CN101148099B - Vapor deposition polyamide resin film and film coil using the same - Google Patents
Vapor deposition polyamide resin film and film coil using the same Download PDFInfo
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- CN101148099B CN101148099B CN2007101661158A CN200710166115A CN101148099B CN 101148099 B CN101148099 B CN 101148099B CN 2007101661158 A CN2007101661158 A CN 2007101661158A CN 200710166115 A CN200710166115 A CN 200710166115A CN 101148099 B CN101148099 B CN 101148099B
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Abstract
The present invention relates to a vapor deposition polyamides resin film acquiring various physical properties balance, physical properties excellent and long size. A vapor deposition polyamides resin film vapors deposition organic/inorganic substance at least on one side of the polyamides resin film. The polyamides resin film removed vapor deposition layer contents following (a) to (d) full conditions: (a) the ratio between the film transverse central portion thickness (T0) and end portion thickness (T1) is 0.9 to 1.1, (b) the ratio of film avulsion transmitting resistance between film longitudinal direction and horizontal direction (longitudinal avulsion transmitting resistance)/(horizontal avulsion transmitting resistance) is 0.7 to 1.3, (c) most stretching elastic moculus directional error is less than 0.5, (d) boiled water shrinkage ratio directional error is under 1.5.
Description
Technical field
The present invention relates to a kind of deposition polyamides resin film vapors deposition and used the film volume of this film, particularly relate to a kind of stacked and can be used to pack the deposition polyamides resin film vapors deposition that retort pouch (retort food) waits and use the film of this film to roll up with film of polyolefin resin.
Background technology
With nylon is the double-axle orientation polyamide resin film of main component, excellences such as tough and tensile and gas shield, anti-pin hole, the transparency, printing, therefore, as the packaging material of various food such as various liquid food, food containing water, frozen food, retort pouch, paste food, poultry meat aquatic food by extensive practicability.But in polyamide-based resin monomer, gas shield is limited, not talkative packing such as the fresh food-stuff products purposes that necessarily is suitable for.As the way of the gas shield that is used to improve polyamide series resin film, the known method that has at surperficial evaporation metal of polyamide series resin film etc.But, when the rerum natura of polyamide series resin film is inhomogeneous, the thickness of metal evaporation layer and aspect the adhesive strength of metal evaporation layer the generation deviation, and gas shield is also inhomogeneous.
Motion has a kind of method in patent documentation 1 and 2, boiling water shrinkage, the boiling water shrinkage direction of the polyamide film volume of described method before with evaporation is poor, thickness etc. is adjusted into specific number range, and regulation is not produced the evaporation double-axle orientation polyamide series resin film of S shape crimping thus to the rate of change of the length direction of these rerum naturas.
[patent documentation 1] spy opens the 2006-334781 communique
[patent documentation 2] spy opens the 2007-021771 communique
In described technology, be conceived to the deviation and the thickness of percent thermal shrinkage of the length direction of polyamide film, thus, can solve S shape edge-curl phenomenon.But, in patent documentation 1 and 2, the anisotropy of the strength and elongation of film is not mentioned.Generally in the polyamide resin membrane of lipoprotein, horizontal (width abbreviates " TD " below sometimes as) and vertical (length direction abbreviates " MD " below sometimes as) according to film has difference on the value of mechanical properties such as strength and elongation.Therefore, there is the problem of following operating position variation: when processing film being become goods such as packaging material, on product strength anisotropy, undercapacity etc. sometimes as a whole.
On the other hand, in recent years, in order to suppress the cost of evaporation operation, the evaporation processer proposes strong requirement to undressed film (former anti-Off イ Le system) manufacturer, wishes undressed film is rolled up the long size rolls of making more than the 30000m.Therefore, the polyamide film before the evaporation need be involved in a step and grow sizeization.But the rerum natura balance of more critically controlling the width of film also keeps the flatness difficulty of film equably, and the film volume that undressed film volume is made more than the 30000m is very difficult.
Summary of the invention
The present inventor concentrates on studies repeatedly to the production technology that is used to produce highly uniform deposition polyamides resin film vapors deposition volume, and the result has finished the present invention.The objective of the invention is to, a kind of deposition polyamides resin film vapors deposition of growing size is provided, the deposition polyamides resin film vapors deposition of described long size is eliminated the problem points of existing deposition polyamides resin film vapors deposition volume, obtains various physical properties balance, and physical properties excellent.
The present invention is based on following opinion and finishes, and by find and control the specific microstructure from polyamide in polyamide film, can obtain having obtained the polyamide resin membrane of lipoprotein of various physical properties balance.That is, the present inventor finds that size, distribution by the control crystallite can productivity manufacturing well obtain the deposition polyamides resin film vapors deposition of various physical properties balance, thereby finish the present invention.
That is, main points of the present invention are as described below.
(1) a kind of deposition polyamides resin film vapors deposition, it is characterized in that at least one evaporation organic/inorganic substance matter of polyamide series resin film the polyamide series resin film before the evaporation satisfies the full terms of following (a)～(d):
(a) ratio (T0/T1) of the horizontal central portion thickness (T0) of film and end portion thickness (T1) is 0.9～1.1,
(b) ratio (tear propogation resistance longitudinally)/(horizontal tear propogation resistance)=0.7～1.3 that vertically reaches film tear propogation resistance transversely of relevant film,
(c) maximum tension elastic modelling quantity direction difference is below 0.5,
(d) boiling water shrinkage direction difference is below 1.5.
As (1) described deposition polyamides resin film vapors deposition, it is characterized in that (2) there is 1～1000 crystallite from polyamide that average grain diameter is 0.1～10 μ m in the scope of 100 * 100 μ m on the pellicular front of polyamide series resin film.
As (2) described deposition polyamides resin film vapors deposition, it is characterized in that (3) particle diameter more than 70% from the crystallite of polyamide of polyamide series resin film is positioned at 0.5～1.5 times scope of the average grain diameter of aforementioned crystallite.
As each described deposition polyamides resin film vapors deposition in (1)～(3), it is characterized in that (4) the crystallization completeness of polyamide series resin film is more than 70%.
(5) a kind of manufacture method of deposition polyamides resin film vapors deposition, it is for being used for making the method for each described deposition polyamides resin film vapors deposition of above-mentioned (1)～(4), it is characterized in that, to press against from the resin sheet that the mouth mould melt extrudes on the casting roller and the air layer thickness between casting roller and resin sheet when obtaining non-stretched film is 50～220 μ m, and make non-stretched film make its suction by the pick trough more than 2 grooves that contain water temperature mutually different the 1st section and the 2nd section, simultaneously, the water temperature of the 1st section pick trough of this moment is set at the arbitrary temp in 30～50 ℃ the scope, and carry out temperature control, so that it is in the scope of aforementioned temperature ± 8 ℃, it is biaxial stretch-formed that the non-stretched film after the suction is carried out the while.
(6) a kind of deposition polyamides resin film vapors deposition volume is characterized in that each deposition polyamides resin film vapors deposition is wound into web-like in above-mentioned (1)～(4).
(7) as (6) described deposition polyamides resin film vapors deposition volume, it is characterized in that, use the polyamide series resin film that is wound into web-like of width 1～5m and length 30000m～50000m, the evaporation inorganic substances, coiling forms.
(8) a kind of deposition polyamides resin film vapors deposition volume, it is characterized in that, by being cut also again the coiling shape, the deposition polyamides resin film vapors deposition of above-mentioned (7) described deposition polyamides resin film vapors deposition volume obtains, the width of the deposition polyamides resin film vapors deposition after the cutting is 0.2～3m, and length is 500～6000m.
(9) a kind of vapor-deposited polyamide-based laminated resin film is characterized in that, each deposition polyamides resin film vapors deposition and film of polyolefin resin are laminated in above-mentioned (1)～(4).
In the deposition polyamides resin film vapors deposition of the present invention, the microstructure of the polyamide resin membrane of lipoprotein by controlling evaporation to be performed can be produced the film of the rerum natura balance excellence and the flatness excellence of vertical and horizontal.Therefore, the long sizeization in the time of can making the film volume can reduce the evaporation cost significantly.
Description of drawings
Fig. 1 is the figure of an example of the expression manufacturing installation that is used to make polyamide resin membrane of lipoprotein of the present invention.
The specific embodiment
Below, explain the present invention.
The objective of the invention is to, be conceived to from a such variable of the crystallite of polyamide, the flatness of controlling film is thus promptly rolled up the formedness of appearance, uneven thickness, intensity, rerum natura balance (deviation).
In deposition polyamides resin film vapors deposition of the present invention, implement the full terms that the preceding polyamide series resin film of evaporation satisfies following (a)～(d).
(a) ratio (T0/T1) of the horizontal central portion thickness (T0) of film and end portion thickness (T1) is 0.9～1.1,
(b) ratio (tear propogation resistance longitudinally)/(horizontal tear propogation resistance)=0.7～1.3 that vertically reaches the tear propogation resistance of film transversely of relevant film,
(c) maximum tension elastic modelling quantity direction difference is below 0.5,
(d) boiling water shrinkage direction difference is below 1.5.
To above-mentioned (a)～(d) at length describe.
Deposition polyamides resin film vapors deposition of the present invention, the central portion thickness (T0) in the thin-film width direction of the polyamide series resin film before the enforcement evaporation and the ratio (T0/T1) of end portion thickness (T1) are 0.9～1.1.When it is this scope, when processing film, obtain not having the film of sag and gauffer, in the operation of evaporation processing, stacked processing, do not produce badly, can productivity make goods well.In addition, in this film, the film of making near full width can be made goods, its productivity height.
When ratio (T0/T1) departs from 0.9～1.1 scope, can not obtain surpassing the long size film volume of 30000m.Even formed, also can add and produce sag and gauffer man-hour at evaporation.
Here, the central part in the thin-film width direction is meant along the center of thin-film width direction.The end is meant along the thin-film width direction from the film end part to terminal 10% the position for overall width of distance to the center.End portion thickness is meant the average thickness value at both ends.
Secondly, the ratio that vertically reaches the tear propogation resistance of film transversely to relevant film describes.In the present invention, the ratio that vertically reaches tear propogation resistance transversely of the polyamide series resin film before the evaporation need be (tear propogation resistance longitudinally)/(horizontal tear propogation resistance)=0.7～1.3.Be preferably 0.85～1.1.By being in this scope, become film vertically/horizontal rerum natura balance is good, and the film of excellent in dimensional stability.The good goods that reverse etc. of printing skew when its result is not produced printing and bag making and bag product.
When departing from above-mentioned scope, vertically/horizontal poor properties, poor dimensional stability.Reversing etc. of printing skew when in this film, producing printing and bag making and bag product, the fraction defective rising of bag processing.
Secondly, maximum tension elastic modelling quantity direction difference is described.With regard to tensile modulus of elasticity direction difference, with the lateral set of film is 0 °, cutting out sample by this 0 ° of direction respectively along clockwise 30 °, 60 °, 90 ° (vertically), 120 °, 150 ° direction, each sample is measured 20 ℃, during tensile modulus of elasticity during 65%RH, it is poor that the difference of its maximum and minimum of a value is set at the tensile modulus of elasticity direction.Here, tensile modulus of elasticity direction difference is that 3 surveys of the both ends of the width of film and central part are asked, and it is poor that 3 maximums are set at maximum tension elastic modelling quantity direction.
Deposition polyamides resin film vapors deposition of the present invention, the maximum tension elastic modelling quantity direction difference of the polyamide series resin film of evaporation to be performed need be for below 0.5.Preferred below 0.35, more preferably below 0.25, when being this scope, become the rerum natura balance and the excellent in dimensional stability of deposition polyamides resin film vapors deposition, and the film of various flexibility (adaptability) of operation excellences.When maximum tension elastic modelling quantity direction difference surpasses 0.5, become the film of rerum natura balance, poor dimensional stability, flexibility (adaptability) of operation reduces.
Need to prove that the tensile break strength of film also depends on the purpose of use, but is preferably more than the 180MPa at least.When it is lower than 180MPa, be easy to generate following bad: with compare as the desired intensity of polyamide resin membrane of lipoprotein, be the intensity of deficiency.
Below, boiling water shrinkage direction difference is described.Here, at thin-film width is that 2500mm is when above, to be the center in the central part of distance film set positions right respectively and left 1000mm, at thin-film width during less than 2500m, to apart from the set positions of two ends 150mm the center, on film, draw the circle of diameter 200mm, with the lateral set of film is 0 °, in direction along clockwise 45 ° and 135 °, obtain the poor of boiling water shrinkage by the diameter of a circle difference before and after the boiling water treating, it is poor that the mean value of the difference of the boiling water shrinkage that will measure in the left and right sides is set at the boiling water shrinkage direction.
Deposition polyamides resin film vapors deposition of the present invention, the boiling water shrinkage direction difference of implementing the preceding polyamide series resin film of evaporation need be for below 1.5.Be preferably below 1.25.Boiling water shrinkage direction difference brings very big influence for the edge-curl phenomenon produce when boiling water treating, as long as can be suppressed to below 1.5, and the deflection in the time of just can suppressing boiling water treating as much as possible, and can prevent the generation of S shape edge-curl phenomenon.
All satisfied aforementioned (a)～(d) over-all properties polyamide series resin film very the difficulty, but the present inventor finds, the microstructure of the polyamide series resin film before the evaporation is relevant strongly with the film rerum natura, the microstructure of control film, can make the polyamide resin membrane of lipoprotein that balance has satisfied various rerum naturas well thus, thereby finish the present invention.
Below, crystallite is described.Said crystallite among the present invention is the crystallite that utilizes observation by light microscope, and is different with the crystallite of measuring by X-ray diffraction etc. etc.
When utilizing biaxial stretch-formed legal system to make film, form the granular microstructure that also can observe with the microscopical multiple of optics sometimes.This microstructure is by adjusting the film forming condition of film, and its form changes, and manifests density, size etc. and change.
Even these crystallites apply polarised light, can not observe distinctive Ma Erte cruciform joint pattern, different with spherulitic crystal structure.In addition, have only film only indulged to stretch or horizontal stretching, can not observe granular microstructure, just form when having only the various conditions such as stretching ratio of vertical and horizontal stretching complete.Particularly can not observe in the biaxial stretch-formed method one by one, only the situation of biaxial stretch-formed method can observed its specific structure at the same time.
The polyamide resin membrane of lipoprotein carries out crystallization when stretching, crystallization is carried out orientation at draw direction.In stretching one by one, carry out crystallization when initial vertical stretchings, in the horizontal stretching thereafter, owing to carried out crystallization in vertical the stretching, so compare with indulging stretching, the degree of carrying out of crystallization is dwindled, the crystallization that has become at portrait orientation.Therefore think and do not produce granular crystallite.But, biaxial stretch-formed at the same time in owing to carry out longitudinal and transverse stretching simultaneously,, and generate granular crystallite so it has been generally acknowledged that crystallization is is center and balance is carried out well with the vertical, horizontal.
The present inventor finds that this crystallite is relevant strongly with the film rerum natura, and the microstructure of control film can be made the polyamide resin membrane of lipoprotein that balance has satisfied various rerum naturas well thus, thereby finish the present invention.
In order to obtain deposition polyamides resin film vapors deposition of the present invention, the crystallite from polyamide that need to have 1～1000 average grain diameter in the scope of 100 * 100 μ m on the pellicular front of the polyamide series resin film of evaporation to be performed be 0.1～10 μ m (below, be also referred to as " polyamide crystallite ").
As mentioned above, for the size of polyamide crystallite, needing average grain diameter is 0.1～10 μ m, is preferably 0.5～8 μ m, more preferably 1～5 μ m.Here, average grain diameter is meant, along the direction of film, to 3 points (n=4 amounts to 12 points) of both ends and central portion, to using 100 of the crystallizations arbitrarily that polarized light microscope observing crosses, longest edge is defined as particle diameter, and the mean value of the particle diameter of 100 * 12 point=1200 particle.During less than 0.1 μ m, can not stably obtain film of the present invention in average grain diameter.On the contrary, during greater than 10 μ m, mist degree increases in average grain diameter, and operability variation such as tension failure pilosity.For the optional position on the pellicular front, all need there be 1～1000 polyamide crystallite in the scope of 100 * 100 μ m, preferably there are 2～200.Thus, the flatness that can obtain film is promptly rolled up the appearance excellence, and the aspect ratio of tear propogation resistance is suitable, and the direction difference of tensile modulus of elasticity is little, has obtained the film of balance.When one of locating arbitrarily when not satisfying above-mentioned condition, can not obtain having obtained the film of balance.
In polyamide resin membrane of lipoprotein of the present invention, for more than 70% of polyamide crystallite, preferably its particle diameter is in 0.5～1.5 times the scope of average grain diameter of these crystallites.As long as in this scope, just can obtain the high polyamide series resin film of crystallization completeness height and hot strength.
The polyamide crystallite of 0.5～1.5 times scope that is positioned at the average grain diameter of polyamide crystallite is lower than at 70% o'clock, and when promptly the dispersion of particle diameter was big, the crystallization completeness reduced, and hot strength is dwindled.In addition, for more than 70% of polyamide crystallite, its particle diameter is not in 0.5～1.5 times scope of the average grain diameter of these crystallites the time, and when promptly particle diameter concentrated on path or big footpath side, the crystallization completeness reduced, and hot strength is dwindled.
Employed polyamide series resin film among the present invention is promptly implemented the preceding polyamide series resin film of evaporation, and preferred crystallization completeness is more than 70%.The crystallization completeness is following index: use the value of being obtained by following (i) formula, film is analyzed with the X-ray diffraction method, at this moment, observed crystallite (crystallization of the reality in the polyamide) forms the structure that how much approaches complete crystallization.
The crystallization completeness
＝{[d(200)/d(002)，(202)]-1}/0.211×100
(i) formula
When the crystallization completeness is 70% when above, the hot strength height of film.When the crystallization completeness less than 70% the time, film strength reduces easily.
The polyamide-based resin of Shi Yonging in the present invention, can enumerate for example is the nylon 6 of primary raw material with the epsilon-caprolactams.In addition, other polyamides can be enumerated: the polyamide that the polycondensation reaction by 3 yuan of lactams, omega-amino acid, binary acid and diamines etc. more than the ring obtains.Specifically, lactams except that before shown in epsilon-caprolactams, can enumerate: butyrolactam, oenantholcatam, spicy inner formyl amine, lauric lactam.The omega-amino-acids can be enumerated: 6-aminocaprolc acid, 7-aminoheptylic acid, 9 aminononanoic acid, 11-aminoundecanoic acid.The binary acids can be enumerated: adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid, hexadecandioic acid (hexadecane diacid), eicosane diacid, 20 carbon, two enedioic acids, 2,2,4-trimethyladipic acid, terephthalic acids, isophthalic acid, 2.6-naphthalene dicarboxylic acids, dimethylbenzene dicarboxylic acids.Two amines can be enumerated: ethylenediamine, propane diamine, tetramethylenediamine, hexamethylene diamine, pentamethylenediamine, 11 methylene diamines, 2,2,4 (or 2,4,4)-trimethyl hexamethylene diamine, cyclohexanediamine, two-(4,4 '-aminocyclohexyl) methane, m-xylene diamine etc.And, they are carried out polycondensation reaction and the polymer or their copolymer that obtain for example can use: nylon 4,6,7,11,12,6.6,6.9,6.11,6.12,6T, 6I, MXD6 (poly hexamethylene adipamide m-xylene diamine 6), 6/6.6,6/12,6/6T, 6/6I, 6/MXD6 etc.During the polyamide series resin film that in making the present invention, uses, can above-mentioned polyamide-based resin independent or mix more than 2 kinds or make multilayer and use.
In above-mentioned polyamide-based resin, particularly preferably be relative viscosity among the present invention and be the polyamide-based resin of 2.0～3.5 scope.This be because: the relative viscosity of polyamide-based resin brings influence for the obdurability of the biaxially oriented film obtain and extensibility etc., relative viscosity less than 2.0 polyamide-based resin in, impact strength has not enough tendency, on the contrary, surpass in 3.5 the polyamide-based resin in relative viscosity, along with the increase of tensile stress, biaxial stretch-formed property has the tendency of variation.In the present invention, relative viscosity is meant, uses the solution that is dissolved with polymer 0.5g in 97.5% sulfuric acid 50ml, the value when measuring down for 25 ℃.
In the polyamide series resin film that constitutes evaporated film of the present invention, in the scope that does not hinder its characteristic, also can contain various additives such as lubricant, anticlogging agent, heat stabilizer, antioxidant, antistatic additive, photostabilizer, resistance to impact modifying agent.Particularly, preferably contain various inorganic particulates in order to have the sliding of good biaxially oriented film.And, when adding the organic lubricants such as ethylenebis stearic acid of bringing into play the effect that reduces surface energy, constitute the excellent in sliding property of the film of film volume, therefore preferably.The scope of preferred 0.01～1 quality % of the addition of these lubricants.
And, in the polyamide series resin film that constitutes evaporated film of the present invention,, also can implement heat treatment and damping and handle for according to purposes improvement dimensional stability.And, in order to have the cementability on good film surface, also can implement sided corona treatment, coating processing, flame treatment etc., perhaps implement printing and wait processing.
Below, the preferred manufacture method that is used to obtain deposition polyamides resin film vapors deposition of the present invention is described.Deposition polyamides resin film vapors deposition of the present invention obtains by the following method: will melt extrude and obtain non-stretched film as the polyamide of raw material bits sheet, to its carry out biaxial stretch-formed after, make by surperficial evaporation inorganic substances at this biaxially oriented film.In the manufacturer of the undressed film situation different etc. down, behind undressed film coiling, this volume is transported to the evaporation workshop with the dealer who carries out the evaporation operation, then can be on one side with the film debatching, Yi Bian carry out evaporation.
During the polyamide series resin film that in making deposition polyamides resin film vapors deposition of the present invention, uses, preferably utilize simultaneously that biaxial stretch-formed method stretches.With the situation that biaxial stretch-formed method or inflation method one by one stretch, granular microstructure can not be observed or be considerably less.It has been generally acknowledged that to have only the granular microstructure of formation under the following situation, that is, promote the growth of crystallization by stretching, simultaneously, when crystalline growth, complete in balance and other conditions of vertical stretching and horizontal stretching.
With the manufacture method of the polyamide series resin film before the evaporation that uses in the deposition polyamides resin film vapors deposition of the present invention, use figure describes.
Fig. 1 is the process chart of the general manufacture method of drawing polyamide film.At first, to charging hopper 1 base feed resin particle, carry out the plasticization fusion with extruder 2, the resin that fusion is good is extruded into sheet by the T mouth mould 3 of the front end that is installed in extruder 2, carries out cooling curing with casting roller 4.At this moment, the temperature setting range of casting roller is set at 20～80 ℃, utilizes air that polyamide is pressed against on the casting roller, obtain non-stretched film.At this moment, for the air layer thickness between casting roller and polyamide, the end is thicker than roller central portion, but no matter gets which position, all is necessary for 50～220 μ m.Be preferably 85～190 μ m.
On the casting roller 4 that molten sheet is pressed against cooling usefulness and when carrying out cooling curing, as the method for pushing, have the two ends of the width of pair molten sheet blow the air nozzle method of air, to the whole width of molten sheet blow air the air knife method, utilize high-voltage electrode that electric charge is separated out and statically attached to the electrostatic adherence method on the molten sheet etc.Wherein, in the static driving fit method that air layer thickness does not almost have, can not manifest the polyamide crystallite.In air knife method or air nozzle method, only when the thickness of air layer is above-mentioned scope, manifest the polyamide crystallite.
During less than 50 μ m, the crystallization of the non-stretched film that obtains is spent low, does not produce crystallite at the thickness of air layer, even or produce, also be very little crystallite, therefore, the size of the polyamide crystallite of the film that finally obtains only is below the 0.1 μ m.In addition, when the thickness of air layer surpassed 220 μ m, crystallite was too grown, and produces big grain boundary, and the size of the polyamide crystallite of the film that finally obtains has surpassed 10 μ m.So, produce problems such as film albefaction.
Casting roller and the distance between drawing sheet (air layer thickness) not for example can be used laser to focus on extensometer (manufacturing of Keyence company) and measure.
Owing in oriented film, produce curved (bowing) phenomenon of bow, thus crystallization carry out the position difference of degree because of the width of oriented film.Therefore, for the rerum natura that makes width and tilted direction is even, preferably makes the size of the micro-crystallization that in being pressed to the operation of chill roll, generates and distribute final even in each position of film.For the size and the distribution of the crystallite in each position that makes film is located within the scope of the present invention, it is inadequate only controlling air layer.
Usually, non-stretched film is stretched at biaxially oriented in length and breadth simultaneously by stretching process 6 after by suction treatment process 5 shown in Figure 1, is reeled as the goods 7 of drawing polyamide film.
For the size and the distribution of the crystallite in each position that makes film is located within the scope of the present invention, need control suction treatment process.Make non-stretched film by the suction treatment process, determine the size and the distribution of crystallite thus with crystallite.Therefore, the suction treatment process is preferably implemented in the pick trough more than 2 different grooves of temperature, and the water temperature of the pick trough in the 1st stage influences the size and the distribution of crystallite.The water temperature of the pick trough in the 1st stage is set at 30～50 ℃ the interior arbitrary value of scope, need carry out temperature control in ± 8 ℃ scope.Be preferably ± 5 ℃ scope, more preferably ± 3 ℃ scope.
If 30 ℃ of the water temperature deficiencies of the pick trough in the 1st stage then hinder the growth of polyamide crystallite.On the contrary, when it surpasses 50 ℃, occur gauffer easily on non-stretched film, the quality of the oriented film that obtains descends.
When the water temperature of the pick trough in the 1st stage was according to the place difference and more than deviation ± 8 ℃, the distribution of polyamide crystallite produced deviation, and consequently, the percent thermal shrinkage of the polyamide oriented film that finally obtains, the deviation of elongation at break become big.
By after the pick trough in the 1st stage, in the pick trough after water temperature being set at the 2nd stage of 40～90 ℃, the moisture rate of film is adjusted to 2～10 quality %.And, import biaxial stretch-formed machine simultaneously, stretch vertical 2～5 times, horizontal 2～5 times scopes, and be that the scope 0.1～10% was carried out relaxation processes, can obtain desired film after 180～240 ℃ scope was heat-treated at design temperature.
The polyamide series resin film that obtains like this is wound into web-like, constitute the film volume, but do not have uneven thickness, and the poor properties in vertically reaching laterally is little, and rerum natura balance excellence all has close rerum natura in which direction, which position of film.And, can grow size rollsization, the width that therefore also can make film is that 1～5m, length are the film of 30000m～50000m.Therefore, can reduce the cost of the evaporation operation of conduct back operation significantly.
Stacked inorganic evaporation layer on polyamide series resin film, this inorganic evaporation layer is given high gas shield to the deposition polyamides resin film vapors deposition that obtains.Material with inorganic matter evaporation layer of this effect can be enumerated: metal such as Si, Al, Ti, Zn, Zr, Mg, Sn, Cu, Fe and their oxide, nitride, fluoride, sulfide etc.Particularly can illustration: SiOx (x=1.0～2.0), aluminium oxide, magnesia, zinc sulphide, titanium dioxide, zirconia, cerium oxide or their mixture.Inorganic evaporation layer can be 1 layer, or also can be the duplexer more than 2 layers.Preferred 5～the 500nm of the thickness of inorganic evaporation layer, more preferably 5～200nm.During less than 5nm, worry can not obtain sufficient gas shield at thickness.On the contrary, when it surpasses 500nm, can not produce the raising effect of the gas shield suitable with it, in addition, resistance to bend(ing) reduces, and unfavorable aspect manufacturing cost.
The formation method of inorganic evaporation layer can adopt chemical vapor deposition methods such as physical vapor depositions such as known method, for example vacuum vapour deposition, sputtering method, ion plating method and PECVD etc.
In vacuum vapour deposition, deposition material uses compound and their mixtures such as Al, Si, Ti, Mg, Zr, Ce, Zn etc., SiOx (x=1.0～2.0), aluminium oxide, magnesia, zinc sulphide, titanium dioxide, zirconia.Heating means adopt resistance heated, induce heating, the heating of electronics line etc.Reacting gas uses oxygen, nitrogen, hydrogen, argon, carbon dioxide, steam etc.Also can adopt the reactive vapour deposition method of ways such as having used that interpolation ozone, ion are assisted.And, also can adopt to polyamide series resin film apply bias voltage or with the polyamide resin membrane of lipoprotein heat, method such as cooling.Above-mentioned deposition material, reacting gas, bias voltage apply, heats cold can be used in sputtering method, CVD method also.Need to prove, between metal evaporation layer and polyamide series resin film, tackifier coating (anchor coat) can be set also as required.
The oxygen permeability of deposition polyamides resin film vapors deposition of the present invention, the viewpoint of the gas shield when making goods is considered, is preferably 50ml/m
2Below the MPaday, 40ml/m more preferably
2Below the MPaday, be preferably 30ml/m especially
2Below the MPaday.
Deposition polyamides resin film vapors deposition of the present invention does not have uneven thickness, and the poor properties in vertically reaching laterally is little, and rerum natura balance excellence all has close rerum natura in which direction, which position of film.And, can grow size rollsization, the width that therefore also can make film is that 1～5m and length are the film of 30000m～50000m.
Deposition polyamides resin film vapors deposition of the present invention, the film unwinding on one side that will have the film volume of this thin-film width and film length usually, cutting on one side, again be wound into web-like, the width of the film that can for example be cut into is that 0.2～3m and length are the other film volume of 500～6000m thus.
Deposition polyamides resin film vapors deposition of the present invention can be stacked and constitute vapor-deposited polyamide-based laminated resin film with film of polyolefin resin.This stacked resin film, stacked processability is good, and the bag processability is good.By the bag that this stacked resin film obtains, the gas shield excellence, and anisotropy is few on product strength, does not show S shape edge-curl phenomenon.Therefore, go for the sterilization processing purposes of food.
Embodiment
Below, utilize embodiment to specifically describe the present invention.
The assay method of the various rerum naturas in the following examples comparative example is as described below.Need to prove that any is measured all is that test film is implemented after 2 hours in placement under the environment of 20 ℃ of temperature, relative humidity 65% under the environment of 20 ℃ of temperature, relative humidity 65%.
[observation of microstructure]
Along the width of film, for the part at both ends and 3 places of central portion, film sample is cut into the foursquare shape of 50cm * 50cm, the point (4 point) that enters distance four corner 5cm inboards on the diagonal of this sample is amounted at 12 measure.
To point of observation separately, use polarization microscope to observe with 100～400 times multiple.To any 100 crystallizations of observing, stipulate particle diameter according to its longest granular limit, and its mean value is set at average grain diameter.
The number of crystallite is obtained by the granular crystallite in the scope of any 100 * 100 μ m among 12 of aforementioned pellicular front is counted, as every mm
2Number promptly have density (* 10
2Individual/mm
2) manifest.At this moment, because crystallite also exists in film inside,, observed crystallite is there counted so make any 1 point of the microscopical direction of film thickness in focus.
By any 100 crystallizations of observing being calculated in 0.5～1.5 times the scope of the average grain diameter whether particle diameter more than 70% of judging crystallite is crystallite.
[uneven thickness of film]
Used thickness meter MT-12B (manufacturing of HEIDENHAIN company) has measured thickness.That is, to film laterally be the thin-film width direction, measured central part and be center (T0) and end promptly from end to the center thickness (mean values at T1, both ends) to the part of terminal 10% the position for overall width of distance.And T0/T1 obtains uneven thickness by ratio, and it is qualified that this ratio is that 0.9～1.1 situation is set at.
[tear propogation resistance]
Use AutographAG-1 (manufacturing of company of Shimadzu Seisakusho Ltd.) to measure, use unit (cell) to be 100kg or 5kg, test speed is 200mm/min.Test film is an oblong-shaped, and width is 25mm, and length is 75mm, cuts the slit of 50mm along its length at the center of 25mm width.Test film film vertically and laterally respectively make 5 points, ask for the mean value of the measured value of relevant each test film, and ask for the film ratio of the horizontal mean value of mean value and film longitudinally.
[the tensile modulus of elasticity direction is poor]
Use AutographAG-1 (manufacturing of company of Shimadzu Seisakusho Ltd.) to measure tensile modulus of elasticity.Test film is the oblong-shaped of width 10mm, length 150mm, uses the unit to be 100kg, and test speed is 500mm/min, and chuck is spaced apart 100mm.
About tensile modulus of elasticity, be that width (laterally) section 5 samples that go out that test film is parallel to film are measured tensiles modulus of elasticity to measuring sample, its mean value is set at 0 ° data.Similarly, cutting out test film respectively, measured tensile modulus of elasticity by horizontal edge clockwise 30 °, 60 °, 90 ° (vertically), 120 °, 150 ° direction.And it is poor that the difference of the maximum of the tensile modulus of elasticity relevant with all directions and minimum of a value is set at the tensile modulus of elasticity direction.
Tensile modulus of elasticity direction difference amounts to the position at 3 places and obtains in thin film center portion and film end, 2 place, it is poor that the value of maximum is set at maximum tension elastic modelling quantity direction.
[the boiling water shrinkage direction is poor]
Test film is made by the following method: cut out the square of 5 210 * 210mm abreast with the width of film, the central authorities with sample are the center respectively, draw the circle of the about 200mm of diameter.In this test film, be 0 ° with the lateral set of film, draw by straight line, with the distance L 0 between two intersection points of straight line and circle along clockwise 45 ° position and center
45Length before the processing when being set at 45 °.Then, similarly, draw, with the distance L 0 between two intersection points of straight line and circle by straight line along clockwise 135 ° position and center
135Length before the processing when being set at 135 °.
5 test films are measured L0
45And L0
135, then, in boiling water, handled 5 minutes, dab off carry out behind the moisture air-dry, further in the placement environment of 20 ℃ * 65%RH under more than 2 hours.
After the boiling water treating again with the distance L 1 between above-mentioned 45 ° locational two intersection points
45Length after the processing when being set at 45 °.Similarly, with the distance L 1 between locational two intersection points of 135 °
135Length after the processing when being set at 135 °.And, obtain the boiling water shrinkage of the position of 45 ° the boiling water shrinkage of position and 135 ° by following formula, absolute value of its difference is set at the poor of boiling water shrinkage.
Length (%) before boiling water shrinkage=handle (length after the length-processing before handling) * 100/
At thin-film width is that 2500mm is when above, obtain the poor of separately boiling water shrinkage for the horizontal central part of distance film position right respectively and left 1000mm, in addition, at thin-film width during less than 2500mm, obtain the poor of separately boiling water shrinkage for the position of distance edges at two ends 150mm, it is poor that the mean value of right-hand member and left end is set at the boiling water shrinkage direction.
[crystallization completeness]
Use wide-angle X line scattering method to measure.That is, use Rad-X type X-ray diffraction device (of science motor company make) to measure, use CuK α line as line source.75 of the film overlaies of the 3 * 3cm that will cut out from film are used as sample.About (002) face, utilize bounce technique to measure the X-ray diffraction peak value with output 50kV, 50mA, calculate interplanar every d (002).About (200) face, with 67.5 ° of sample rotations, utilize transmission beam method to measure the X-ray diffraction peak value with output 50kV, 50mA, calculate interplanar every d (200).
Crystallization completeness (%) is calculated according to following (i) formula.
The crystallization security
＝{[d(200)/d(002)，(202)]-1}/0.211×100
(i) formula
Thin film center portion and both ends are carried out the complete mensuration of crystallization, their mean value is set at the crystallization completeness of this film.
[volume appearance]
State to the volume of the Biaxially oriented polyamide based resin film before the evaporation of the specific length of only having reeled is observed, according to following standard evaluation the volume appearance of gauffer etc.
◎: even coiling 50000m does not have gauffer yet, the volume appearance is good.
Zero: the volume appearance is good during coiling 30000m, but when coiling 50000m, has produced gauffer and sag.
*: when coiling 30000m, produced gauffer and sag.
* *: gauffer and sag are obvious, and 30000m can not reel.
[S shape edge-curl phenomenon]
With Biaxially oriented polyamide resin film before the evaporation and sealant film (CP; Tohcello company makes no stretched polypropene film, RX-21, thickness 40 μ m), using the ammonia ester is that bonding agent (the military field manufacturing TAKERACK A-525/A-52 of pharmaceutical industries company two-liquid type) carries out stacked (the adhesive applicating amount 3g/m of dry type
2), made laminate film thus.
The laminate film that obtains is folded into 2 in the mode that forms folding line longitudinally, the service test encapsulant carries out heat seal continuously with the every 20mm of two edges portion, under 180 ℃ simultaneously, in addition, at interval width 10mm is carried out heat seal continuously in direction rectangular with 150mm, obtain the semi-finished product bag of the about 200mm of width with it.This semi-finished product bag is vertically being cut off,, then,, made 10 three limit sealing bags in perpendicular direction, in the cut-out of the border of sealing so that the hermetic unit of two edges portion is 10mm.With the heat treatment after 30 minutes in boiling water of these three limits sealing bags, under 20 ℃, the environment of 65%RH, keep diel, and then it is these 10 three limit sealing bags are overlapping, from the last loading that the whole face of bag is applied 1kg, keep taking down loading behind the diel, observed the degree of the bending (S shape crimping) of bag.And, estimate according to following standard.
◎: 10 all do not have bending
Zero: have and see crooked bag a little
*: have and obviously see crooked bag
[oxygen permeability]
It carries out the oxygen displacement through 2 angels under the environment of 20 ℃ of temperature, humidity 65%RH with the film behind the evaporation.According to JIS-K-7126 (B method), use oxygen permeability determinator (OX-TRAN2/20:MOCOM company manufacturing) measure thereafter.
The making of＜masterbatch sheet (master chip) 〉
The relative viscosity that to measure in 95% concentrated sulfuric acid, under the condition of 25 ℃ of temperature, concentration 0.5g/dl is that 3.0 nylon 6 resin (UNITIKA company makes, A1030BRF) carries out drying, melting mixing 6 mass parts silica in every this 100 mass parts (サ イ ロ イ De SY-150: Suisawa Chemical Industry Co., Ltd. makes) have been made the masterbatch sheet.
Embodiment 1
Nylon 6 resin that drying is good (manufacturing of UNITIKA company, A1030-BRF) and above-mentioned masterbatch sheet mix, the cooperation ratio that makes silica is 0.05 quality %, put into extruder, fusion in temperature is heated to 270 ℃ cylindrical shell, be extruded into sheet by T mouth nib, utilization is set at it casting roller of 40 ℃ and cools off to pushing from the air of nozzle ejection, obtains the non-stretched film of thickness 180 μ m.After distance between casting roller and the non-stretched film (air layer thickness) used laser to focus on extensometer (manufacturing of Keyence company) to measure, minimum of a value was 92 μ m, and maximum is 157 μ m.
Then, this non-stretched film be impregnated at ± 5 ℃ down in the water of the 1st pick trough of 45 ℃ of the water temperatures of control, in the 2nd pick trough of 60 ℃ of water temperatures, make it moisture then, moisture rate is adjusted to 6 quality %.Then, it is imported biaxial stretch-formed machine simultaneously, and after 175 ℃ of following preheatings, under 190 ℃ of draft temperatures, stretch with vertical 3.5 times, horizontal 3.3 times multiple.Then,, carry out 3% relaxation processes then, obtain nylon 6 films of thickness 15 μ m under 220 ℃ of the temperature, between film mobile process 3m, heat-treat.The film that obtains is wound into web-like with winding speed 130m/ minute, obtains the film volume.Uneven thickness, the maximum tension elastic modelling quantity direction of the state of the crystallite of the nylon film of creating conditions, obtaining of film (exist number, average grain diameter, particle diameter in the prescribed limit are positioned at ratio, the crystallization completeness of crystallite of 0.5～1.5 times scope of average grain diameter), the nylon film that obtains is poor, the boiling water shrinkage direction is poor, the ratio of tear propogation resistance, the measurement result of rolling up appearance, S shape edge-curl phenomenon are shown in table 1～table 3.
The locational tensile modulus of elasticity of each of the nylon film that obtains is as shown in table 4, and maximum tension elastic modelling quantity direction difference is 0.22.
[table 1]
| Manufacture method | The volume appearance | ||||||
| The casting roller temperature (℃) | The thickness of air layer | The 1st pick trough | Drawing process | ||||
| Minimum (μ m) | Maximum (μ m) | Temperature (℃) | Span of control limit of control (℃) | ||||
| Embodiment 1 | 40 | 92 | 157 | 45 | ±5 | Stretch simultaneously | ◎ |
| Embodiment 2 | 40 | 90 | 161 | 30 | ±5 | Stretch simultaneously | ◎ |
| |
40 | 89 | 165 | 45 | ±3 | Stretch simultaneously | ◎ |
| Embodiment 4 | 40 | 103 | 185 | 45 | ±5 | Stretch simultaneously | ◎ |
| Embodiment 5 | 40 | 61 | 154 | 45 | ±5 | Stretch simultaneously | ○ |
| Embodiment 6 | 20 | 92 | 187 | 45 | ±5 | Stretch simultaneously | ◎ |
| |
30 | 99 | 174 | 45 | ±5 | Stretch simultaneously | ◎ |
| Comparative example 1 | 40 | 92 | 155 | 45 | ±10 | Stretch simultaneously | × |
| Comparative example 2 | 40 | 25 | 157 | 45 | ±5 | Stretch simultaneously | × |
| Comparative example 3 | 60 | 10 | 55 | 45 | ±5 | Stretch simultaneously | × |
| Comparative example 4 | 15 | 61 | 154 | 45 | ±5 | Stretch simultaneously | × |
| Comparative example 5 | 40 | 103 | 185 | 65 | ±5 | Stretch simultaneously | ×× |
| Comparative example 6 | 40 | 130 | 250 | 45 | ±5 | Stretch simultaneously | × |
| Comparative example 7 | 20 | 10 | 15 | - | - | Stretch one by one | ○ |
[table 2]
| Crystallite | Crystallization completeness (%) | ||||||||
| There is density (* 10 2Individual/mm 2) | Average grain diameter (μ m) | There is ratio (%) | |||||||
| The position | Measured value (individual) | On average (individual) | |||||||
| Embodiment 1 | Right-hand member | 19 | 27 | 92 | 69 | 37.3 | 4 | 85 | 82 |
| Central authorities | 8 | 73 | 13 | 18 | |||||
| Left end | 30 | 11 | 21 | 66 | |||||
| Embodiment 2 | Right-hand member | 45 | 29 | 26 | 55 | 32.2 | 4 | 91 | 91 |
| Central authorities | 20 | 39 | 4 | 13 | |||||
| Left end | 16 | 28 | 33 | 41 | |||||
| Embodiment 3 | Right-hand member | 89 | 25 | 26 | 40 | 42.9 | 4 | 84 | 84 |
| Central authorities | 56 | 15 | 23 | 49 | |||||
| Left end | 48 | 36 | 75 | 33 | |||||
| Embodiment 4 | Right-hand member | 92 | 88 | 75 | 79 | 68.6 | 3 | 77 | 75 |
| Central authorities | 53 | 64 | 33 | 87 | |||||
| Left end | 35 | 69 | 88 | 60 | |||||
| Embodiment 5 | Right-hand member | 190 | 175 | 116 | 146 | 153 | 3 | 71 | 74 |
| Central authorities | 155 | 185 | 131 | 127 | |||||
| Left end | 61 | 123 | 129 | 135 | |||||
| Embodiment 6 | Right-hand member | 5 | 5 | 4 | 8 | 9.5 | 1 | 81 | 88 |
| Central authorities | 9 | 3 | 7 | 12 | |||||
| Left end | 15 | 6 | 11 | 29 | |||||
| Embodiment 7 | Right-hand member | 12 | 30 | 19 | 22 | 18.8 | 8 | 74 | 74 |
| Central authorities | 19 | 10 | 14 | 12 | |||||
| Left end | 22 | 11 | 20 | 35 | |||||
| Comparative example 1 | Right-hand member | 32 | 16 | 12 | 29 | 27.1 | 9 | 48 | 66 |
| Central authorities | 0 | 31 | 0 | 22 | |||||
| Left end | 74 | 26 | 61 | 22 | |||||
| Comparative example 2 | Right-hand member | 88 | 31 | 61 | 89 | 39.9 | 3 | 62 | 61 |
| Central authorities | 1 | 0 | 0 | 0 | |||||
| Left end | 74 | 26 | 61 | 48 | |||||
| Comparative example 3 | Right-hand member | 1560 | 1220 | 1113 | 1410 | 1331 | 0.1 | 58 | 74 |
| Central authorities | 89 | 94 | 1652 | 1295 | |||||
| Left end | 1623 | 1852 | 2439 | 1629 | |||||
| Comparative example 4 | Right-hand member | 0 | 0 | 1 | 2 | 0.33 | 2 | 19 | 39 |
| Central authorities | 0 | 1 | 0 | 0 | |||||
| Left end | 0 | 0 | 0 | 0 | |||||
| Comparative example 5 | Right-hand member | 2 | 3 | 5 | 11 | 6.42 | 1 | 39 | 58 |
| Central authorities | 9 | 8 | 3 | 1 | |||||
| Left end | 16 | 11 | 5 | 3 | |||||
| Comparative example 6 | Right-hand member | 4 | 2 | 0 | 1 | 2.08 | 30 | 12 | 21 |
| Central authorities | 3 | 0 | 1 | 3 | |||||
| Left end | 1 | 5 | 3 | 2 | |||||
| Comparative example 7 | Right-hand member | 0 | 0 | 0 | 0 | 0 | - | - | - |
| Central authorities | 0 | 0 | 0 | 0 | |||||
| Left end | 0 | 0 | 0 | 0 | |||||
[table 3]
| Tensile modulus of elasticity (unit: GPa) | Boiling water shrinkage (%) | Uneven thickness | The tear propogation resistance | S shape crimping | ||||||
| The position | Maximum | Minimum of a value | The tensile modulus of elasticity direction is poor | Maximum tension elastic modelling quantity direction is poor | 45 ° and 135 ° poor | The boiling water shrinkage direction is poor | T0/T1 | Vertically/laterally | ||
| Embodiment 1 | Right-hand member | 1.64 | 1.51 | 0.13 | 0.19 | 1.19 | 1.215 | 1 | 0.99 | ◎ |
| Central authorities | 1.69 | 1.61 | 0.08 | |||||||
| Left end | 1.81 | 1.62 | 0.19 | 1.24 | ||||||
| Embodiment 2 | Right-hand member | 1.62 | 1.61 | 0.01 | 0.07 | 1.25 | 1.215 | 0.98 | 0.9 | ◎ |
| Central authorities | 1.64 | 1.63 | 0.01 | |||||||
| Left end | 1.64 | 1.57 | 0.07 | 1.18 | ||||||
| Embodiment 3 | Right-hand member | 1.61 | 1.46 | 0.15 | 0.15 | 1.22 | 1.205 | 1.03 | 1 | ◎ |
| Central authorities | 1.67 | 1.64 | 0.03 | |||||||
| Left end | 1.82 | 1.82 | 0 | 1.19 | ||||||
| Embodiment 4 | Right-hand member | 1.49 | 1.37 | 0.12 | 0.21 | 1.39 | 1.295 | 1.07 | 1.01 | ◎ |
| Central authorities | 1.54 | 1.37 | 0.17 | |||||||
| Left end | 1.52 | 1.31 | 0.21 | 1.2 | ||||||
| Embodiment 5 | Right-hand member | 1.54 | 1.31 | 0.23 | 0.31 | 1.35 | 1.39 | 1.02 | 0.95 | ○ |
| Central authorities | 1.57 | 1.26 | 0.31 | |||||||
| Left end | 1.56 | 1.33 | 0.23 | 1.43 | ||||||
| Embodiment 6 | Right-hand member | 1.81 | 1.76 | 0.05 | 0.26 | 1.3 | 1.19 | 0.97 | 0.96 | ◎ |
| Central authorities | 1.81 | 1.66 | 0.15 | |||||||
| Left end | 2.04 | 1.78 | 0.26 | 1.08 | ||||||
| Embodiment 7 | Right-hand member | 1.69 | 1.59 | 0.1 | 0.21 | 1.39 | 1.275 | 1.05 | 0.99 | ◎ |
| Central authorities | 1.91 | 1.7 | 0.21 | |||||||
| Left end | 1.95 | 1.78 | 0.17 | 1.16 | ||||||
| Comparative example 1 | Right-hand member | 1.64 | 1.44 | 0.2 | 0.22 | 1.43 | 1.38 | 1.21 | 0.81 | ○ |
| Central authorities | 1.65 | 1.48 | 0.17 | |||||||
| Left end | 1.7 | 1.48 | 0.22 | 1.33 | ||||||
| Comparative example 2 | Right-hand member | 1.62 | 1.45 | 0.17 | 0.68 | 1.45 | 1.56 | 1.16 | 0.59 | ○ |
| Central authorities | 1.89 | 1.21 | 0.68 | |||||||
| Left end | 1.74 | 1.47 | 0.27 | 1.67 | ||||||
| Comparative example 3 | Right-hand member | 2.04 | 1.78 | 0.26 | 0.26 | 1.47 | 1.53 | 1.23 | 0.67 | ○ |
| Central authorities | 1.68 | 1.59 | 0.09 | |||||||
| Left end | 1.91 | 1.7 | 0.21 | 1.59 | ||||||
| Comparative example 4 | Right-hand member | 1.68 | 1.06 | 0.6 | 1.05 | 1.62 | 1.595 | 1.18 | 1.92 | × |
| Central authorities | 1.62 | 1.01 | 0.61 | |||||||
| Left end | 2.12 | 1.07 | 1.05 | 1.57 | ||||||
| Comparative example 5 | Right-hand member | 1.68 | 1.45 | 0.23 | 0.31 | 1.38 | 1.425 | 1.21 | 1.31 | ○ |
| Central authorities | 1.78 | 1.47 | 0.31 | |||||||
| Left end | 1.66 | 1.37 | 0.29 | 1.47 | ||||||
| Comparative example 6 | Right-hand member | 1.95 | 1.78 | 0.17 | 0.59 | 1.62 | 1.58 | 1.19 | 0.67 | × |
| Central authorities | 1.91 | 1.7 | 0.21 | |||||||
| Left end | 2.07 | 1.48 | 0.59 | 1.54 | ||||||
| Comparative example 7 | Right-hand member | 2.54 | 1.06 | 1.48 | 1.57 | 1.29 | 1.185 | 1.02 | 1.87 | ◎ |
| Central authorities | 2.57 | 1 | 1.57 | |||||||
| Left end | 1.95 | 1.05 | 0.9 | 1.08 | ||||||
[table 4]
| The position | 0 ° laterally | 30° | 60° | 90 ° vertically | 120° | 150° | Maximum | Minimum of a value | The tensile modulus of elasticity direction is poor | |
| Embodiment 1 | Right-hand member | 1.51 | 1.51 | 1.61 | 1.64 | 1.58 | 1.53 | 1.64 | 1.51 | 0.13 |
| Central authorities | 1.63 | 1.65 | 1.67 | 1.69 | 1.63 | 1.61 | 1.69 | 1.61 | 0.08 | |
| Left end | 1.62 | 1.62 | 1.71 | 1.81 | 1.70 | 1.65 | 1.81 | 1.62 | 0.19 |
Unit: GPa
Below, to having measured film residual after the rerum natura, profit carries out evaporation in the following method.
[aluminium-vapour deposition]
The emboliform aluminium (purity 99.9%) that uses size about 8～10mm on the surface of the polyamide series resin film that obtains as described above, utilizes the electron beam evaporation plating method to form the aluminium film as vapor deposition source.Use electron gun as heating source, emission current is set at 0.5A.The film speed of dividing a word with a hyphen at the end of a line is set at 130m/min, has made the thick film of 50nm.Environmental pressure during evaporation is adjusted into 1 * 10
-2Pa.The temperature of the roller of the film when being used to cool off evaporation is adjusted into-10 ℃.
[aluminium oxide evaporation]
Use the emboliform Al of size about 3～5mm
2O
3(purity 99.9%) on the surface of the polyamide series resin film that obtains as described above, utilizes the electron beam evaporation plating method to form aluminum oxide film as vapor deposition source.Use electron gun as heating source, emission current is set at 1.3A.The film speed of dividing a word with a hyphen at the end of a line is set at 130m/min, has made the thick film of 20nm.Environmental pressure during evaporation is adjusted into 1 * 10
-2Pa.The temperature of the roller of the film when being used to cool off evaporation is adjusted into-10 ℃.
[silica evaporation]
Use the emboliform Si (purity 99.99%) and the SiO of size about 3～5mm
2(purity 99.9%) on the surface of the polyamide series resin film that obtains as described above, utilizes the electron beam evaporation plating method to form silicon oxide film as vapor deposition source.Two kinds of deposition materials do not mix but are divided into two parts ground and drop into.Use electron gun as heating source, respectively with Si and SiO
2Cut apart by the time and to heat.The emission current of electron gun at this moment is set at 0.8A, heats each material, so that Si and SiO
2Ratio of components be 1: 9 (mass ratio).The film speed of dividing a word with a hyphen at the end of a line is set at 130m/min, has made the thick film of 20nm.Environmental pressure during evaporation is adjusted into 1 * 10
-2Pa.The temperature of the roller of the film when being used to cool off evaporation is adjusted into-10 ℃.
Uneven thickness, the maximum tension elastic modelling quantity direction of the evaporated film that obtains is poor, the boiling water shrinkage direction is poor, the measurement result of the ratio of tear propogation resistance, volume appearance, oxygen permeability is shown in table 5.
[table 5]
| The evaporation thing | The volume appearance | Oxygen permeability (ml/m 2·MPa·day) | Maximum tension elastic modelling quantity direction is poor | The boiling water shrinkage direction is poor | Uneven thickness T0/T1 | The tear propogation resistance | |
| Vertically/laterally | |||||||
| Embodiment 1 | Aluminium | ◎ | 16 | 0.12 | 1.21 | 1.05 | 0.91 |
| Aluminium oxide | ◎ | 24 | 0.11 | 1.23 | 0.98 | 0.93 | |
| Silica | ◎ | 19 | 0.11 | 1.19 | 1.01 | 0.89 | |
| Embodiment 2 | Aluminium | ◎ | 17 | 0.09 | 1.22 | 1.06 | 0.93 |
| |
Aluminium | ◎ | 18 | 0.11 | 1.2 | 1.04 | 1.05 |
| Embodiment 4 | Aluminium | ◎ | 19 | 0.22 | 1.28 | 1.05 | 1.11 |
| Embodiment 5 | Aluminium | ○ | 14 | 0.35 | 1.34 | 1.01 | 0.97 |
| Embodiment 6 | Aluminium | ◎ | 16 | 0.28 | 1.22 | 0.99 | 0.93 |
| |
Aluminium | ◎ | 15 | 0.26 | 1.29 | 1.04 | 0.94 |
| Comparative example 1 | Aluminium | × | 18 | 0.26 | 1.37 | 1.23 | 0.85 |
| Comparative example 2 | Aluminium | × | 19 | 0.62 | 1.59 | 1.19 | 0.57 |
| Comparative example 3 | Aluminium | × | 15 | 0.24 | 1.55 | 1.22 | 0.66 |
| Comparative example 4 | Aluminium | × | 18 | 1.14 | 1.6 | 1.17 | 1.93 |
| Comparative example 6 | Aluminium | × | 14 | 0.66 | 1.59 | 1.21 | 0.67 |
| Comparative example 7 | Aluminium | ○ | 16 | 1.59 | 1.12 | 1.01 | 1.88 |
Embodiment 2
Compare with embodiment 1, the water temperature of the 1st pick trough is changed to 30 ℃.In addition, operation similarly to Example 1.Air layer thickness, minimum of a value are 90 μ m, and maximum is 161 μ m.
State, uneven thickness, the maximum tension elastic modelling quantity direction of the crystallite of the nylon film of creating conditions and obtaining of film is poor, the boiling water shrinkage direction is poor, the measurement result of the ratio of tear propogation resistance, volume appearance, S shape edge-curl phenomenon is shown in table 1～table 3.
To the film that obtains, under condition similarly to Example 1, carry out aluminium-vapour deposition, obtain deposition polyamides resin film vapors deposition.Uneven thickness, the maximum tension elastic modelling quantity direction of the evaporated film that obtains is poor, the boiling water shrinkage direction is poor, the measurement result of the ratio of tear propogation resistance, volume appearance, oxygen permeability is shown in table 5.
Compare with embodiment 1, the temperature span of control limit of control of the 1st pick trough is changed to ± 3 ℃.In addition, operation similarly to Example 1.Air layer thickness, minimum of a value are 89 μ m, and maximum is 165 μ m.
State, uneven thickness, the maximum tension elastic modelling quantity direction of the crystallite of the nylon film of creating conditions and obtaining of film is poor, the boiling water shrinkage direction is poor, the measurement result of the ratio of tear propogation resistance, volume appearance, S shape edge-curl phenomenon is shown in table 1～table 3.
To the film that obtains, under condition similarly to Example 1, carry out aluminium-vapour deposition, obtain deposition polyamides resin film vapors deposition.Uneven thickness, the maximum tension elastic modelling quantity direction of the evaporated film that obtains is poor, the boiling water shrinkage direction is poor, the measurement result of the ratio of tear propogation resistance, volume appearance, oxygen permeability is shown in table 5.
Embodiment 4,5
Compare with embodiment 1, regulate from the amount of the air of nozzle ejection, and the thickness of change air layer.In addition, operation similarly to Example 1.
State, uneven thickness, the maximum tension elastic modelling quantity direction of the crystallite of the nylon film of creating conditions and obtaining of film is poor, the boiling water shrinkage direction is poor, the measurement result of the ratio of tear propogation resistance, volume appearance, S shape edge-curl phenomenon is shown in table 1～table 3.
To the film that obtains, under condition similarly to Example 1, carry out aluminium-vapour deposition, obtain deposition polyamides resin film vapors deposition.Uneven thickness, the maximum tension elastic modelling quantity direction of the evaporated film that obtains is poor, the boiling water shrinkage direction is poor, the measurement result of the ratio of tear propogation resistance, volume appearance, oxygen permeability is shown in table 5.
Compare with embodiment 1, the temperature of change casting roller simultaneously, is regulated from the amount of the air of nozzle ejection, and the thickness of change air layer.In addition, operation similarly to Example 1.
State, uneven thickness, the maximum tension elastic modelling quantity direction of the crystallite of the nylon film of creating conditions and obtaining of film is poor, the boiling water shrinkage direction is poor, the measurement result of the ratio of tear propogation resistance, volume appearance, S shape edge-curl phenomenon is shown in table 1～table 3.
To the film that obtains, under condition similarly to Example 1, carry out aluminium-vapour deposition, obtain deposition polyamides resin film vapors deposition.Uneven thickness, the maximum tension elastic modelling quantity direction of the evaporated film that obtains is poor, the boiling water shrinkage direction is poor, the measurement result of the ratio of tear propogation resistance, volume appearance, oxygen permeability is shown in table 5.
Comparative example 1
Compare with embodiment 1, the temperature span of control limit of control of the 1st pick trough is changed to ± 10 ℃.In addition, operation obtains nylon 6 films similarly to Example 1.At this moment, the water temperature on the top of the 1st pick trough is 49 ℃, and the water temperature of bottom is 33 ℃.The film that obtains after operating like this, uneven thickness is big, and the volume appearance is bad.
State, uneven thickness, the maximum tension elastic modelling quantity direction of the crystallite of the nylon of creating conditions and obtaining 6 films of film is poor, the boiling water shrinkage direction is poor, the measurement result of the ratio of tear propogation resistance, volume appearance, S shape edge-curl phenomenon is shown in table 1～table 3.
To the film that obtains, under condition similarly to Example 1, carry out aluminium-vapour deposition, obtain deposition polyamides resin film vapors deposition.Uneven thickness, the maximum tension elastic modelling quantity direction of the evaporated film that obtains is poor, the boiling water shrinkage direction is poor, the measurement result of the ratio of tear propogation resistance, volume appearance, oxygen permeability is shown in table 5.
Comparative example 2
Compare with embodiment 1, change the ejection flow from the air of nozzle, the minimum of a value that makes air layer thickness is that 25 μ m, maximum are 157 μ m.In addition, operation obtains nylon 6 films similarly to Example 1.
State, uneven thickness, the maximum tension elastic modelling quantity direction of the crystallite of the nylon film of creating conditions and obtaining of film is poor, the boiling water shrinkage direction is poor, the measurement result of the ratio of tear propogation resistance, volume appearance, S shape edge-curl phenomenon is shown in table 1～table 3.
To the film that obtains, under condition similarly to Example 1, carry out aluminium-vapour deposition, obtain deposition polyamides resin film vapors deposition.Uneven thickness, the maximum tension elastic modelling quantity direction of the evaporated film that obtains is poor, the boiling water shrinkage direction is poor, the measurement result of the ratio of tear propogation resistance, volume appearance, oxygen permeability is shown in table 5.
Comparative example 3
Compare with embodiment 1, the temperature of casting roller is changed to 60 ℃, simultaneously, change the ejection flow from the air of nozzle, the minimum of a value that makes air layer thickness is that 10 μ m, maximum are 55 μ m.In addition, operation obtains nylon 6 films similarly to Example 1.
State, uneven thickness, the maximum tension elastic modelling quantity direction of the crystallite of the nylon of creating conditions and obtaining 6 films of film is poor, the boiling water shrinkage direction is poor, the measurement result of the ratio of tear propogation resistance, volume appearance, S shape edge-curl phenomenon is shown in table 1～table 3.
To the film that obtains, under condition similarly to Example 1, carry out aluminium-vapour deposition, obtain deposition polyamides resin film vapors deposition.Uneven thickness, the maximum tension elastic modelling quantity direction of the evaporated film that obtains is poor, the boiling water shrinkage direction is poor, the measurement result of the ratio of tear propogation resistance, volume appearance, oxygen permeability is shown in table 5.
Comparative example 4
Compare with embodiment 1, the temperature of casting roller is changed to 15 ℃, simultaneously, change the ejection flow from the air of nozzle, the minimum of a value that makes air layer thickness is that 61 μ m, maximum are 154 μ m.In addition, operation obtains nylon 6 films similarly to Example 1.
State, uneven thickness, the maximum tension elastic modelling quantity direction of the crystallite of the nylon of creating conditions and obtaining 6 films of film is poor, the boiling water shrinkage direction is poor, the measurement result of the ratio of tear propogation resistance, volume appearance, S shape edge-curl phenomenon is shown in table 1～table 3.
To the film that obtains, under condition similarly to Example 1, carry out aluminium-vapour deposition, obtain deposition polyamides resin film vapors deposition.Uneven thickness, the maximum tension elastic modelling quantity direction of the evaporated film that obtains is poor, the boiling water shrinkage direction is poor, the measurement result of the ratio of tear propogation resistance, volume appearance, oxygen permeability is shown in table 5.
Comparative example 5
Compare with embodiment 4, the water temperature of the 1st pick trough is changed to 65 ℃.In addition, operation obtains nylon 6 films similarly to Example 4.But, nylon 6 films that obtain, uneven thickness is big, and the volume appearance is bad.
State, uneven thickness, the maximum tension elastic modelling quantity direction of the crystallite of the nylon of creating conditions and obtaining 6 films of film is poor, the boiling water shrinkage direction is poor, the measurement result of the ratio of tear propogation resistance, volume appearance, S shape edge-curl phenomenon is shown in table 1～table 3.
Nylon 6 films that obtain are because the volume appearance is bad, so can not carry out evaporation processing.
Comparative example 6
Compare with embodiment 1, change the ejection flow from the air of nozzle, the minimum of a value that makes air layer thickness is 130 μ m, and maximum is 250 μ m.In addition, operation obtains nylon 6 films similarly to Example 1.
State, uneven thickness, the maximum tension elastic modelling quantity direction of the crystallite of the nylon of creating conditions and obtaining 6 films of film is poor, the boiling water shrinkage direction is poor, the measurement result of the ratio of tear propogation resistance, volume appearance, S shape edge-curl phenomenon is shown in table 1～table 3.
To the film that obtains, under condition similarly to Example 1, carry out aluminium-vapour deposition, obtain deposition polyamides resin film vapors deposition.Uneven thickness, the maximum tension elastic modelling quantity direction of the evaporated film that obtains is poor, the boiling water shrinkage direction is poor, the measurement result of the ratio of tear propogation resistance, volume appearance, oxygen permeability is shown in table 5.
Comparative example 7
Nylon 6 resin that drying is good (manufacturing of UNITIKA company, A1030-BRF) and above-mentioned masterbatch sheet mix, the cooperation ratio that makes silica is 0.05 quality %, put into extruder, fusion in temperature is heated to 260 ℃ cylindrical shell, be extruded into sheet by T mouth nib, with the sheet of extruding utilize the air knife The tape casting make casting roller and not the minimum value and value between the drawing sheet be 90 μ m, make the casting roller driving fit of 20 ℃ of itself and surface temperatures and cool off, obtain the non-stretched film that thickness is 150 μ m.
This non-stretched film is supplied with the longitudinal stretching machine that is made of the different warm-up mill group of peripheral speed, attempt under 55 ℃ of temperature, indulge stretching for 2.7 times with stretching ratio.But the film that mostly occurs cuts off, and can not obtain oriented film.
Relative with it, by shortening casting roller and the distance between the drawing sheet not, the situation that film cuts off alleviates.And, final at casting roller with when the minimum value and value between the drawing sheet is not 10 μ m, can stretch.Promptly, to supply with the longitudinal stretching machine that constitutes by the different warm-up mill group of peripheral speed by utilizing casting roller to cool off the non-stretched film that drawing sheet not obtains, under 55 ℃ of temperature, longitudinally stretch for 2.7 times with stretching ratio, this longitudinal stretching film is carried out preheating by preheating part under 60 ℃, under 90 ℃ of temperature, laterally stretch with 3.8 times of edges of stretching ratio, then, under 211 ℃, heat-treat, then, laterally carry out 2% relaxation processes in 210 ℃ of lower edges of temperature, obtain nylon 6 films of thickness 15 μ m.
State, uneven thickness, the maximum tension elastic modelling quantity direction of the crystallite of the nylon of creating conditions and obtaining 6 films of film is poor, the boiling water shrinkage direction is poor, the measurement result of the ratio of tear propogation resistance, volume appearance, S shape edge-curl phenomenon is shown in table 1～table 3.
To the film that obtains, under condition similarly to Example 1, carry out aluminium-vapour deposition, obtain deposition polyamides resin film vapors deposition.Uneven thickness, the maximum tension elastic modelling quantity direction of the evaporated film that obtains is poor, the boiling water shrinkage direction is poor, the measurement result of the ratio of tear propogation resistance, volume appearance, oxygen permeability is shown in table 5.
Result by table 1～table 3 shows, in embodiment 1～7, the average grain diameter of the crystallite in the film is 0.1～10 μ m, there is 1～1000 in this crystallite in the scope of 100 * 100 μ m of pellicular front, therefore, can obtain thin film center portion and the end portion thickness inequality is little, and the difference film little, that obtained balance of the rerum natura that produces because of the direction of film.In addition because the particle diameter more than 70% of crystallite is in 0.5～1.5 times the scope of average grain diameter, therefore, for the crystallization completeness up to more than 70%, the film of transparent and physical properties excellent.
Relative with it, in comparative example 1,2, there is the deviation that has density of crystallite big and because of film position causes the non-existent part of crystallite, in addition, exist the deviation of ratio also big.Therefore, the bad film of volume appearance of and volume big for the uneven thickness of film.In addition, the deviation of rerum natura is also bad.
Film in comparative example 3, though crystallite exists, its average grain diameter is very little, and therefore, mist degree worsens, and in addition, the aspect ratio of tear propogation resistance is little, balance is bad.
The film of comparative example 4 and comparative example 7 and since crystallite exist density little, so the tear propogation resistance when maximum tension elastic modelling quantity direction difference is big in length and breadth, balance is bad.
The film of comparative example 6, because the average grain diameter of crystallite is big, so the mist degree deterioration, in addition, hot strength is little, and is little and maximum tension elastic modelling quantity direction difference is big, balance is bad for the aspect ratio of tear propogation resistance.
Claims (8)
1. deposition polyamides resin film vapors deposition, it is characterized in that at least one evaporation organic/inorganic substance matter of polyamide series resin film the polyamide series resin film before the evaporation satisfies the full terms of following (a)～(d):
(a) the ratio T0/T1 of the horizontal central portion thickness T0 of film and end portion thickness T1 is 0.9～1.1,
(b) relevant film vertically and the ratio of film tear propogation resistance transversely tear propogation resistance/horizontal tear propogation resistance=0.7～1.3 longitudinally,
(c) maximum tension elastic modelling quantity direction difference is below 0.5,
(d) boiling water shrinkage direction difference is below 1.5;
There is 1～1000 crystallite from polyamide that average grain diameter is 0.1～10 μ m in the scope of 100 * 100 μ m on the pellicular front of polyamide series resin film.
2. deposition polyamides resin film vapors deposition as claimed in claim 1 is characterized in that, the particle diameter more than 70% from the crystallite of polyamide of polyamide series resin film is positioned at 0.5～1.5 times scope of the average grain diameter of aforementioned crystallite.
3. deposition polyamides resin film vapors deposition as claimed in claim 1 or 2 is characterized in that, the crystallization completeness of polyamide series resin film is more than 70%.
4. the manufacture method of a deposition polyamides resin film vapors deposition, it is the method that is used for making each described deposition polyamides resin film vapors deposition of claim 1～3, it is characterized in that:
To press against from the resin sheet that the mouth mould melt extrudes on the casting roller and the air layer thickness between casting roller and resin sheet when obtaining non-stretched film is 50～220 μ m,
Make non-stretched film make its suction by the pick trough more than 2 grooves that contain water temperature mutually different the 1st section and the 2nd section, simultaneously, the water temperature of the 1st section pick trough of this moment is set at the arbitrary temp in 30～50 ℃ the scope, and carry out temperature control, so that it is in the scope of aforementioned temperature ± 8 ℃
It is biaxial stretch-formed that non-stretched film after the suction is carried out the while.
5. a deposition polyamides resin film vapors deposition volume is characterized in that each deposition polyamides resin film vapors deposition is wound into web-like in the claim 1～3.
6. deposition polyamides resin film vapors deposition volume as claimed in claim 5 is characterized in that, uses the polyamide series resin film that is wound into web-like of width 1～5m and length 30000m～50000m, the evaporation inorganic substances, and coiling forms.
7. a deposition polyamides resin film vapors deposition is rolled up, it is characterized in that, by being cut also again the coiling shape, the deposition polyamides resin film vapors deposition of the described deposition polyamides resin film vapors deposition volume of claim 6 obtains, the width of the deposition polyamides resin film vapors deposition after the cutting is 0.2～3m, and length is 500～6000m.
8. a vapor-deposited polyamide-based laminated resin film is characterized in that, each deposition polyamides resin film vapors deposition and film of polyolefin resin are laminated in the claim 1～3.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007-265017 | 2007-10-11 | ||
| JP2007265017A JP5247110B2 (en) | 2007-10-11 | 2007-10-11 | Evaporated polyamide resin film and film roll using the same |
| JP2007265017 | 2007-10-11 |
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| CN101148099A CN101148099A (en) | 2008-03-26 |
| CN101148099B true CN101148099B (en) | 2011-12-28 |
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| JP (1) | JP5247110B2 (en) |
| CN (1) | CN101148099B (en) |
| HK (1) | HK1111130A1 (en) |
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| CN102586914A (en) * | 2012-03-06 | 2012-07-18 | 芜湖恒一塑料设备制造有限公司 | Silk dividing device of flat plastic silk drawing machine set |
| CN102586915A (en) * | 2012-03-06 | 2012-07-18 | 芜湖恒一塑料设备制造有限公司 | Static flow-casting device of flat plastic silk drawing machine set |
| WO2016067727A1 (en) * | 2014-10-30 | 2016-05-06 | 東洋紡株式会社 | Gas barrier laminated film and packaging bag |
| JP6841484B2 (en) * | 2016-06-15 | 2021-03-10 | ユニチカ株式会社 | Polyamide-based film and its manufacturing method |
| JP7141674B2 (en) * | 2016-08-08 | 2022-09-26 | ユニチカ株式会社 | Polyamide film and laminates and packaging materials using the same |
| CN111497405B (en) * | 2020-04-30 | 2021-12-31 | 厦门长塑实业有限公司 | High-barrier type linear easy-to-tear nylon film and preparation method thereof |
| JP2021088190A (en) * | 2021-02-10 | 2021-06-10 | ユニチカ株式会社 | Polyamide-based film and method for producing the same |
| CN113910632B (en) * | 2021-10-16 | 2022-09-23 | 宿迁海宏塑业有限公司 | Double-stage film blowing and wire drawing machine |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2006334781A (en) * | 2005-05-06 | 2006-12-14 | Toyobo Co Ltd | Vapor deposition polyamide resin film roll and its manufacturing method |
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| JP3369381B2 (en) * | 1995-12-11 | 2003-01-20 | ユニチカ株式会社 | Method for producing polyamide film |
| JP4162802B2 (en) * | 1999-05-12 | 2008-10-08 | ユニチカ株式会社 | Method for producing biaxially stretched polyamide film |
| JP2001158069A (en) * | 1999-12-03 | 2001-06-12 | Toyobo Co Ltd | Gas barrier laminated film |
| JP2001219460A (en) * | 2000-02-09 | 2001-08-14 | Unitika Ltd | Method for manufacturing polyamide film |
| JP4641673B2 (en) * | 2001-07-06 | 2011-03-02 | ユニチカ株式会社 | Method for producing polyamide film |
| JP2004181777A (en) * | 2002-12-03 | 2004-07-02 | Toyobo Co Ltd | Polyamide based film roll and its manufacturing method |
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| JP2006334781A (en) * | 2005-05-06 | 2006-12-14 | Toyobo Co Ltd | Vapor deposition polyamide resin film roll and its manufacturing method |
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| JP2009090587A (en) | 2009-04-30 |
| JP5247110B2 (en) | 2013-07-24 |
| HK1111130A1 (en) | 2008-08-01 |
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