to the temperature of drum cooler is set at higher than in the past, if therefore this operation not, then the crystallization of drawing sheet can excessively not carry out, and its surface crystallization index surpasses 1.0, so the uneven thickness of film can become greatly certainly, ruptures easily when stretching with expander.30 ℃ of warm water temperature less thaies in the suction of phase I is handled or dip time less than are in the time of 5 seconds, and then the surface crystallization index of drawing sheet can not surpass 1.0 equally, and the uneven thickness of the film after the stretching becomes greatly, the fracture frequency raises.If the warm water temperature during the suction of phase I is handled surpasses 49 ℃, then can produce speckled bad order on the drawing sheet, or the membrane portions albefaction after stretching and product property is exerted an influence, or produce uneven thickness.
For will be not the water absorption rate of drawing sheet be adjusted to more than the 3.0 quality % i.e. 3.0～7.0 quality %, the water treatment of essential second stage.When 50 ℃ of the warm water temperature less thaies of second stage or the dip time less than in warm water in the time of 60 seconds, the water absorption rate less than 3.0 quality % of drawing sheet not, the plasticizing of drawing sheet is not insufficient, therefore the surface crystallization index of drawing sheet does not surpass 1.0, it is big that the uneven thickness of stretching caudacoria becomes, fracture when not only stretching increases, and also albefaction easily of the polyamide resin surface after stretching.Otherwise, when warm water temperature surpassed 65 ℃ or dip time in warm water and surpasses 150 seconds, then water absorption rate surpassed 7.0 quality %, and intensity appears in the polyamide resin after the stretching to be reduced, or the membrane portions albefaction after stretching and product property is exerted an influence, or produce uneven thickness.
For not drawing sheet by the polyamide that obtains with upper type, two ends are clamped in the clamp portion of expander, be heated to the above temperature of glass transition temperature, carry out stretch processing at the biaxially oriented of vertical and horizontal according to the mode that the area multiplying power is reached more than 9 times.Thus, can make it have the also feature of excellence of mechanical property excellences such as hot strength and pin hole performance, other gas barrier property.
After the stretch processing, implement following heat setting operation: under 150～220 ℃, film is carried out heat fixation in the expander after carrying out stretch processing, then, apply 0～10%, preferred 2～6% vertical and/or horizontal relaxation processes as required.Again through the refrigerating work procedure under 20～100 ℃ the temperature conditions, film batched be web-like.
Functional for film is given, can also handle the online coating (in-line coating) that biaxial stretching polyamide film carry out following smears: for example be used to improve with the easy bonding agent of the cementability of other film or bonding agent or printing ink etc., the antistatic additive that is used to suppress generation of static electricity, the online coating that is used to improve the various functional smears such as obstruct smears of barrier and handle.
Be used for the method that the online coating of this purpose handles and have no particular limits, for example can adopt gravure roll method, reverse roll method, air knife method, reverse gravure method, coiling rod (Mayer bar) method, reverse roll method or by their various coating methods that are combined to form.Perhaps also can adopt various spray patterns etc.
The thickness of the biaxial stretching polyamide film by method manufacturing of the present invention has no particular limits, and is preferably 10 μ m～30 μ m when being used to pack purposes.
Embodiment
By the following examples the present invention is specifically described.Also have, the evaluation method of the various rerum naturas in following embodiment, the comparative example is as follows.
(1) water absorption rate
Get the unstretching film after suction is handled, put into measuring cup, in 80 ℃ drying under reduced pressure machine dry 8 hours then, calculate water absorption rate by the mass change before and after dry.
(2) the surface crystallization index of drawing sheet not
The FT-IR device (FT-IR device IRSpectrometer SPECTRUM2000) that uses Perkin Elmer company to make is measured not drawing sheet at 1199cm with total reflection FT-IR method
-1Neighbouring peak crystallization (I1199) and 1169cm
-1Near noncrystalline peak (I1169), with I1199/I1169 as the surface crystallization index.Mensuration is on the width of film, whole width are measured every 10cm, with peak as the surface crystallization index.
(3) uneven thickness
According to JIS C-2318, the contact pin type thickness instrumentation that uses Heidenhain company to make is decided the thickness of biaxial stretching polyamide film.Mensuration is on the width of film, whole width are measured every 10cm, to be benchmark with the average thickness, be considered as well (zero) with the situation of the difference less than 5% of maximum or minimum of a value, more than 5% and the situation of less than 10% be considered as (common), the situation more than 10% is considered as bad (*).
(4) film albefaction
On biaxial stretching polyamide film, confirm to have can be by visual easy affirmation degree being considered as of albefaction part bad (*), be not be considered as good (zero) of this situation.
(5) draftability (breaks)
The breaks when production of measuring biaxial stretching polyamide film continues a week, on the expander.Between one-period the fracture number of times be 0 be considered as qualified.
The raw material that uses in following embodiment, the comparative example is as follows.
" polyamide "
In as closed reaction vessel polymeric kettle, that mixer is installed, drop into epsilon-caprolactams 100 mass parts, benzoic acid 0.12 mass parts (is 10mmol/kg with respect to epsilon-caprolactams) and water 3 mass parts, heat up, under 260 ℃ of pressure 0.5MPa, temperature, carry out polycondensation reaction.Then, after from reaction vessel, going out clearly, be cut into the section shape, it is carried out obtaining polyamide after refining, the drying.In this section, terminal carboxyl group is 44mmol/kg, and terminal amino group is 36mmol/kg, and relative viscosity is 3.1.
" masterbatch section "
In as closed reaction vessel polymeric kettle, that mixer is installed, drop into epsilon-caprolactams 100 mass parts, benzoic acid 0.12 mass parts (is 10mmol/kg with respect to epsilon-caprolactams), water 3 mass parts and inorganic particles (silica, marshy land chemical industry society system, Syloid SY-150) 6 mass parts, heat up, under 260 ℃ of pressure 0.5MPa, temperature, carry out polycondensation reaction.Then, after from reaction vessel, going out clearly, be cut into the section shape, it is carried out obtaining after refining, the drying masterbatch section of polyamide.In this section, terminal carboxyl group is 46mmol/kg, and terminal amino group is 34mmol/kg, and relative viscosity is 3.1.
Embodiment 1
Above-mentioned polyamide 96 mass parts and masterbatch 4 mass parts of cutting into slices are mixed, it is dropped in extruder, in temperature is heated to 270 ℃ machine barrel, carry out fusion, be extruded into sheet by T type mouth mould.Then, make the sheet of extruding stick to surface temperature with air knife method (air pressure 400mmAq) and be adjusted on 25 ℃ the drum cooler that imposes the hard chrome plating and carry out quenching, obtain the unstretching film that thickness is 150 μ m.
Then, handle as first suction, above-mentioned unstretching film was flooded 10 seconds in 40 ℃ warm water tank, handle as second suction, dipping is 120 seconds in 52 ℃ warm water tank.Then, import the expander formula simultaneously in the biaxial stretch-formed machine, be held in the anchor clamps, under 175 ℃ draft temperature, by vertical 3.0 times, horizontal 3.3 times to carry out the while biaxial stretch-formed.And then, in expander, apply 195 ℃ of heat fixation temperature, 3.5 seconds, the heat setting operation of transverse relaxation rate 3%, obtain the polyamide resin that thickness is 15 μ m.
The operation of so making biaxial stretching polyamide film is carried out a week double tides continuously.This moment is by measuring water absorption rate that is provided to expander not drawing sheet before and the surface crystallization index that utilizes total reflection FT-IR method once a day.In addition, be determined in the continued operation in a week breaks in the stretching process.It is the results are shown in the table 1.
[table 1]
As shown in table 1, for embodiment 1, the water absorption rate that is provided to expander not drawing sheet before is 4.2～4.5 quality %, and the surface crystallization index is in 0.64～0.76 scope in a week.
Consequently, fracture does not once take place yet in the continued operation in a week, and the albefaction of film and uneven thickness all are good.
Embodiment 2～10
With the surface temperature of drum cooler, warm water tank temperature and dip time, the warm water tank temperature of the second suction processing and the condition that dip time is set at table 1 that first suction is handled.In addition, obtain the polyamide resin that thickness is 15 μ m by the mode identical with embodiment 1.
The operation and the embodiment 1 that so make biaxial stretching polyamide film are carried out a week in the same manner double tides continuously.At this moment, equally by measuring water absorption rate that is provided to expander not drawing sheet before and the surface crystallization index that utilizes total reflection FT-IR method once a day.In addition, be determined in the continued operation in a week film thickness in the stretching process, film outward appearance and breaks.It is the results are shown in the table 1.
As shown in table 1, for embodiment 2～10, the water absorption rate that is provided to expander not drawing sheet before is 3.0～7.0 quality %, and the surface crystallization index was below 1.0 in a week.Consequently, fracture does not once take place yet in the continued operation in a week, and the albefaction of film and uneven thickness all are good.
Comparative example 1～10
With the surface temperature of drum cooler, be used for warm water tank temperature and dip time that first suction handles, be used for the condition that warm water tank temperature that second suction handles and dip time are set at table 1.In addition, obtain the polyamide resin that thickness is 15 μ m by the mode identical with embodiment 1.
When so making the operation of biaxial stretching polyamide film, measure water absorption rate that is provided to expander not drawing sheet before and the surface crystallization index that utilizes total reflection FT-IR method.It is the results are shown in the table 1.
In comparative example 1, the surface temperature of drum cooler is set at 13 ℃.Consequently, the water absorption rate that is provided to expander not drawing sheet before is 4.3 quality %, and the surface crystallization index is 0.54, but can find albefaction, the uneven thickness of film, therefore can not carry out the continued operation in a week.Also have, the surface attachment of drum cooler dew.
In comparative example 2, the surface temperature of drum cooler is set at 35 ℃.Consequently, the water absorption rate that is provided to expander not drawing sheet before is 4.3 quality %, and the surface crystallization index is that 2 fractures took place in 1.48,3 hours, therefore can not carry out the continued operation in a week.Also have,, uneven thickness occurred though do not find the albefaction of film.
In comparative example 3, the warm water tank temperature that second suction is handled is set at 35 ℃.Consequently, the water absorption rate that is provided to expander not drawing sheet before is 2.0 quality %, and the surface crystallization index is that 2 fractures took place in 1.37,3 hours, therefore can not carry out the continued operation in a week.Also have, found albefaction, the uneven thickness of film.
In comparative example 4, the warm water tank temperature that second suction is handled is set at 75 ℃.Consequently, the water absorption rate that is provided to expander not drawing sheet before is 10.0 quality %, and the surface crystallization index is 0.50, has found the albefaction of film, and uneven thickness is big, can not carry out the continued operation in a week.
In comparative example 5, the dip time in the warm water tank of the second suction processing is set at 30 seconds.Consequently, the water absorption rate that is provided to expander not drawing sheet before is 1.9 quality %, and the surface crystallization index is that 2 fractures took place in 1.84,3 hours, therefore can not carry out the continued operation in a week.Also have, found albefaction, the uneven thickness of film.
In comparative example 6, the dip time of the warm water tank that second suction is handled is set at 240 seconds.Consequently, the water absorption rate that is provided to expander not drawing sheet before is 11.5 quality %, and the surface crystallization index is 0.55, has found the albefaction of film, and uneven thickness is big, can not carry out the continued operation in a week.
In comparative example 7, the warm water tank temperature that first suction is handled is set at 25 ℃.Consequently, the water absorption rate that is provided to expander not drawing sheet before is 2.4 quality %, and the surface crystallization index is that 2 fractures took place in 1.52,3 hours, therefore can not carry out the continued operation in a week.Also have,, uneven thickness occurred though do not find the albefaction of film.
In comparative example 8, the warm water tank temperature that first suction is handled is set at 70 ℃.Consequently, the water absorption rate that is provided to expander not drawing sheet before is 4.5 quality %, and the surface crystallization index is 0.82, has found the albefaction of film, and uneven thickness is big, can not carry out the continued operation in a week.
In comparative example 9, the dip time of the warm water tank that first suction is handled is set at 3 seconds.Consequently, the water absorption rate that is provided to expander not drawing sheet before is 2.3 quality %, and the surface crystallization index is that 2 fractures took place in 1.48,3 hours, therefore can not carry out the continued operation in a week.Also have,, uneven thickness occurred though do not find the albefaction of film.
In comparative example 10, not carrying out the suction in two stages handles, only carrying out second suction handles, wherein, the warm water tank temperature is made as 52 ℃, dip time was made as 120 seconds, the water absorption rate that is provided to the not drawing sheet before the expander is 2.7 quality %, and the surface crystallization index is 1.24,2 fractures took place in 3 hours, therefore can not carry out the continued operation in a week.Also have,, uneven thickness occurred though do not find the albefaction of film.
Claims (4)
1. the manufacture method of Biaxially oriented polyamide resin film, it is characterized in that, to be squeezed in through the polyamide of extruder heating and melting on 15～30 ℃ the drum cooler and the not drawing sheet that obtains, be immersed in 30～49 ℃ the warm water more than 5 seconds, be immersed in 50～65 ℃ the warm water 60～150 seconds again and make not that the water absorption rate of drawing sheet is 3.0～7.0 quality %, and the total reflection FT-IR method of passing through that makes drawing sheet not to measure the surface crystallization index that obtains be below 1.0, drawing sheet is not provided to the expander formula to carry out the while simultaneously in the biaxial stretch-formed machine biaxial stretch-formed then.
2. the manufacture method of Biaxially oriented polyamide resin film as claimed in claim 1 is characterized in that, it is 0.4～1.0 that the total reflection FT-IR method of passing through that is provided to the not drawing sheet before the expander is measured the surface crystallization index that obtains.
3. the manufacture method of Biaxially oriented polyamide resin film as claimed in claim 1 is characterized in that, polyamide contains the above nylon 6 of 95 quality %.
4. the manufacture method of Biaxially oriented polyamide resin film as claimed in claim 1 is characterized in that, the thickness of resulting polyamide resin is 10～30 μ m.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008-085088 | 2008-03-28 | ||
| JP2008085088A JP2009234131A (en) | 2008-03-28 | 2008-03-28 | Production process of biaxially stretched polyamide resin film |
| JP2008085088 | 2008-03-28 |
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|---|---|
| CN101327646A CN101327646A (en) | 2008-12-24 |
| CN101327646B true CN101327646B (en) | 2011-02-02 |
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| CN2008101307882A Active CN101327646B (en) | 2008-03-28 | 2008-07-21 | Manufacturing method of biaxially stretched polyamide resin |
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| JP (1) | JP2009234131A (en) |
| CN (1) | CN101327646B (en) |
| HK (1) | HK1121995A1 (en) |
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| JP5599214B2 (en) * | 2010-03-31 | 2014-10-01 | ユニチカ株式会社 | Method for producing simultaneous biaxially stretched film |
| JP5858635B2 (en) * | 2011-04-13 | 2016-02-10 | 花王株式会社 | Method for predicting the crystallization index of cellulose |
| TWI803697B (en) * | 2018-10-05 | 2023-06-01 | 日商東洋紡股份有限公司 | Biaxially oriented polyamide film and roll of polyamide film |
| JP7234794B2 (en) * | 2019-05-17 | 2023-03-08 | 大日本印刷株式会社 | Exterior material for power storage device, method for producing the same, power storage device, and polyamide film |
| WO2020235534A1 (en) * | 2019-05-17 | 2020-11-26 | 大日本印刷株式会社 | Exterior material for power storage device, method for manufacturing same, power storage device, and polyamide film |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1395599A (en) * | 2000-05-30 | 2003-02-05 | 尤尼吉可株式会社 | Polyester film for metal sheet laminating, metal sheet laminated with this film, and metal vessel formed from this metal sheet |
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- 2008-03-28 JP JP2008085088A patent/JP2009234131A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1395599A (en) * | 2000-05-30 | 2003-02-05 | 尤尼吉可株式会社 | Polyester film for metal sheet laminating, metal sheet laminated with this film, and metal vessel formed from this metal sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2009234131A (en) | 2009-10-15 |
| HK1121995A1 (en) | 2009-05-08 |
| CN101327646A (en) | 2008-12-24 |
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