Patent Grant
8465831
This is a 371 U.S. national phase application of PCT/JP2005/023512 filed 21 Dec. 2005, claiming priority of Japanese Patent Applications No. 2005-171487 filed 10 Jun. 2005, and No. 2005-203303 filed 12 Jul. 2005, respectively, the contents of which are incorporated herein by reference.
The present invention relates to a film roll by taking up a polyamide based resin laminated film having high quality and homogeneous mechanical properties over a long length, and specifically, to a polyamide-based resin laminated film roll with excellent workability (in particular, workability under high humidity) in use of packaging such as retort food by laminating with a polyolefin based resin film.
A biaxially oriented polyamide based resin film composed of nylon in major components is excellent in toughness, gas-barrier, pinhole resistance, transparency, printing property and the like, so that it is widely utilized as a packaging material in various kinds of foods such as a variety of liquid food, aqueous food, frozen food, retort food, paste food, cattle meat and aquatic food. Particularly in recent years, it is used extensively in packaging of retort food. Such polyamide based resin film is laminated with polyolefin based resin films such as polyethylene and polypropylene, folded in two parallel to its machine direction, then thermally adhered in three sides and cut out to give a bag with one side opened and three edges sealed in an opened state, in which various kinds of food etc. are filled and sealed, then sterilized by heating in boiling water before being supplied to market.
In the case of using polyamide based resin film, however, there are some instances that warpage occurs at corners of packaging bag after heat sterilization treatment to yield a curling phenomenon of four sides in S-shape (hereinafter called S-shaped curl phenomenon), resulting in remarkable deterioration of appearance as packaging goods. Therefore, regarding a method of reducing such curl phenomenon, as shown in Patent reference 1, there has been proposed a method to adjust a biaxially oriented polyamide based resin film to a specified value of product of its boiling water shrinkage percentage and percentage change of molecular orientation angle in the direction of film width, but the method needs an extremely high temperature in thermal fixation or excess thermal relaxation after stretching to enhance dimensional stability in boiling water treatment, thus it poses problems that the toughness and pinhole resistance of the resultant film are deteriorated.
Therefore, the present inventors have devised and proposed a method for obtaining a biaxially oriented polyamide based resin film free from S-shaped curl phenomenon without lowering toughness and pinhole resistance by adjusting boiling water shrinkage percentage and refraction index of film within a specified numeric range as described in Patent reference 2.
Problems to be Solved by the Invention
According to the method of Patent reference 2 described above, it becomes possible to obtain a biaxially oriented polyamide based resin film free from S-shaped curl phenomenon having excellent toughness and pinhole resistance. However, in a bag forming processing by lamination, since conditions of pressure and time in thermal adhesion are finely adjusted for every film roll used, even in the case where the average values of boiling water shrinkage percentage and refraction index of the film winded up in a film roll are in the range of Patent reference 2, when degree of variation in one film roll is large, wrinkle takes place between films each other on lamination in a bag forming processing, which tends to pose troubles such as bad yield ratio.
On the other hand, the present inventors have proposed, in a production method of biaxially stretched film roll by winding up a biaxially stretched film after melt extrusion of a plurality of resins mixed, as a method to reduce variation of coefficient of dynamic friction, a method to reduce segregation of feedstock by homogenizing the shape of feedstock chip or enlarging the angle of slope of a funnel-shaped hopper as a feed section of feedstock into an extruder (Japanese Unexamined Patent Publication 2004-181777). However, the method also cannot necessarily be conclusive for a method to suppress the variation and fluctuation of mechanical properties such as boiling water shrinkage percentage and refraction index of film winded in a film roll.
As a result of committed research on production techniques to produce a biaxially stretched film roll with high homogeneity, the present inventors invented a polyamide based resin film roll with high homogeneity in film thickness, boiling water shrinkage percentage and refraction index, and other physical properties and capable of bag forming processing smoothly with good yield ratio free of wrinkles between films efficiently at lamination (Japanese Unexamined Patent Publication 2004-262922).
Problems to be Solved by the Invention
According to the polyamide based resin film roll with high homogeneity in film thickness, boiling water shrinkage percentage, and refraction index and other physical properties, the workability at the time of laminating can be improved without impairing satisfactory toughness and pinhole resistance of polyamide-based resin film and without generating any S-shaped curl phenomenon. However, even in the event of the polyamide-based resin film roll with highly uniform physical properties as described above, there are cases in which satisfactory lubricity is not developed on rolls of a laminating machine when lamination is performed under high humidity in the summertime, etc., and it was identified that satisfactory processing characteristics are not always obtained.
The present invention has been achieved as a result of committed research and development on production techniques to increase the lubricity of polyamide-based resin film under high humidity and to be free of variations, and it is the object of the present invention to provide a biaxially oriented polyamide based resin laminated film roll which solves the problems of conventional polyamide based resin film rolls, which is capable of bag forming processing by lamination smoothly and scarcely free of trouble even under high humidity in the summertime, etc., and which is able to form packages free of S-shaped curls efficiently. It is another object of the present invention to provide a biaxially oriented polyamide based laminated film roll with which processed goods are able to be obtained at a good yield ratio in the post-processing of bag forming processing, etc. It is still another object of the present invention to provide a manufacturing process that can efficiently manufacture such a biaxially oriented polyamide based laminated film roll.
Means to Solve the Problems
Of the present inventions, the constituent of the invention described in claim 1 is a polyamide based resin laminated film roll formed by winding up of the polyamide based resin film in a width of 0.2 m or more to 3.0 m or less, and a length of 300 m or more to 30000 m or less, wherein when the polyamide based resin laminated film roll has a first sample cutout portion set up within 2 m from the winding end of film; and a final cutout portion set up within 2 m from the winding start of film, as well as has a sample cutout portion set up in approximately every 100 m from the first sample cutout portion, the polyamide based resin laminated film roll satisfies the following requirements (1) through (5):
The constituent of the invention described in claim 2 is, in the invention described in claims 1, the roll wherein when a coefficient of dynamic friction is measured for each sample cut out from each cutout portion under the atmosphere of 23° C. and 80% RH, the average coefficient of dynamic friction which is the average value of coefficients of dynamic friction of the samples is within a range of 0.3 to 0.8 and at the same time a degree of variability of the coefficient of dynamic friction of all the samples is within a range of ±5% to ±30% to the average coefficient of dynamic friction.
The constituent of the invention described in claim 3 is, in the invention described in claims 1, the roll wherein when the content of inorganic particles is measured for each sample cut out from each cutout portion, the average content which is the average value of the content of inorganic particles is within a range of 0.01 to 0.5% by weight and at the same time a degree of variability of the content of inorganic particles of all the samples is within a range of ±2% to ±10% to the average content of inorganic particles.
The constituent of the invention described in claim 4 is, in the invention described in any of claims 1, the roll wherein when refraction index in the thick direction of each sample cut out from each of the cutout portions is measured, an average refraction index which is the average value of the refraction indexes is 1.500 or more, 1.520 or less, and a degree of variability in the refraction indexes of all samples is within a range of ±2% relative to the average refraction index.
The constituent of the invention described in claim 5 is, in the invention described in claims 1, the polyamide based resin laminated film roll wound up wherein the average particle size of inorganic particles contained in the core layer is brought to be larger than or equal to the thickness of the skin layer.
The constituent of the invention described in claim 6 is, in the invention described in claim 1, the roll wherein the major component of polyamide composing the polyamide based resin laminated film roll is nylon 6.
The constituent of the invention described in claim 7 is, in the invention described in claim 1, the roll wherein polyamide based resin laminated film wound up is formed from a mixture of two or more different types of mixed substances of polyamide based resin.
The constituent of the invention described in claim 8 is, in the invention described in claim 1, the roll wherein the polyamide based resin laminated film wound up is laminated with a polyolefin based resin film.
The constituent of the invention described in claim 9 is, in the invention described in claims 1, the roll wherein a polyamide based resin laminated film formed by biaxially stretching an unoriented sheet-like material obtained by extruding melted polyamide based resin from a T-die and being brought in contact with a metal roll to cool is wound up.
The constituent of the invention described in claim 10 is, in the invention described in claim 1, the roll which is a polyamide based resin laminated film wound up is stretched by a tenter stretching method.
The constituent of the invention described in claim 11 is, in the invention described in claim 1, the roll which is a polyamide based resin laminated film wound up is sequentially biaxially stretched.
The constituent of the invention described in claim 12 is, in the invention described in claims 1, the roll wherein a polyamide based resin laminated film biaxially stretched in the longitudinal direction and in the transverse direction is wound up.
The constituent of the invention described in claim 13 is, in the invention described in claim 1, the roll which is a polyamide based resin laminated film wound up is a practically unoriented sheet-like substance of polyamide based resin stretched in at least two stages in the longitudinal direction to be threefold or more at a higher temperature than the glass transition temperature of the polyamide based resin plus 20° C., and then stretched in the transverse direction to be threefold or more.
The constituent of the invention described in claim 14 is, in the invention described in claim 1, the roll which is a polyamide based resin laminated film wound up is thermally fixed after a final stretching treatment.
The constituent of the invention described in claim 15 is, in the invention described in claim 1, the roll which is a polyamide based resin laminated film wound up is thermally fixed after relaxing treatment.
The constituent of the invention described in claim 16 is, in the invention described in claim 1, the roll wherein at least one kind selected from lubricant, anti-blocking agent, thermal stabilizer, antioxidant, antistatic agent, light resistant agent and impact modifier is added into the polyamide based resin laminated film wound up.
The constituent of the invention described in claim 17 is, in the invention described in claim 1, the roll wherein inorganic particle is added into the polyamide based resin laminated film wound up.
The constituent of the invention described in claim 18 is, in the invention described in claim 17, the roll wherein the inorganic particle is a silica particle of 0.5-5.0 μm in an average diameter.
The constituent of the invention described in claim 19 is, in the invention described in claim 1, the roll wherein a higher fatty acid is added into the polyamide based resin laminated film wound up.
The constituent of the invention described in claim 20 is a process for producing polyamide based resin laminated film roll according to claim 1, including: a film forming step of forming unstretched laminated sheet with multiple polyamide based resin sheets laminated by melt-extruding polyamide based resin from multiple extruders by coextrusion; and a biaxial stretching step of the unstretched laminated sheet obtained in the film forming process in the longitudinal direction and in the transverse direction, and satisfies the following requirements (1) and (5):
The constituent of the invention described in claim 21 is, in the invention described in claims 20, a process wherein the high-concentration material chips used in the film forming process are polyamide based resin chips with inorganic particles added by 5% by weight or more and less than 20% by weight.
The constituent of the invention described in claim 22 is, in the invention described in claims 20, a process wherein the inorganic particles added to the polyamide based resin sheet to be laminated on the uppermost layer has the pore volume of 0.5 to 2.0 mL/g and the average particle size of 1.0 to 5.0 μm.
The constituent of the invention described in claim 23 is, in the invention described in claims 20, a process further including a preheating process executed before the longitudinal stretching process and a heat-treatment process executed after the longitudinal stretching process, wherein a variation width of surface temperature of film at any point of the longitudinal stretching process, the preheating process and the heat-treatment process is adjusted throughout the full length of the film within a range of ±1° C. to the average temperature.
Effect of the Invention
According to the polyamide based resin laminated film roll of the present invention, bag forming processing can be conducted smoothly by lamination with almost no troubles under high humidity in the summertime, etc. to give a package free from S-shaped curl efficiently. In addition, it becomes possible to obtain a processed goods with high yield ratio in a post-processing of bag forming processing, etc. Additionally, the use of polyamide based resin laminated film roll of the present invention imparts high toughness and superb pinhole resistance to bags for food packaging after bag forming processing by lamination.
The polyamide based resin laminated film roll of the present invention is adjusted in such a manner that the average boiling water shrinkage percentage, which is the average value of the maximum boiling water shrinkage percentages, is 2% or more and 6% or less when the maximum boiling water shrinkage percentage is measured, which is the maximum value of the boiling water shrinkage percentages in all directions, for all the samples in the event that samples are cut out by the later-described method.
Also, in the case of cutting out a sample in a method described later, when a directional difference of boiling water shrinkage percentage of a polyamide based resin laminated film roll of the present invention is measured, the directional difference of boiling water shrinkage percentage being the difference between a boiling water shrinkage percentage in the direction of +45° to the longitudinal direction and a boiling water shrinkage percentage in the direction of −45° to the longitudinal direction for all samples in an absolute value, an average directional difference of boiling water shrinkage percentage which is the average of the directional differences of boiling water shrinkage percentage is adjusted to be 1.5% or less.
The cutout of sample in the present invention is first set up to be a first sample cutout portion within 2 m from the winding end of film and a final cutout portion within 2 m from the winding start of film, and a sample cutout portion is to be set up in approximately every 100 m from the first sample cutout portion. Additionally, “approximately every 100 m” means that a sample may be cut out in about 100 m±1 m.
The above-mentioned cutout of sample will be more specifically described as follows; for example, when a roll of polyamide based film roll is winded in a length of 498 m, a first sample (1) is cut out within 2 m from the winding end of film. Additionally, the cutout of sample is for convenience cut into a rectangle having a side along the longitudinal direction and a side perpendicular to the longitudinal direction (not to be cut out on a slant). Subsequently, a second sample (2) is cut out in a part 100 m apart toward the winding start side from the part cut out. Similarly a third sample (3) in a part 200 m apart toward the winding start side, a fourth sample (4) in a part 300 m apart toward the winding start side, and a fifth sample (5) in a part 400 m apart toward the winding start side are cut out. When samples are cut out in this way, the rest becomes shorter than 100 m, thus a sixth (final) sample (6) is cut out in any part within 2 m from winding start of film. Then the following values of each sample cut out are measured in the following methods. They are, boiling water shrinkage percentage (hereinafter called BS), maximum boiling water shrinkage percentage (hereinafter called BSx), average boiling water shrinkage percentage (hereinafter called BSax), directional difference of boiling water shrinkage percentage (hereinafter called BSd) and average directional difference of boiling water shrinkage percentage (hereinafter called BSad).
[Measuring methods of boiling water shrinkage percentage (BS), maximum boiling water shrinkage percentage (BSx), average boiling water shrinkage percentage (BSax), directional difference of boiling water shrinkage percentage (BSd) and average directional difference of boiling water shrinkage percentage (BSad)]
A biaxially oriented polyamide based resin laminated film cut out from each of cutout portions of polyamide based resin laminated film roll is cut out into a square, allowed to stand in an atmosphere of 23° C. and 65% RH for 2 hours and more. A circle centered on this sample (about 20 cm in diameter) is drawn, a longitudinal direction (direction of film drawn out) is set to be 0°, liner lines passing to the center of circle are clockwise drawn at intervals of 15° in the direction of 0 to 165°, diameter in each direction is measured as the length before treatment. Then, after the sample cut out is thermally treated in boiling water for 30 minutes, it is brought back and water attached on its surface is wiped out, dried in air, allowed to stand in an atmosphere of 23° C. and 65% RH for 2 hours or more, the length of linear line drawn to each diametrical direction is measured as the length after treatment as described above. Then, according to the following formulas 1 to 5, the following values are measured, which are, a BS (boiling water shrinkage percentage), BSx (maximum boiling water shrinkage percentage), BSax (average boiling water shrinkage percentage), BSd (directional difference of boiling water shrinkage percentage) and BSad (average directional difference of boiling water shrinkage percentage).
BS=[(length before treatment−length after treatment)/length before treatment]×100(%) 1
BSx=maximum shrinkage percentage (%) of values measured in 0 to 165° directions at intervals of 15° 2
BSax=summation of BSx's of all samples/number of samples 3
BSd=|(BS in 45° direction)−(BS in 135° direction)| 4
BSad=summation of BSd's of all samples/number of samples 5
Additionally, BSx value of polyamide based resin laminated film composing a polyamide based resin laminated film roll is important from the points for enhancing toughness and pinhole resistance of film itself as well as for securing the thermal resistance when the film is formed into a bag shape and is allowed to undergo hot-water treatment (it is called laminate strength or heat-resistant laminate strength). When BSx value is less than 2%, toughness and pinhole resistance become insufficient, whereas when more than 6%, lamination becomes poor, heat-resistant laminate strength in hot-water treatment becomes insufficient, which is not preferable. Preferable range of BSx is 3.5-5.0% for enhancing toughness, pinhole resistance, lamination property and heat-resistant laminate strength.
Also, BSd value of polyamide based resin laminated film composing a polyamide based resin laminated film roll greatly affects a curl phenomenon occurring in boiling water treatment. That is, the larger the BSd, the more easily a bag is warped into a notable curl. However, when BSd is suppressed to 2.0% or less, preferably 1.5% or less more preferably 1.2% or less, warpage of bag in boiling water treatment can be remarkably suppressed, which can prevent the occurrence of S-shaped curl phenomenon.
Also, for a polyamide based resin laminated film roll of the present invention, it is necessary that a degree of variability in the maximum boiling water shrinkage percentage (BSx) of all samples cut out is adjusted within ±2% to ±10% (±2% or more and ±10% or less) relative to the average boiling water shrinkage percentage (BSa). Here, a degree of variability in the maximum boiling water shrinkage percentages (BSx) of all samples means, when the maximum and the minimum in the maximum boiling water shrinkage percentages (BSx) of all samples are obtained, from which a larger value of the difference between either the maximum or the minimum and the average boiling water shrinkage is obtained, a ratio of which relative to the average boiling water shrinkage percentage.
Namely, in a polyamide based resin laminated film roll of the present invention, when boiling water shrinkage percentage of samples (1) through (6) is denoted as Xn (n=1 to 6), both the difference between Xmax, the maximum value of Xn and average boiling water shrinkage percentage (BSax) and the difference between Xmin, the minimum value and average boiling water shrinkage percentage (BSax) are required to be within ±10%. In other words, |BSax−Xn| (additionally | | indicates absolute value) are all required to be 10% or less.
Additionally, in a polyamide based resin laminated film roll of the present invention, a degree of variability in the maximum boiling water shrinkage percentages (BSx) of all samples cut out is preferably within ±9% relative to the average boiling water shrinkage percentage (BSa), more preferably within ±8%, and further preferably within ±7%.
In addition, in a polyamide based resin laminated film roll of the present invention, a lower degree of variability in the maximum boiling water shrinkage percentages (BSx) of all samples cut out is preferable, but we are considering that the lower limit of the degree of variability is limited to about 2% from the consideration of precision in the measurement.
Also, for a polyamide based resin laminated film roll of the present invention, a degree of variability in the directional differences of boiling water shrinkage percentages (BSd) of all samples cut out is required to be adjusted within ±2% to ±20% (±2% or more and ±20% or less) relative to the average directional difference of boiling water shrinkage percentage (BSad). Here, a degree of variability in the directional differences of boiling water shrinkage percentages (BSd) of all samples means, when the maximum and the minimum in the directional differences of boiling water shrinkage percentages (BSd) of all samples are obtained, from which a larger value of the difference between either the maximum or the minimum and the average directional difference of boiling water shrinkage is obtained, a ratio of which to the average boiling water shrinkage percentage.
Namely, in a polyamide based resin laminated film roll of the present invention, when directional difference of boiling water shrinkage percentage of samples (1) through (6) is denoted as Yn (n=1 to 6), both the difference between Ymax, the maximum value of Yn and average directional difference of boiling water shrinkage percentage (BSad) and the difference between Ymin, the minimum value and average directional difference of boiling water shrinkage percentage (BSad) are required to be within ±20%, in other words, |BSad−Yn| (additionally | | indicates absolute value) are all required to be 20% or less.
Additionally, in a polyamide based resin laminated film roll of the present invention, a degree of variability in the directional differences of boiling water shrinkage percentage (BSd) of all samples cut out is preferably within ±15% relative to the average directional difference of boiling water shrinkage percentage (BSad), more preferably within ±10%, and further preferably within ±8%.
In addition, in a polyamide based resin laminated film roll of the present invention, a lower degree of variability in the directional differences of boiling water shrinkage percentage (BSd) of all samples cut out is preferable, but we are considering that the lower limit of the degree of variability is limited to about 2% from the consideration of precision in the measurement.
The polyamide based resin laminated film roll of the present invention must have the average surface roughness (SRaa), which is the average value of the three dimensional surface roughness (SRa) of all the cutout samples, set in a range of 0.01 to 0.06 μm, and it is preferable that it is included in a range of 0.02 to 0.05 μm (Additionally, one example of the measurement method of three-dimensional surface roughness will be explained in an Example). When the average surface roughness is below 0.01 mm, satisfactory lubricity under high humidity is unable to be obtained, which is not preferable, and on the contrary, when the average surface roughness exceeds 0.06 μm, adhesion with films such as polyolefin is degraded at the time of lamination, which is not preferable.
In addition, the polyamide based resin laminated film roll of the present invention must have the degree of variability of three-dimensional surface roughness (SRa) of all the cutout samples adjusted to be in the range of ±5% to ±20% (±5% or more and ±20% or less) of the average surface roughness (SRaa). The degree of variability of three-dimensional surface roughness (SRa) of all the samples referred to here means a ratio of the difference between the maximum or the minimum differences of three-dimensional surface roughness and the average difference of three-dimensional surface roughness, whichever larger, to the average difference of three-dimensional surface roughness, when the maximum and the minimum of three-dimensional surface roughness (SRa) of all samples are found.
That is, in a polyamide based resin laminated film roll of the present invention, when three-dimensional surface roughness of samples (1) through (6) is denoted as SRn (n=1 to 6), both the difference between SRmax, the maximum value of SRn and average surface roughness (SRaa), and the difference between SRmin, the minimum value and average surface roughness (SRaa) must be within ±20%, in other words, all |SRaa−SRn| (Additionally, | | indicates the absolute value) must be 20% or less.
In addition, in a polyamide based resin laminated film roll of the present invention, a degree of variability in the three-dimensional surface roughness (SRa) of all samples cut out is preferably within ±15% relative to the average surface roughness (SRaa), more preferably within ±10%, and further preferably within ±8%. In addition, in a polyamide based resin laminated film roll of the present invention, a lower degree of variability in the three-dimensional surface roughness (SRa) of all samples cut out is preferable, but it is considered that the lower limit of the degree of variability is limited to about 5% with the measurement accuracy taken into account.
Also, in a polyamide based resin laminated film roll of the present invention, the average haze which is the average value of hazes of all the cutout samples must be within the range of 1.0 to 4.0, and more preferably within the range of 1.5 to 3.0. When the average haze exceeds 4.0, the appearance of bags formed when bag-forming processing is provided become degraded, which is not preferable. Additionally, the average haze is smaller, which is more preferable, but it is considered that the lower limit of the average haze is limited to about 1.0% with the measurement accuracy taken into account.
In addition, the polyamide based resin laminated film roll of the present invention must have the degree of variability of haze (SRa) of all the cutout samples adjusted to be within the range of ±2% to ±15% (±2% or more and ±15% or less) of the average haze. The degree of variability of haze of all the samples referred to here means a ratio of the difference between the maximum or the minimum differences of haze and the difference of average haze, whichever larger, to the difference of average haze, when the maximum and the minimum of average haze of all samples are found.
That is, in a polyamide based resin laminated film roll of the present invention, when haze of samples (1) through (6) is denoted as Hn (n=1 to 6), both the difference between Hmax, the maximum value of Hn and average haze (Han), and the difference between Hmin, the minimum value and average haze (Han) must be within ±15%, in other words, all |Han−Hn| (Additionally, | | indicates the absolute value) must be 15% or less.
In addition, in a polyamide based resin laminated film roll of the present invention, a degree of variability of a haze of all samples cut out is preferably within ±10% relative to the average haze, more preferably within ±8%. In addition, in a polyamide based resin laminated film roll of the present invention, a lower degree of variability in the haze of all samples cut out is preferable, but it is considered that the lower limit of the degree of variability is limited to about 2% with the measurement accuracy taken into account.
Also, in a polyamide based resin laminated film roll of the present invention, a degree of variability in thickness over the entire length in the longitudinal direction must be adjusted within a range of ±2% to ±10% (±2% or more and ±10% or less) relative to the average thickness. Here, a degree of variability in thickness over the entire length in the longitudinal direction means a ratio of the difference between the maximum or the minimum thickness and the average thickness, whichever larger, to the average thickness, when the maximum and the minimum in the thickness over the entire length in the longitudinal direction of all samples are found.
Namely, in a polyamide based resin laminated film roll of the present invention, both the difference between Tmax, the maximum value in thickness over the entire length in the longitudinal direction and the average thickness (Ta, average thickness over the entire length in the longitudinal direction) and the difference between Tmin, the minimum value and the average thickness (Ta) are required to be within ±10%.
Additionally, in a polyamide based resin laminated film roll of the present invention, a degree of variability in thickness over the entire length in the longitudinal direction is preferably within a range of ±8% relative to the average thickness (Ta), more preferably within a range of ±6%.
In addition, in a polyamide based resin laminated film roll of the present invention, a lower degree of variability in thickness over the entire length in the longitudinal direction is preferable, but it is considered that the lower limit of the degree of variability is limited to about 2% in view of the performance of film forming apparatus.
On the other hand, in the polyamide based resin laminated film roll of the present invention, the average coefficient of dynamic friction (μda), which is the average value of coefficient of dynamic friction (μd) at 23° C.×80% RH of all the cutout samples is preferably between a range of 0.3 and 0.8, and more preferably between a range of 0.4 and 0.6. When the average coefficient of dynamic friction at 23° C.×80% RH is below 0.3, film displacement is generated on rolls at the time of bag-forming processing and the processing capabilities are degraded, which is not preferable, and on the contrary, when the average coefficient of dynamic friction exceeds 0.8, satisfactory lubricity under high humidity is unable to be obtained, which is not preferable, either.
Also, in a polyamide based resin laminated film roll of the present invention, a degree of variability in the coefficient of dynamic friction (μd) of all the cutout samples is adjusted, within a range of ±5% to ±30% (±5% or more and ±30% or less) relative to the average coefficient of dynamic friction, which is preferable. Here, a degree of variability in coefficient of dynamic friction (μd) of all the samples means a ratio of the difference between the maximum or the minimum coefficient of dynamic friction and the average coefficient of dynamic friction, whichever larger, to the average coefficient of dynamic friction, when the maximum and the minimum in the coefficient of dynamic friction of all samples are found.
That is, in a polyamide based resin laminated film roll of the present invention, when the coefficient of dynamic friction of the above-mentioned samples (1) through (6) is denoted as μn (n=1 to 6), both the difference between the maximum value μmax of μn and the average coefficient of dynamic friction (μda) and the difference between the minimum value μmin and average coefficient of dynamic friction are preferably within ±30%, in other words, |μda−μn,| (Additionally, | | indicates the absolute value) are preferably 30% or less.
Additionally, in a polyamide based resin laminated film roll of the present invention, a degree of variability in coefficient of dynamic friction (μd) of all the cutout samples is preferably within ±20% relative to the average coefficient of dynamic friction, more preferably within the range of ±15%, and still more preferably within the range of ±10%. In addition, in a polyamide based resin laminated film roll of the present invention, a lower degree of variability in coefficient of dynamic friction (μd) of the all cutout samples is preferable, but it is considered that the lower limit of the degree of variability is limited to about 5% with measurement accuracy taken into account.
In the polyamide based resin laminated film roll of the present invention, it is preferable that the average inorganic particle content, which is the average value of the inorganic particle content of all the cutout samples, are set in a range of 0.01 to 0.05% by weight, and it is not preferable that it is included in a range of 0.05 to 0.3% by weight (Additionally, one example of the measurement method of inorganic particle content will be explained in an Example). When the average inorganic particle content is below 0.01% by weight, satisfactory lubricity under high humidity is unable to be obtained, which is not preferable, and on the contrary, when the average inorganic particle content exceeds 0.5% by weight, it becomes difficult to recover and recycle polyamide resin deleted in the producing process, which is not preferable.
In addition, the polyamide based resin laminated film roll of the present invention must have the degree of variability of inorganic particle content of all the cutout samples adjusted to be in the range of ±2% to ±10% (±2% or more and ±10% or less) of the average content, which is preferable. The degree of variability of inorganic particle content of all the samples referred to here means a ratio of the difference between the maximum or the minimum differences of inorganic particle content and the average difference of inorganic particle content, whichever larger, to the average difference of inorganic particle content, when the maximum and the minimum of inorganic particle content of all samples are found.
That is, in a polyamide based resin laminated film roll of the present invention, it is preferable that when inorganic particle content of samples (1) through (6) is denoted as Cn (n=1 to 6), both the difference between Cmax, the maximum value of Cn and average inorganic particle content (Ca), and the difference between Cmin, the minimum value and average inorganic particle content (Ca) must be within ±10%, in other words, it is preferable that all |Ca−Cn| (Additionally, | | indicates the absolute value) must be 10% or less.
In addition, in a polyamide based resin laminated film roll of the present invention, a degree of variability in the inorganic particle content of all samples cut out is preferably within a range of ±8% relative to the average inorganic particle content, more preferably within a range of ±6%. In addition, in a polyamide based resin laminated film roll of the present invention, a lower degree of variability in the inorganic particle content of all samples cut out is preferable, but it is considered that the lower limit of the degree of variability is limited to about 2% with the measurement accuracy taken into account.
In addition, in a polyamide based resin laminated film roll of the present invention, in the case where a sample is cut out in the foregoing method, when refraction index (Nz) in the thickness direction of all samples are determined, an average refraction index (Nza) which is the average of the refractive indexes is preferably adjusted to be 1.500 or more, 1.520 or less. Additionally, the average refraction index is calculated by the following formula 6.
Nza=summation of Nz's of all samples/number of samples 6
Additionally, Nz value of polyamide based resin laminated film composing polyamide based laminated film roll greatly affects film grade such as laminate strength and thickness irregularity. Thus, the requirement of average refraction index of 1.500 or more and 1.520 or less is an essential requirement in use of biaxially oriented polyamide based resin laminated film laminated with a polyolefin based resin film. When Nz is less than 1.500, laminate strength with a polyolefin based resin film etc., becomes insufficient, which tends to cause peeling between the film and laminated substrate in boiling water treatment after bag forming. Moreover, the Nz is lowered sequentially in a process of biaxial stretching of unstreched polyamide based resin laminated film. In other words, Nz is thought to be an index of stretching, larger Nz indicates insufficient stretching, thus a film with Nz of more than 1.520 remarkably displays thickness irregularity due to insufficient stretching, giving an unsatisfactory film grade. Particularly preferable range of Nz is in a range of 1.507 to 1.516 from the considerations of both laminate strength and film grade.
Also, in a polyamide based resin laminated film roll of the present invention, a degree of variability in the refraction index (Nz) of all samples cut out is preferably adjusted within ±2% relative to the average of refraction indexes (hereinafter called an average refraction index) Here, a degree of variability in the refraction index (Nz) of all samples means, when the maximum and the minimum in the refraction index (Nz) of all samples are obtained, from which a larger value of the difference between either the maximum or the minimum and the average refraction index is obtained, a ratio of which to the average refraction.
Namely, in a polyamide based resin laminated film roll of the present invention, when refraction index of samples (1) through (6) is denoted as Nz1 to Nz6, both the difference between Nzmax, the maximum value of Nz1 to Nz6 and the average refraction index, and the difference between Nzmin, the minimum value of Nz1 to Nz6 and the average refraction index are preferably within ±2%, in other words, all of |average refraction index −Nz1| to |average refraction index −Nz6| are preferably 2% or less. Also, in a polyamide based resin laminated film roll of the present invention, a degree of variability in the refraction index (Nz) of all samples cut out is more preferably within ±1% relative to the average refraction index.
In addition, in a polyamide based resin laminated film roll of the present invention, a lower degree of variability in the refraction index (Nz) of all samples cut out is preferable, but we are considering that the lower limit of the degree of variability is limited to about 0.1% from the considerations of precision in the measurement and precision of machine.
As described above, by adjusting the maximum boiling water shrinkage percentage, directional difference of boiling water shrinkage percentage within given range values, the surface roughness and the like, and also by lowering the degree of variability in the maximum boiling water shrinkage percentage, directional difference of boiling water shrinkage percentage, the surface roughness and the like in one polyamide based resin laminated film roll, it becomes possible to prevent appearance deterioration in bag forming processing and lamination processing, and process the film smoothly with good yield ratio even under high humidity.
As a polyamide resin used in the present invention, for example, there can be listed nylon 6 of ε-caprolactam as a major raw material. Also, as other polyamide resins, there can be listed a polyamide resin obtained by polycondensation of lactam with three-membered ring or more, ω-amino acid, dicarboxylic acid and diamine. Specifically, lactams include enantlactam, capryllactam, lauryllactam other than ε-caprolactam above-mentioned; ω-amino acids include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic and 11-aminoundecanoic acid. Also, dicarboxylic acids include adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedione acid, dodecadione acid, hexadecadione acid, eicosandione acid, eicosadienedione acid, 2,2,4-trimethyladipic acid, terephtahlic acid, isophthalic acid, 2,6-naphtahalene dicarboxylic acid, and xylylenedicarboxylic acid. Further, diamines include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, pentamethylenediamine, undecamethylenediamine, 2,2,4 (or, 2,4,4)-trimethylhexamethylenediamine, cyclohexanediamine, bis-(4,4′-aminocyclohexyl)methane, and methaxylylenediamine. Polymers obtained by polycondensation of these chemicals and copolymers thereof, for example, nylons 6, 7, 11, 12, 6.6, 6.9, 6.11, 6.12, 6T, 6I, MXD6 (methaxylyleneadipamide 6), 6/6.6, 6/12, 6/6T, 6/6I, 6/MXD6 can be used. In addition, in the case of producing polyamide film roll of the present invention, the above polyamide resin can be used alone or in a mixture of 2 kinds or more thereof.
Additionally, of the above polyamide based resins, particularly preferable resin in the present invention has relative viscosity in a range of 2.0 to 3.5. The relative viscosity of polyamide based resin affects toughness of biaxially stretched film obtained and stretching property. That is, when relative viscosity is less than 2.0, impact strength becomes somewhat insufficient, whereas when relative viscosity is more than 3.5, sequentially biaxially stretching property tends to be bad because of increase in stretching stress. Additionally, the relative viscosity in the present invention means a value that a solution of 0.5 g of polymer dissolved in 50 ml of 97.5% sulfuric acid is measured at 25° C.
The polyamide based resin laminated film roll of the present invention is produced by winding up unstretched film (unstretched laminated film or unstretched laminated sheet) obtained by melt-extruding polyamide resin chips, which is a material, in a form of a roll after biaxially stretching in the longitudinal (long direction) direction and transverse (width direction) direction.
The polyamide based laminated film must have a configuration of A/B (two-type two-layer) or A/B/A (two-type three-layer) or A/B/C (three-type three-layer) From the viewpoint of curl, the A/B/A configuration which is symmetrical layer configuration is preferable. Additionally, in the following description, of each layer which composes the laminated film, the layer at the center part which is not located on the outermost side (that is, B-layer in the case of A/B/A or A/B/C layer configuration) and a thick layer in the case of two-types two-layers configuration (that is, B-layer in the case of A/B layer configuration of thin A-layer and a thick B-layer) are called core-layers. In addition, a layer located on the outermost side (that is, A and B layers in the case of A/B layer configuration or A and C layers in the case of A/B/A or A/B/C layer configuration), and a thin layer in the case of two-types two-layers configuration (that is, A layer in the case of A/B layer configuration of thin A-layer and thick B-layer) are called skin layers.
The thickness ratio of each layer of the polyamide based resin laminated film is preferably between 5% and 50% for A-layer or A-layer and C-layer, and more preferably between 10% and 20%, and particularly preferably between 12% and 18%. In the case of two-type and three-layer A/B/A configuration, the thickness ratio of the A-layer of the surface layer described above means the sum of thickness ratios of both surface layers, and in the case of three-type three-layer A/B/C configuration, the thickness ratio of A-layer and C-layer of the surface layer mentioned above means the sum of thickness ratio of both surface layers. When the thickness ratio of A-layer or A-layer and C-layer is less than 5%, the degree of variability of turbidity degree by irregular thickness becomes large and is not preferable. On the other hand, when the thickness ratio of A-layer or A-layer and C-layer exceeds 30%, resistance to bending fatigue is degraded and the number of pinholes increases and at the same time, transparency is degraded, which is not preferable.
Additionally, in order to produce the laminated film as described above, a method for obtaining a practically unoriented polyamide sheet by melting and coextruding each polymer that composes each layer by the use of separate extruders, casting from a nozzle on a rotating drum, and rapidly cooling and solidifying (so-called coextrusion) can be preferably adopted.
Next discussion will be made on a preferable producing process for obtaining a polyamide based resin laminated film roll of the present invention. The present inventors have studied on thickness irregularity of film roll in the longitudinal direction (thickness irregularity throughout the full length of the film roll), and variations and fluctuations of physical properties such as boiling water shrinkage percentage, and as a result, they have found that the thickness irregularity in the longitudinal direction and variation and fluctuations of the physical properties are greatly susceptible to various factors primarily in a casting process for converting the melted resin into unstretched film. That is, if the temperature of resin when it is fed into a funnel-shape hopper (hereinafter referred to as simply a hopper) directly connected to an extruder is low or the temperature of resin of the moisture content of resin fed into the hopper is high, the thickness irregularity in the longitudinal direction in the unstretched film increases and variations and fluctuations of the physical properties in the biaxially stretched film increase. In addition, the present inventors have found that if the contact point between the resin and the meal roll is displaced when the resin extruded from a T-die is wrapped around a metal roll, the thickness irregularity in the longitudinal direction in the unstretched film increases and variations and fluctuations of the physical properties in the biaxially stretched film increase. Furthermore, the inventors also have found that inappropriate stretching conditions in the biaxially stretching process exacerbate thickness irregularity in the longitudinal direction in the unstretched film, and promote variations and fluctuations of physical properties.
Furthermore, the present inventors have keenly studied on the basis of the foregoing facts, and as a result, have identified that taking the following measures at the time of producing the film roll can provide a film roll with little variations in physical properties and with maintain satisfactory lubricity even under high humidity.
In the production of film roll of the present invention, in the case of adopting a blend method, a plurality of polyamide resin chips of raw materials different in composition are blended in a hopper, then melt blended and extruded from an extruder to form a film (additionally, in the production of a film roll of the present invention, as described above, multiple extruders are used). For example, in the case of three kinds of polyamides as feedstock, respective polyamide resin chips are fed into respective three hoppers continuously or intermittently, via a buffer hopper if necessary, and finally while three kinds of polyamide resin chips are being mixed in a hopper just before or just above an extruder (hereinafter called “final hopper”), feedstock chips are quantitatively fed into the extruder in accordance with the extrusion rate of extruder to form a film.
However, depending on a capacity or shape of final hopper, when the remaining amount of chip in the final hopper is large or when the amount of chip in the final hopper becomes small, there occurs a phenomenon of feedstock segregation, namely, a phenomenon in which chip composition fed to an extruder from the final hopper becomes uneven. Also, such segregation phenomenon appears remarkably, in particular when chip shape or specific gravity is different. Further, resulting from such segregation phenomenon, in the case of producing a long film, there occur the variations of maximum boiling water shrinkage, directional difference of boiling water shrinkage, film thickness and refraction index in the thickness direction.
Namely, in the presence of different chip sizes, when a mixture of chips falls in a final hopper, smaller chip is apt to fall first, when the remaining amount of chip in the final hopper becomes small, the ratio of larger chip becomes more, which causes the chip segregation. Therefore, in order to obtain a film with less variation of physical properties, it is necessary to uniform the shape of polyamide resin chip with a plurality of kinds being used to suppress a phenomenon of feedstock segregation in the final hopper (each of final hoppers for feeding the chips to each extruder).
Feedstock chip of polyamide is generally formed by being drawn off in a strand of melted state from polymerization equipment after polymerization, immediately water-cooled, and then cut by a strand cutter. Thus, polyamide chip is of elliptic cylinder with elliptic cross section. As the result of studies on the relationship between shape of polymer chip and feedstock segregation, an average major axis (mm), average minor axis (mm) of elliptic cross section and average chip length (mm) of polyamide chip mixed other than a polyamide chip with the largest amount used is adjusted each within a range of ±20% relative to the average major axis (mm), average minor axis (mm) of elliptic cross section and average chip length (mm) of the polyamide chip with the largest amount used, thereby it becomes possible to reduce the above-mentioned feedstock segregation. Additionally, it is more preferable, to result in a remarkable segregation preventing effect, that an average major axis, average minor axis of elliptic cross section and average chip length of polyamide chip mixed other than a polyamide chip with the largest amount used is adjusted each within a range of ±15% relative to the average major axis, average minor axis of elliptic cross section and average chip length of the polyamide chip with the largest amount used.
(2) Suitable Shape of Hopper
It is effective for reducing feedstock segregation that using a funnel-shaped hopper as a final hopper whose angle of slope is set to 65° or more, thereby large chip can fall easily in the same manner as small chip, and the upper part of contents goes down while keeping its horizontal plane. More preferable angle of slope is 70° or more. Additionally, angle of slope of hopper means an angle between oblique line of hopper and horizontal line segment. A plurality of hoppers may be used in the upstream of final hopper, in this case, any hopper must have an angle of slope of 65° or more, 70° or more is more preferable.
Also, reducing the ratio of fine powder formed due to shaving feedstock chip used is preferable to suppress the variation of boiling water shrinkage percentage. Since the fine powder advances feedstock segregation, it is preferable to eliminate fine powder formed in process to reduce the ratio of fine powder contained in a hopper. The ratio of fine powder contained is preferably within 1% by weight through the entire steps before feedstock chip enters into an extruder, more preferably within 0.5% by weight. As a specific method for reducing the ratio of fine powder, there can be listed a method of sieving in chip forming step by a strand cutter or passing through a cyclone type air filter in transporting feedstock chip with air.
In addition, as a means for reducing feedstock segregation in a hopper, setting a suitable capacity of hopper used is also a preferable means. Here, the suitable capacity of hopper is in a range of 15-120% by weight relative to the extrusion amount per one hour of extruder, more preferable is in a range of 20-100% by weight relative to the extrusion amount per one hour of extruder.
As a method for blending feedstock chips of polyamide having two or more kinds different in composition, the most preferable method is to blend in a hopper (final hopper) just above an extruder while quantitatively feeding each feedstock into the extruder continuously. Also, it is possible to feed into a final hopper and extruder via several intermediate hoppers (buffer hoppers) after premixing feedstock chip whose size is controlled within the range described above. In blending a plurality of feedstock, there can be listed a method of blending while feeding a plurality of feedstock quantitatively into a hopper from an apparatus quantitatively feeding feedstock chip continuously, or a method of blending beforehand using a blender or a paddle drier, in the case of adopting the latter, it is preferable to make the size of feedstock chip small not to generate feedstock segregation in discharging a mixture.
(3) Reduction of Water Content in Drying Resin Chip
Chip fed into a hopper is generally heated by a machine like blender to reduce moisture therein. In drying the chip, it has been thought that the lower content in drying in production of polyester film roll or polypropylene film roll generally yields the better film roll due to suppression of hydrolysis in an extrusion step. However, the following fact has been found from the result of the studies by the present inventors: in production of polyamide based resin laminated film roll, a mere reduction of water content in drying makes stretching difficult to yield no film roll of homogenous physical properties, but the water content is controlled within a given range to reserve some level of moisture, which leads to a suitable plasticization without being hydrolyzed in an extrusion step to thereby give a film roll with homogenous physical properties. Namely, to obtain the film roll of the present invention, it is necessary to control the water content of chip in 800 ppm or more, and 1000 ppm or less. When the water content of chip exceeds 1000 ppm, hydrolysis is advanced when melted, which lowers viscosity. Therefore, thickness irregularity of unstretched film in the longitudinal direction becomes bad and the thickness irregularity of biaxially stretched film in the longitudinal direction is increased, which causes the variation and fluctuation of physical properties. On the other hand, when the water content of chip is less than 800 ppm, viscosity when melted becomes too high, which deteriorates film forming property (ease of stretching) Additionally, most suitable water content of chip fed to a hopper is 850 ppm or more, and 950 ppm or less.
(4) Retention of Temperature in Feeding Resin to Hopper
As described above, even in the case of adjusting water content of chip to 800 ppm or more, and 1000 ppm or less, a film roll with homogenous physical properties cannot be obtained when chip after heat-drying being allowed to stand down to ambient (room) temperature is fed into a hopper. Namely, to obtain a film roll of the present invention, it is necessary to feed into hoppers (each hopper for feeding the chips to each extruder) while keeping the chips heat-dried by blender, etc., at a high temperature. Specifically, it is necessary to feed into a hopper while keeping the chip heat-dried by a blender at 80° C. or more, it is more preferably to feed into a hopper while keeping at 90° C. or more. When the temperature of chip fed to a hopper is below 80° C., resin charging becomes bad. This causes thickness irregularity in the longitudinal direction, and variation and fluctuation of physical properties, which produces no film roll of the present invention. Additionally, in drying chip by a blender etc., drying temperature is required at 150° C. or less. When the drying temperature is above 150° C., it is not preferable because hydrolysis may occur in drying. Also, when the temperature of chip heat-dried by a blender is below 80° C., it is necessary to reheat the chip so as to be 80° C. or more before feeding it into a hopper.
(5) Suction for Contacting Melted Resin with Metal Roll
In obtaining an unstretched film by melt extrusion of chip, chip is melted by each extruder at 200-300° C., and extruded through a T-die to form a laminated film (laminated sheet), (i.e., by casting), then quenched by a method of winding on a cooling roll such as metal roll being cooled at a given temperature. Additionally, from the points of thickness irregularity in the longitudinal direction, and variation and fluctuation of physical properties, preferable temperature of melt extrusion is 240° C. to 290° C. To obtain a film roll of the present invention, in the case of winding melted resin on a metal roll, it is preferable to force the melted resin to contact a metal roll by the following manner: air gap (namely, a distance between the exit of T-die lip and a surface of chilling roll in the vertical direction) is adjusted to 20-60 mm, and the part contacting the melted resin with the surface of cooling roll is sucked over the entire width of melted resin in the opposite direction to the winding direction by utilizing a suction unit such as vacuum box (vacuum chamber) having a wide suction inlet. Also, in this case, wind velocity of suction air in the suction inlet must be adjusted to 2.0-7.0 m/sec., and it is more preferably adjusted to 2.5-5.5 m/sec. Further, vacuum box may have a single suction inlet, and it is preferable that the suction inlet divided into a predetermined number of sections in the lateral direction can adjust the wind velocity of suction in each section to make the adjustment of wind velocity of suction easy in the suction inlet. Also, when the casting speed increases, accompanying stream takes place according to the rotation of metal roll, which disturbs close contact of melted resin with a metal roll, thus to make suction more effective by a suction unit, and to improve close contact of melted resin with the metal roll, it is preferable to shield the accompanying stream by equipping a masking shield of flexible material like Teflon being formed in broad range in the upstream adjacent to the suction unit (the opposite side to the rotation direction of metal roll relative to the suction unit). Further, to obtain a film roll of the present invention, fluctuation of wind velocity of suction (set value) in a vacuum box is required to be suppressed within ±20% to the average wind velocity of suction, more preferably suppressed within ±10%. In addition, to prevent wind velocity of suction in a vacuum box from variation due to oligomer dust etc., it is preferable to control suction power by equipping a filter in a vacuum box and feed back the differential pressure across the filter.
Furthermore, in order to obtain a film roll of the present invention, it is necessary to apply direct current negative electric charges of 90-105 mA at 2-15 kV from a needle-like electrode to a melted resin sheet when the melted resin is wrapped around a cooling roll, and to continuously bring in contact with the metal roll and rapidly cool while glow-discharging. Additionally, in such event, adjusting the direct current negative electric charge to be applied to a range from 7 to 14 kV reduces thickness irregularity in the longitudinal direction as well as variations and fluctuations of physical properties, which is preferable. In addition, in order to obtain the film roll of the present invention, it is necessary to suppress variations of direct current negative electric charge to be applied within ±20% of the average negative electric charge (set value) and more preferably to suppress within ±10%.
(6) Suitable Stretching Condition
As a method of biaxially stretching an unstretched film, it is necessary to adopt a longitudinal and transverse stretching method that an unstretched film is stretched by a roll-type stretching machine in the longitudinal direction, stretched by a tenter-type stretching machine in the transverse direction, then thermally fixed and relaxed. Further, to obtain a film roll by the present invention, as a method of biaxial stretching, it needs to adopt so called longitudinal-longitudinal-transverse stretching method. Such the longitudinal-longitudinal-transverse stretching method is the following method: in longitudinal-stretching of an essentially unoriented polyamide film, the first-stage stretching is conducted, without cooling at Tg or less, and continuously the second-stage stretching is conducted, and then transverse stretching is conducted in a ratio of 3.0 times or more, preferable 3.5 times or more, and further thermally fixed. Moreover, to obtain a film roll of the present invention, in conducting the longitudinal-longitudinal-transverse stretching described above, a longitudinal stretching ratio in the first stage must be higher than a longitudinal stretching ratio in the second stage. Namely, by setting a longitudinal stretching ratio in the first stage higher than a longitudinal stretching ratio in the second stage, it becomes possible to obtain a film roll having excellent physical properties such as boiling water shrinkage percentage and less fluctuation of these physical properties. Additionally, in the case of conducting the longitudinal-longitudinal-transverse stretching, generally, when a longitudinal stretching ratio in the first stage is lower than a longitudinal stretching ratio in the second stage, stretching is easily carried out without adhesion on a roll in the first stage. On the other hand, even when a longitudinal stretching ratio in the first stage is higher than a longitudinal stretching ratio in the second stage, stretching can be easily carried out without adhesion on a roll by using a special roll such as roll made of Teflon (registered trademark).
In the case of conducting the longitudinal-longitudinal-transverse stretching described above, it is preferable that a longitudinal stretching in the first stage is carried out in a temperature of 80-90° C. and a ratio of about 2.0-2.4 times. It is not preferable that the stretching ratio in the first stage is high beyond the foregoing range because thickness irregularity in the longitudinal direction becomes large. In addition thereto, it is preferable that a longitudinal stretching in the second stage is carried out in a temperature of 65-75° C. and a ratio of about 1.3-1.7 times. It is not preferable that the stretching ratio in the second stage is low beyond the foregoing range because distortion in boiling is too large to have a practical use. Reversely, it is not preferable that the stretching ratio in the second stage is high beyond the foregoing range because strength (strength at 5% extension) in the longitudinal direction is too low to have a practical use.
Also, in the case of conducting the longitudinal-longitudinal-transverse stretching described above, a longitudinal stretching method can employ a heated roll stretching or an infrared radiation stretching. Also, in the case where a polyamide based resin laminated film roll of the present invention is produced by such longitudinal-longitudinal-transverse stretching method, it is possible to reduce not only thickness irregularity, the variation and fluctuation of physical properties in the longitudinal direction but also the variation and fluctuation of physical properties in the transverse direction. Also, in the case of conducting the longitudinal-longitudinal-transverse stretching, the total longitudinal stretching condition is preferably 3.0 to 4.5 times.
Also, in the case of conducting the longitudinal-longitudinal-transverse stretching, it is preferable that transverse stretching is carried out in a temperature of 120-140° C. and a ratio of about 4.0-5.5 times. It is not preferable that the transverse stretching ratio is low beyond the foregoing range because strength (strength at 5% extension) in the transverse direction is too low to have a practical use, reversely, it is not preferable that the transverse stretching ratio is high beyond the foregoing range because thermal shrinkage in the transverse direction becomes high. Moreover, it is not preferable that temperature in transverse stretching is low beyond the foregoing range because distortion in boiling is too large to have a practical use, reversely, it is not preferable that temperature in transverse stretching is high beyond the foregoing range because strength (strength at 5% extension) in the transverse direction is too low to have a practical use.
Further, to obtain a film roll of the present invention, thermal fixation treatment after the longitudinal-longitudinal-transverse stretching is preferably conducted in a temperature of 180-230° C. When the temperature in the thermal fixation treatment is low beyond the foregoing range, it is not preferable because thermal shrinkage in the longitudinal direction and transverse direction is large, and reversely, when the temperature in the thermal fixation treatment is high beyond the foregoing range, it is not preferable because impact strength of biaxially stretched film becomes low.
In addition, to obtain a film roll of the present invention, relaxation treatment after thermal fixation is preferably carried out in a relaxation of 2-10%. When the relaxation treatment ratio is low beyond the foregoing range, it is not preferable because thermal shrinkage in the longitudinal direction and transverse direction becomes large, and reversely, when the relaxation treatment ratio is high beyond the foregoing range, it is not preferable because strength (strength at 5% extension) in the longitudinal direction and the width direction is too low to have a practical use.
Also, width of film roll is not particularly limited, but the lower limit of width of film roll is preferably 0.35 m or more from the point of easy handling, more preferably 0.50 m or more. On the other hand, the upper limit of width of film roll is preferably 2.5 m or less, more preferably 2.0 m or less, and further preferably 1.5 m or less. In addition, winding length is also not particularly limited, but the lower limit of width of film roll is preferably 500 m or more from the points of easy winding and easy handling, more preferably 1000 m or more. On the other hand, the upper limit of winding length of film roll is preferably 25000 m or less, more preferably 20000 m or less, and further preferably 15000 m or less. Additionally, in the case of film thickness of about 15 μm, 12000 m or less is particularly preferable. Also, winding core can ordinarily employ a paper, plastic or metal core with 3 inches, 6 inches, 8 inches and the like.
Moreover, thickness of film composing polyamide based resin laminated film roll of the present invention is also not particularly limited, for example, as a polyamide based film for packaging, 8-50 μm is preferable, 10-30 μm is further preferable.
In addition, a polyamide based resin laminated film that composes the film roll of the present invention can contain various kinds of additives, within the range that the characteristics are not damaged, such as lubricant, anti-blocking agent, thermal stabilizer, antioxidant, antistatic agent, light resistant agent, and impact modifier. In particular, it is preferable to contain various kinds of inorganic particles so as to improve lubricity of biaxially stretched film. Furthermore, it is preferable to add an organic lubricant such as ethylene-bis-stearic acid, etc. which exhibits the effect of lowering surface energy because excellent lubricity can be imparted to the film that composes the film roll.
Further, polyamide based resin laminated film composing a film roll of the present invention can be subjected to thermal treatment or humidity adjusting treatment to improve the dimensional stability according to the applications. In addition, it can be provided with corona treatment, coating treatment or flame treatment to give better adhesion of film surface, and also processed by printing, deposition or the like.
(7) Use of High-concentration Material Chips
As described above, in order to improve the lubricity under high humidity of the biaxially oriented film, it is preferable to allow various inorganic particles to be contained in polyamide based resin and adjust the surface roughness of the film but in such event, by adding inorganic particles by a specific addition method, satisfactory lubricity under high humidity can be developed. That is, when inorganic particles are added to polyamide based resin, it is preferable not to add and knead powdery inorganic particles in an extruder but to adopt a method for preparing master batch polymer chips with high-concentration inorganic particles added in polyamide based resin in advance and blend-diluting the master chips (high-concentration material chips) with polyamide based resin free of inorganic particles. By adopting this kind of means, dispersibility of inorganic particles is improved by allowing inorganic particles to grind one another on a melt-line, and as a result, good effect would be exerted on the lubricity under high humidity.
Furthermore, it is preferable to add inorganic particles to polyamide based resin by 5-20% by weight when high-concentration material chips are produced, and more preferable to add by 10-15% by weight. When the adding amount of the inorganic particles exceeds 20% by weight, the dispersibility of inorganic particles is lowered, and a possibility of forming foreign matters in the film are generated, which is not preferable. On the contrary, when the adding amount of the inorganic particles exceeds 5% by weight, the economic efficiency is degraded, which is not preferable. In addition, when such high-concentration material chips are prepared, kneading with inorganic particles after polyamide resin is made into powdery fine particles by a method of pulverizing in a frozen state, the dispersibility of inorganic particles into the resin is improved, which is preferable.
(8) Adjustment of Inorganic Particle Characteristics
It becomes possible to develop satisfactory lubricity under high humidity by specializing the characteristics of inorganic particles to be added to polyamide resin that composes the skin layer when organic particles are added to polyamide based resin. That is, for inorganic particles to be added, those with an average particle size (that is, average particle size) of 0.5 to 5.0 μm are preferable and silica particles are particularly preferable. When the average particle size is below 0.5 μm, no satisfactory lubricity can be obtained, whereas when the average particle size exceeds 0.5 μm, it is not preferable because transparency becomes poor and so called “strike-through” on printing occurs. Additionally, the average particle size can be measured by employing a method in which a weight-average diameter can be calculated from a particle distribution obtained by a Coulter counter, it can be determined from the measurement of particles before addition to polyamide resin, and also can be determined from the measurement of particle separated out by dissolving polyamide based resin laminated film in acid. In addition, it is preferable that the pore volume of inorganic particles is between 0.5 and 2.0 mL/g, and more preferably between 0.8 and 1.5 mL/g. When the pore volume is below 0.5 mL/g, film transparency is degraded, which is not preferable. When the pore volume exceeds 2.0 mL/g, film lubricity is degraded, which is not preferable. In addition, it is preferable not only to add inorganic particles in polyamide resin that composes the skin layer but also to add a small amount of inorganic particles by 0.001 to 0.005% by weight in polyamide resin that composes the core layer because the lubricity under high humidity can be remarkably improved, and it is more preferable to add inorganic particles by 0.002 to 0.004% by weight. In addition, it is preferable to make the particle size of inorganic particles to be added to the core layer greater than the thickness of the skin layer because more stable lubricity under high humidity can be achieved. Additionally, it is not clear why the lubricity under high humidity becomes stable in such a manner but the inventors of the present invention consider that the undulation action of the film surface by inorganic particles in the core layer exerts good effects on the lubricity under the high humidity.
(9) Adjustment of Lamination Mode of Film
As described above, by adding inorganic particles to polyamide based resin and forming unevenness on the film surface, lubricity is able to be developed, but in such event, by adjusting the film lamination mode, it becomes possible to develop satisfactory lubricity under high moisture. That is, in the production of the film roll of the present invention, using the coextrusion as described above and melt-extruding resin from multiple extruders, laminated film (laminated sheet) with multiple layer structure is formed, but in such event, it is preferable to adjust the discharge rate of resin melt-extruded as a skin layer in such a manner that the final skin layer thickness after stretching becomes 0.5 to 4.0 μm, and is more preferable to adjust to be 1.0 to 3.0 μm.
Additionally, when the unstretched laminated film is formed, it becomes possible to reduce the thickness irregularity of each layer which composes laminated film by using the means of Paragraphs (1) through (4) as well as Paragraphs (7) through (9) and by using the means of Paragraphs (5) and (6) in the unstretched laminated film stretching process, and eventually, the thickness irregularity of the overall laminated film can be reduced. Then, it is assumed due to this, it would be possible to reduce the variations of physical properties of the film roll remarkably efficiently. It should be noted that any specific one of the means of Paragraphs (1) through (9) only can effectively contribute to reduction of variations of physical properties of the film roll but by using the means of Paragraphs (1) through (9) in combination, it is assumed that the variations of physical properties of the film roll can be very efficiently reduced.
The present invention will be described in detail with reference to Examples below, but it should be noted that the present invention is not limited to the aspects of Examples and can be preferably modified to the extent not departing from the spirit of the present invention. Tables 1 through 3 show properties of material chips A through E used in Examples and comparative examples, composition of material chips used in Examples and comparative examples, and film-forming conditions of film rolls in Examples and comparative examples, respectively. Additionally, chip A consists of 94.85% by weight of nylon 6 (relative viscosity=2.8, Tg=41° C.), 5.00% by weight of polymethaxylyleneadipamide (relative viscosity=2.1), and 0.15% by weight of ethylene bisstearic acid amide and chip B consists of 99.85% by weight of nylon 6 (same physical properties of chip A) and 0.15% by weight of ethylene bisstearic acid amide. In addition, chips C and E consist of 85.00% by weight of nylon 6 (same physical properties of chip A) and 15.0% by weight of silica particles of 2.0 μm in average particle size and 1.2 mL/g of pore volume, and chip D consists of 95.00% by weight of nylon 6 (same physical properties of chip A) and 5.0% by weight of silica particles of 2.0 μm in average particle size and 1.6 mL/g of pore volume. Furthermore, the shapes of chips A through E are all elliptic cylinders, while chips A through D have identical in cross sectional major axis, cross sectional minor axis, and chip length.
By using co-extrusion, from three extruders (Extruders No. 1 through No. 3), polyamide based resin was melt-extruded (laminated in a die and extruded), wrapped around a rotating metal roll cooled to 17° C. and rapidly cooled, and an unstretched film (polyamide based resin laminated sheet) in a thick of 257 μm and of two-types three-layer structure was obtained. The method of forming each layer of unstretched film (process up to melt-extrusion) is described as follows. Additionally, in the following description, the laminated layers are called a first layer, a second layer, and a third layer successively from the surface layer of the polyamide based resin laminated film (that is, the surface of the third layer is the contact surface of the metal roll).
Formation of the First Layer (Outer Layer)
The above-described chips A and C were separately pre-dried while heating at about 120° C. for about 8.0 hours using a blender apparatus of 15 kl. Each chip was sampled from the blender by a predetermined amount and its water content was measured to find that chips A and C both had 800 ppm of water content. Additionally, the water content was measured under the conditions of sample weight of 1 g and sample heating temperature of 230° C. using a Karl Fisher moisture meter (MKC-210 manufactured by KYOTO Electronics Corp.).
Then, chips A and C in each blender were separately supplied to a hopper just above an extruder (extruder No. 1) continuously by a quantitative screw feeder. Additionally, the amount supplied of chip A was set as 99.5% by weight and the amount supplied of chip C was set as 0.5% by weight. The hopper had a capacity to contain 150 kg of material chips, and the hopper inclination angle was adjusted to 70°.
Also, in feeding chips A and C into a hopper, the chips were fed in a short period of time from drying to the hopper so that the temperature of chip in each blender did not become too low. The temperature of both chips A and C just before being fed into the hopper was about 91° C. Then, the chips A and C fed were blended in the hopper, melt-extruded through a T-die at 270° C. from a single screw type extruder.
Formation of the Second Layer (Intermediate Layer)
Chips A and C dried as described above in each blender were separately supplied to a hopper just above an extruder (extruder No. 2) continuously by a quantitative screw feeder. Additionally, the amount supplied of chip A was 99.97% by weight and the amount supplied of chip C was set as 0.03% by weight. The hopper had a capacity to contain 150 kg of material chips and the hopper inclination angle was adjusted to 70°.
Furthermore, when chips A and C were supplied into the hopper, chips were supplied into the hopper in a short time from drying so that the temperature of chips inside each blender does not drop excessively. Temperatures of chips A and C just before they are supplied to the hopper were about 91° C. in both cases. Then, chips A and C supplied were mixed in the hopper and melt-extruded at 270° C. from a T-die by the monoaxial type extruder No. 2.
Formation of the Third Layer (Inner Layer)
Chips A and C dried as described above in each blender were separately supplied to a hopper just above an extruder (extruder No. 3) continuously by a quantitative screw feeder. Additionally, the amount supplied of chip A was set as 99.5% by weight and the amount supplied of chip C was set as 0.05% by weight. The hopper had a capacity to contain 150 kg of material chips and the hopper inclination angle was adjusted to 70°.
Furthermore, when chips A and C were supplied into the hopper, chips were supplied into the hopper in a short time from drying so that the temperature of chips inside each blender does not drop excessively. Temperatures of chips A and C just before they are supplied to the hopper were about 91° C. in both cases. Then, chips A and C supplied were mixed in the hopper and melt-extruded at 270° C. from a T-die by the monoaxial type extruder No. 3.
Additionally, in each extruder of example 1, the average major axis, average minor axis, and average chip length of the polyamide based resin chip (chip C) other than the polyamide based resin chip with the largest amount used were included in the range of ±20%, respectively, with respect to the average major axis, average minor axis, and average chip length of the polyamide based resin chip with the largest amount used (chip A). The discharge rate of the extruders No. 1 through No. 3 in forming the unstretched film was adjusted in such a manner that the thickness ratio of the first layer/the second layer/the third layer achieves 2/11/2.
Also, an air gap in winding melted resin around a metal roll was adjusted to 40 mm, by applying a direct current negative charge of 100 mA at 11±1.1 kV with a needle electrode to yield glow discharge, and melted resin was electrostatically attached closely on the metal roll. Further, in winding melted resin around a metal roll, the part contacting the melted resin with the metal roll was sucked over the entire width of melted resin by using a vacuum box in the opposite direction to the direction of winding the resin to promote close contact of the melted resin with the metal roll. Additionally, the suction wind velocity of the vacuum box was adjusted to be 5.0±0.5 m/sec. throughout the full width of suction inlet (that is, full width of melted resin).
Thereafter, the resultant unstretched film was longitudinally stretched (first longitudinal stretching) in stretching temperature of about 85° C. and about 2.1 times by a Teflon roll (registered trademark), then longitudinally stretched (second longitudinal stretching) in stretching temperature of about 70° C. and about 1.6 times by a ceramic roll. Further, the longitudinal stretched sheet was continuously led to a tenter, transversely stretched at about 130° C. and 4.0 times, thermally fixed at about 210° C., subjected to transverse relaxation treatment of 5.0% and then cooled, by cutting the both edge parts to eliminate, thereby to form a biaxially stretched film of about 15 μm and 2000 m or more continuously and produce a mill roll. When the laminated film obtained after biaxially stretching was sliced thinly in the thickness direction and observed by electron microscope, the thickness of the first layer, the second layer, and the third layer were about 2 μm, about 11 μm, and about 2 μm, respectively.
Additionally, the variation widths of film surface temperature when a film is produced continuously in 2000 m were within ±0.8° C. to the average temperature in the pre-heating step, ±0.6° C. to the average temperature in the stretching step and ±0.5° C. to the average temperature in the thermal treatment step. Further, the resultant mill roll was slit into 400 mm in width and 2000 m in length, and winded up on 3 inch paper tube to give two polyamide based resin film rolls (slit rolls). Then, using the two slit rolls thus obtained (namely, obtained from the same mill roll), the characteristics were evaluated in the following methods. Additionally, for the following measurements of BS (boiling water shrinkage percentage), BSx (maximum boiling water shrinkage percentage), BSd (directional difference of boiling water shrinkage percentage) and refraction index, sample films were prepared as follows: a first sample cutout portion was set up within 2 m from the winding end of film, sample cutout portions from a second to 20th were set up in approximately every 100 m from the first sample cutout portion, a 21st cutout portion was set up within 2 m from the winding start of film, and sample films were cut out from each of cutout portions from the first to the 21st. The evaluation results are shown in Tables 4 to 7. In showing the evaluation results, an average of values of each sample measured and variation range of values of each sample are shown for impact strength and laminate strength. Also, regarding the S-shaped curl, the numbers of samples determined in each evaluation level and the total evaluation level of all samples are shown.
[Boiling Water Shrinkage Percentage]
A biaxially oriented polyamide based resin laminated film (sample film) cut out from each of cutout portions of one slit roll was cut out in a square with a side of 21 cm, allowed to stand in an atmosphere of 23° C. and 65RH % for two hours or more. A circle of about 20 cm in diameter centered on this sample was drawn, a longitudinal direction (direction of film drawn out) was set to be 0°, liner lines passing to the center of circle were clockwise drawn at intervals of 15° in the direction of 0 to 165°, and diameter in each direction was measured as the length before treatment. Then, after the sample cut out was thermally treated in boiling water for 30 minutes, it was brought back and water attached on the surface was wiped out, dried in air, allowed to stand in an atmosphere of 23° C. and 65% RH for 2 hours or more, as described above, and the length of linear line drawn to each diametrical direction was measured as the length after treatment. Then, according to the foregoing formulas 1 to 5, the following values were measured, which were, the BS (boiling water shrinkage percentage), BSx (maximum boiling water shrinkage percentage), BSax (average boiling water shrinkage percentage), BSd (directional difference of boiling water shrinkage percentage) and BSad (average directional difference of boiling water shrinkage percentage).
Thereafter, the maximum and the minimum of the maximum boiling water shrinkage percentage (BSx) of all samples were obtained, a larger difference between either the maximum or the minimum and the average boiling water shrinkage percentage (BSax) was calculated, a ratio of which relative to the average boiling water shrinkage percentage (BSax) was calculated, and thereby a degree of variability in the maximum boiling water shrinkage percentage (BSx) relative to the average boiling water shrinkage percentage (BSax) was obtained. Also, the maximum and the minimum of the directional difference of boiling water shrinkage percentage (BSd) of all samples were obtained, a larger difference between either the maximum or the minimum and the average directional difference of boiling water shrinkage percentage (BSad) was calculated, a ratio (%) of which relative to the average directional difference of boiling water shrinkage percentage (BSad) was calculated, and thereby a degree of variability in the directional difference of boiling water shrinkage percentage (BSd) relative to the average directional difference of boiling water shrinkage percentage (BSad) was obtained.
[Three-dimensional Surface Roughness]
The surface of biaxially oriented polyamide based resin laminated film (sample film) cut out from each cutout portion of one side of the slit roll was measured over a measured length of 1 mm at the cutoff value of 0.25 mm in the longitudinal direction of the film by using a needle contact type three-dimensional surface roughness measuring machine (SE-3AK available from Kosaka Laboratory Ltd.) set at stylus radius of 2 μm, load of 30 mg, and stylus speed of 0.1-mm/s, and was divided into 500 points at intervals of 2 μm, and the surface was measured in the width direction of the film over a measured length of 0.3 mm under the conditions same as described above and was divided into 150 points at intervals of 2 μm. The height in the three-dimensional direction of each point of divided points obtained was analyzed by the use of a three-dimensional surface roughness analyzer (TDA-21 available from Kosaka Laboratory Ltd.), and the three-dimensional average surface roughness (nm) was determined.
[Coefficient of Dynamic Friction μd Under High Humidity]
By using the biaxially oriented film cut out from each cutout portion of a slit roll, in compliance with JIS-C2151, the coefficient of dynamic friction between outer layers were evaluated under the following conditions:
Haze was measured by the use of a haze meter (300A available from Nippon Denshoku Industries Co., Ltd.) for each biaxially oriented film cut out from each cutout portion of a slit roll in compliance with JIS K7 136. Additionally, the measurement was conducted twice and the average value was determined.
[Content of Inorganic Particles]
The weight of residue was determined when the biaxially oriented film cut out from each cut out portion of a slit roll was combusted at 800° C., and the ratio (percentage) of the residue weight to the film weight before combustion was calculated as the content of inorganic particles. Additionally, in measurement of the content of inorganic particles, a method of determining the weight of residues when the biaxially oriented film cut out from each cutout portion is dissolved in a solvent such as sulfuric acid and calculating the ratio (percentage) of the residue weight to the initial film weight can also be adopted.
[Thickness Irregularity in the Longitudinal Direction]
A slit roll for measurement of thickness irregularity was prepared by slitting a slit roll in about 3 cm width over the entire length in the longitudinal direction. Then, the average thickness, the maximum thickness and the minimum thickness were obtained over the entire length in the longitudinal direction using a thickness irregularity measuring apparatus (wide range high sensitive electronic micrometer K-313A) manufactured by Anritsu Corp. Thereafter, from the following formula 7, a degree of variability in thickness over the entire length in the longitudinal direction was calculated as follows: a larger difference between either the maximum thickness or the minimum thickness and the average thickness was calculated, a ratio of which relative to the average thickness was calculated to give the degree of variability in thickness over the entire length in the longitudinal direction.
Degree of variability in thickness=|maximum thickness or minimum thickness−average thickness|/average thickness 7
[Refraction Index]
Using an “Abbe refractometer 4T type” manufactured by Atago Co., Ltd, each sample film cut out from each of cutout portions was allowed to stand in an atmosphere of 23° C. and 65RH % for 2 hours or more, then refraction index in the thickness direction (Nz) was measured. Also, the average refraction index of all samples was calculated, as shown in Table 6, the difference between either the maximum or the minimum of Nz in all samples and the average refraction index was calculated and a ratio of which relative to the average refraction index was calculated as a degree of variability.
[Impact Strength]
Each sample film cut out from each of cutout portions was allowed to stand in an atmosphere of 23° C. and 65RH % for 2 hours or more, then breaking strength was measured using a “Film impact tester TSS type” manufactured by Toyo Seiki Seisaku-Sho, Ltd. with hemispheric collision ball of 12.7 mm in diameter, and the strength was defined as impact strength. The average impact strength of all sample films was also calculated.
[Lamination Processability]
Using another slit roll (obtained from the same mill roll) different from a slit roll by which the above-described boiling water shrinkage percentage, thickness irregularity in the longitudinal direction, refraction index and impact strength were measured, a laminated film roll with a three layer laminated structure consisting of polyamide based resin/LDPE/LLDPE was obtained as follows: to a biaxially oriented polyamide resin laminated film composing the slit roll, urethane based AC agent (“EL443” manufactured by Toyo-Morton, Ltd.) was coated, and then, on which LDPE (low density polyethylene) film of 15 μm in thickness was continuously extruded at 315° C. using a single test laminator apparatus manufactured by Modern Machinery Ltd., and further LLDPE (linear low density polyethylene) film of 40 μm in thickness was continuously laminated thereon. Also, processability in producing a laminated film roll was evaluated as the following three levels. Additionally, the temperature when lamination processability was evaluated was about 25° C. and the humidity was about 75% RH.
Also, a laminate film cut out from the laminate film roll was cut out in 15 mm wide and 200 mm long as a sample piece, and peel strength between polyamide based resin laminated film layer and LDPE layer was measured under the conditions of temperature of 23° C. and relative humidity of 65% using “Tensiron UMT-II-500 type” manufactured by Toyo Boldwin Co. Ltd. Additionally, pulling rate was 10 cm/min., peeling angle was 180 degree, and the measurement was carried out with a peeling part immersed in water. Also, in the measurement of laminate strength, a first sample piece was cut out within 2 m from the winding end of laminate film roll, sample pieces of a second to 20th were cut out in approximately every 100 m from the first sample cutout portion, a 21st sample piece was cut out within 2 m from the winding start of film, and each sample piece from the first to the 21st was measured. The average of the measurements was also calculated.
[S-shaped Curl Phenomenon]
As described above, the laminate film winded out as a laminate film roll was two folded parallel to the winding length direction while continuously conducting heat-sealing on each of both edges in 20 mm at 150° C. in the longitudinal direction using a test sealer manufactured by Nishibe Kikai Co. Ltd. Then, the film was intermittently heat-sealed at intervals of 150 mm in 10 mm in the perpendicular direction thereto to obtain a half-finished product with width of 200 mm. This product was cut in the winding length direction so that both edges have a sealed part of 10 mm, then cut at the boundary of the sealed part in the perpendicular direction thereto, and thereby to prepare a three-edge sealed bag (seal width: 10 mm). Of the three-edge sealed bags, the three-edge sealed bag prepared from the portion within 2 m from winding end of laminate film roll was selected as a first sample, and the three-edge sealed bags prepared from the portions being about 100, 200, . . . 1800, 1900 m apart from the prepared portion of the first sample were selected as a second to 20th sample, respectively, and the three-edge sealed bag prepared from the portion within 2 m from winding start of laminate film roll was selected as a 21st sample. Thereafter, these twenty-one three-edge sealed bags were thermally treated in boiling water for 30 minutes, then allowed to stand in an atmosphere of 23° C. and 65RH % overnight, and further, the twenty-one three-edge sealed bags were overlapped, and 1 kg load was applied on the entire surface of bag from above, being kept overnight, and followed by removing the load. The degree of warpage of bag (S-shaped curl) was evaluated as follows.
When chips A and C in each blender were supplied to a hopper just above the extruder No. 1 as well as the extruder No. 3 in forming the first layer and the third layer, the amount supplied of chip A was set as 99.0% by weight and the amount supplied of chip C was 1.0% by weight, and at the same time, when chips A and C in each blender to a hopper just above the extruder No. 2 in forming the second layer, the amount supplied of chip A was set as 99.94% by weight and the amount supplied of chip C was set as 0.06% by weight. Except for these, all other conditions were same as those of Example 1 and a polyamide based resin laminated film roll was obtained Then, the characteristics of the obtained film roll were evaluated by the method same as that of Example 1. Tables 4 through 7 show the evaluation results.
A polyamide based laminated film roll was obtained in the same manner as in the case of Example 1, except for adjusting the discharge rates of extruders No. 1 through No. 3 in such a manner that the thickness ratio of the first layer/the second layer/the third layer becomes 1/13/1 when material chips were melt-extruded from the extruder No. 1 through No. 3. The lamination film obtained after biaxial stretching was thinly sliced in the thickness direction and observed by electron microscope, and the thicknesses of the first layer, the second layer, and the third layer were about 1 μm, about 13 μm, and about 1 μm, respectively. Then, the characteristics of the obtained film roll were evaluated by the method same as that of Example 1. Tables 4 through 7 show the evaluation results.
A polyamide based laminated film roll was obtained in the same manner as in the case of Example 1, except for using material chip B in place of material chip A (that is, in Example 4, in the polyamide based resin that composes the first layer through third layer, no polymethaxylyleneadipamide was not contained). Then, the characteristics of the obtained film roll were evaluated by the method same as that of Example 1. Tables 4 through 7 show the evaluation results.
When an unstretched laminated resin sheet is formed, a polyamide based laminated film roll was obtained in the same manner as in the case of Example 1, except for forming no third layer and adjusting the discharge rates of the extruders No. 1 and No. 3 in such a manner that the thickness ratio of the first layer/the second layer becomes 2/13. The lamination film obtained after biaxial stretching was thinly sliced in the thickness direction and observed by electron microscope, and the thicknesses of the first layer (outer layer) and the second layer (inner layer) were about 2 μm and about 13 μm, respectively. Then, the characteristics of the obtained film roll were evaluated by the method same as that of Example 1. Tables 4 through 7 show the evaluation results.
As the material for forming the first and the third layers, material chip D was used in place of material chip C, and the amount supplied of chip A to the extruders No. 1 and No. 3 in forming the first and the third layers was set as 94.0% by weight and the amount supplied of chip D was set as 6.0% by weight, and at the same time, the amount of chip A supplied to the extruder No. 2 in forming the second layer was 99.6% by weight and the amount supplied of chip C was set as 0.4% by weight. Except for these, all other conditions were same as those of Example 1 and a polyamide based resin laminated film roll was obtained. Then, the characteristics of the obtained film roll were evaluated by the method same as that of Example 1. Tables 4 through 7 show the evaluation results.
An unstretched film (laminated film) obtained in the same manner as in Example 1 was longitudinally stretched (first longitudinal stretching) at stretching temperature of about 90° C. and about 2.2 times by a Teflon (registered trademark) roll, and then longitudinally stretched (second longitudinal stretching) at stretching temperature of about 70° C. and about 1.5 times by a ceramic roll. Further, in the same manner as in Example 1, the longitudinally stretched sheet was continuously led to a stenter, and transversely stretched at about 130° C. and 4.0 times. Then, it was thermally fixed at about 210° C., subjected to transverse relaxation treatment of 5.0% and cooled. Then, by cutting the both edge parts to eliminate, a biaxially stretched film of about 15 μm and 2000 m or more continuously was formed. Additionally, the variation width of film surface temperature when the film was continuously produced was the same as in Example 1. The obtained biaxially stretched film was slit and winded up in the same manner as in Example 1, to give polyamide based resin laminated film rolls. Then, the characteristics of the obtained film rolls were evaluated in the same methods as in Example 1. The evaluation results are shown in Tables 4 to 7.
An unstretched film (laminated film) obtained in the same manner as in Example 1 was longitudinally stretched in two stages in the same manner as in Example 1. Thereafter, the longitudinally stretched sheet continuously led to a stenter, transversely stretched at about 130° C. and 3.6 times. Then, it was thermally fixed at about 215° C., subjected to transverse relaxation treatment of 3.0% and cooled. Then, by cutting the both edge parts to eliminate, a biaxially stretched film of about 15 μm and 2000 m or more continuously was formed. Additionally, the variation width of film surface temperature when the film was continuously produced was the same as in Example 1. The obtained biaxially stretched film was slit and winded up in the same manner as in Example 1, to give polyamide based resin laminated film rolls. Then, the characteristics of the obtained film roll were evaluated in the same methods as in Example 1. The evaluation results are shown in Tables 4 to 7.
A polyamide based resin laminated film roll was obtained in the same manner as in Example 1 except that an angle of slope of hopper was changed to 65° in supplying feedstock chip in a blender into a hopper just above first to third extruders. Then, the characteristics of the obtained film roll were evaluated in the same methods as in Example 1. The evaluation results are shown in Tables 4 to 7.
A polyamide based resin film roll was obtained in the same manner as in the case of Example 1, except for adopting a single layer without forming the second and the third layers when an unstretched resin sheet was formed and using only material chip A as the material for forming the first layer. Then, the characteristics of the obtained film roll were evaluated by the method same as that of Example 1. Tables 4 through 7 show the evaluation results.
A polyamide based resin laminated film roll was obtained in the same manner as in Example 1 except that feedstock chip E was used instead of feedstock chip C. Additionally, in Comparative example 2, the polyamide based resin chip (chip E) other than the polyamide based resin chip with the largest amount used comprises each its average major axis and average chip length outside the range of ±20% relative to the average major axis and average chip length of the polyamide based resin chip with the largest amount used (chip A). Then, the characteristics of the obtained film roll were evaluated in the same methods as in Example 1. Tables 4 to 7 show evaluation results.
A polyamide based resin laminated film roll was obtained in the same manner as in Example 1 except that an angle of slope of each hopper was changed to 45° in supplying feedstock chip in a blender into each hopper just above first to third extruders. Then, the characteristics of the obtained film roll were evaluated in the same methods as in Example 1. Tables 4 to 7 show evaluation results.
A polyamide based resin laminated film roll was obtained in the same manner as in Example 1 except that feedstock chips A and C were allowed to stand in each of blenders for about 5 hours after pre-drying before being fed into each hopper just above first to third extruders. Additionally, the water contents of chips A and C were both 800 ppm just before being fed to each hopper, and the temperatures of chips A and C just before being fed to each hopper were both about 30° C. Then, the characteristics of the obtained film roll were evaluated in the same methods as in Example 1. Tables 4 to 7 show evaluation results.
A polyamide based resin laminated film roll was obtained in the same manner as in Example 1 except that pre-drying condition of feedstock chips A and C was changed to a method of heating at about 100° C. for about 4.0 hours. Additionally, a predetermined amount of each chip was sampled from the inside of a blender after pre-drying, water content was measured, which showed that the water contents of chips A and C were both 1500 ppm, and the temperatures of chips A and C just before being fed to the hopper were both at about 85° C. Then, the characteristics of the obtained film roll were evaluated in the same methods as in Example 1. Tables 4 to 7 show evaluation results.
An unstretched film obtained in the same manner as in Example 1 was longitudinally stretched (first longitudinal stretching) at stretching temperature of about 90° C. and about 1.5 times by a Teflon (registered trademark) roll, then longitudinally stretched (second longitudinal stretching) at stretching temperature of about 70° C. and about 2.2 times by a ceramic roll. Further, the longitudinally stretched sheet was continuously led to a stenter, in the same manner as in Example 1, transversely stretched, thermally fixed, subjected to transverse relaxation treatment and cooled. Then, by cutting the both edge parts to eliminate, a biaxially stretched film of about 15 μm and 2000 m or more continuously was formed. Additionally, the variation width of film surface temperature when the film was continuously produced was the same as in Example 1. Thereafter, the obtained film was slit and winded up in the same manner as in Example 1 and polyamide based resin laminated film was obtained. Then, the characteristics of the obtained film roll were evaluated in the same methods as in Example 1. Tables 4 to 7 show evaluation results.
[Effect of Film of Examples]
It is known from Tables 4 though 7 that the film rolls of working examples have all remarkably small thickness irregularities in the longitudinal direction throughout the entire rolls and provide small variations in physical properties such as boiling water shrinkage percentage, refractive index, coefficient of dynamic friction under high humidity. In addition, it is known that in film rolls of working examples having small variations in physical properties such as boiling water shrinkage percentage, refractive index to S-shaped curl phenomenon does not occur and satisfactory lamination processability is achieved under high humidity. Moreover, it is known that the films composing film rolls of working examples provide superb impact strength (toughness and pinhole resistance) and high laminate strength. In contrast, it is known that film rolls of comparative examples have large variations in thickness irregularities over the entire roll in the longitudinal direction and large variations in physical properties such as boiling water shrinkage percentage, refraction index and coefficient of dynamic friction under high humidity, provide defective lamination processability, excessively large haze, or develop an S-shaped curl phenomenon.
[Industrial Applicability]
A polyamide based resin laminated film roll of the present invention can be preferably used in an application of retort processing for food since it provides excellent processability as described above.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2005-171487 | Jun 2005 | JP | national |
| 2005-203303 | Jul 2005 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2005/023512 | 12/21/2005 | WO | 00 | 12/10/2007 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2006/132005 | 12/14/2006 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 5741601 | Kishida et al. | Apr 1998 | A |
| 6376093 | Fujita et al. | Apr 2002 | B1 |
| Number | Date | Country |
|---|---|---|
| 927624 | Jul 1999 | EP |
| 1754588 | Feb 2007 | EP |
| 1881022 | Jan 2008 | EP |
| 1900498 | Mar 2008 | EP |
| 07-47545 | Feb 1995 | JP |
| 10-100226 | Apr 1998 | JP |
| 2000-007801 | Jan 2000 | JP |
| 2000-052516 | Feb 2000 | JP |
| 2000-309074 | Nov 2000 | JP |
| 2002-029014 | Jan 2002 | JP |
| 2002120281 | Apr 2002 | JP |
| 2002-166512 | Jun 2002 | JP |
| 2003-170494 | Jun 2003 | JP |
| 2004-181777 | Jul 2004 | JP |
| 2004181777 | Jul 2004 | JP |
| 2007-130759 | May 2007 | JP |
| Entry |
|---|
| Machine—English—Translation—of—JP—2004—181777—A, Oda et. al., “Polyamide Based Film Roll and its Manufacturing Method”, Jul. 2, 2004, JPO, pp. 1-13. |
| Machine—English—Translation—JP—2004/181777—A, Oda et al., “Polyamide Based Film Roll and its Manufacturing Method”, JPO, Jul. 2, 2004, pp. 1-15. |
| European Patent Office, Supplemental European Search Report in corresponding European patent application No. 05820356.3 dated Jun. 8, 2009. |
| Number | Date | Country | |
|---|---|---|---|
| 20090191369 A1 | Jul 2009 | US |
