WO2006132005A1 - ポリアミド系樹脂積層フィルムロール、およびその製造方法 - Google Patents
ポリアミド系樹脂積層フィルムロール、およびその製造方法 Download PDFInfo
- Publication number
- WO2006132005A1 WO2006132005A1 PCT/JP2005/023512 JP2005023512W WO2006132005A1 WO 2006132005 A1 WO2006132005 A1 WO 2006132005A1 JP 2005023512 W JP2005023512 W JP 2005023512W WO 2006132005 A1 WO2006132005 A1 WO 2006132005A1
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- WO
- WIPO (PCT)
- Prior art keywords
- polyamide
- based resin
- average
- film
- laminated film
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/915—Cooling of flat articles, e.g. using specially adapted supporting means with means for improving the adhesion to the supporting means
- B29C48/916—Cooling of flat articles, e.g. using specially adapted supporting means with means for improving the adhesion to the supporting means using vacuum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1355—Elemental metal containing [e.g., substrate, foil, film, coating, etc.]
- Y10T428/1359—Three or more layers [continuous layer]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
- Y10T428/24372—Particulate matter
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
- Y10T428/24372—Particulate matter
- Y10T428/24421—Silicon containing
Definitions
- the present invention relates to a film roll having a uniform physical property and a high quality over a long length obtained by winding a polyamide-based resin-laminated film, and more specifically, laminating with a polyolefin-based resin film.
- the present invention relates to a polyamide-based resin film laminated film roll having good processability (especially processability under high humidity) when used for packaging retort foods.
- a biaxially oriented polyamide resin film mainly composed of nylon is tough and has excellent gas barrier properties, pinhole resistance, transparency, printability, etc. It has been widely used as a packaging material for various foods such as frozen foods, retort foods, pasty foods, livestock and fishery products, and in recent years, it has been widely used for packaging retort foods.
- a strong polyamide-based resin film is laminated with, for example, a polyolefin-based resin film such as polyethylene-polypropylene, folded in two parallel to the flow direction, then heat-sealed and cut out three sides. It is an open three-sided seal bag that is opened, filled with various foods and sealed inside, then sterilized by heating in boiling water and put on the market.
- Patent Document 1 Japanese Patent Laid-Open No. 4 103335
- Patent Document 2 JP-A-8-174663
- the applicants described the fluctuation of the dynamic friction coefficient by using a method for producing a biaxially stretched film roll that mixes a plurality of resins and melt-extrudes them and then scoops the biaxially stretched film.
- a method for reducing the size we proposed a method to reduce the segregation of the raw material by aligning the shape of the raw material chip and increasing the inclination angle of the funnel-shaped hot bar serving as the raw material supply unit to the extruder (Japanese Patent Application Laid-Open No. 2005-125867). 2004—181777).
- the method of applying force is not necessarily a definitive method as a method for suppressing fluctuations and variations in physical properties such as boiling water shrinkage and refractive index of a film wound on a film roll.
- the present invention has been achieved as a result of earnest research and development on production technology for increasing the slipperiness of polyamide-based resin films under high humidity and keeping them unchanged. Eliminates the problems of conventional polyamide-based resin film rolls, enables smooth bag-making by laminating without any trouble even in high humidity such as in summer, and packaging without S-curls
- An object of the present invention is to provide a biaxially oriented polyamide-based resin film roll capable of efficiently obtaining a product.
- Another object of the present invention is to provide a biaxially oriented polyamide-based resin laminated film roll capable of obtaining a processed product with a high yield in post-processing such as bag making.
- An object of the present invention is to provide a production method that can efficiently produce such a biaxially oriented polyamide-based resin-laminated film roll. Means for solving the problem
- the configuration of the invention described in claim 1 is that a polyamide-based resin laminated film obtained by laminating a plurality of polyamide-based resin sheets has a width of 0.2 m or more.
- the final cutout part is provided within 2 m and the first sample cutout part force is provided every about 100 m, the following requirements (1) to (5) are satisfied.
- the average of the maximum boiling water shrinkage is measured.
- the average boiling water shrinkage which is the value, is 2% to 6%, and the fluctuation rate of the maximum boiling water shrinkage of all the samples is within ⁇ 2% to 10% of the average boiling water shrinkage.
- the average boiling water shrinkage direction difference which is the average value of the boiling water shrinkage direction differences, was 2.0% or less, and fluctuations in the boiling water shrinkage direction difference of all samples.
- the rate is within a range of ⁇ 2% to 20% with respect to the difference in average boiling water shrinkage direction.
- the average surface roughness that is the average value of the three-dimensional surface roughness Is within the range of 0.01 to 0.06 m, and the variation of the three-dimensional surface roughness of all samples is within a range of ⁇ 5% to 20% with respect to the average surface roughness.
- the average haze which is the average value of those hazes, is in the range of 1.0 to 4.0,
- the variation rate of haze of all samples is within the range of ⁇ 2% to 15% with respect to the average haze.
- Thickness variation rate power over the entire length in the longitudinal direction of the roll taken off is within a range of ⁇ 2% to 10% with respect to the average thickness.
- each sample cut out from each cut-out portion is in an atmosphere of 80% RH at 23 ° C.
- the average dynamic friction coefficient which is the average value of these dynamic friction coefficients, was in the range of 0.3 to 0.8, and the fluctuation rate of the dynamic friction coefficient of all samples was The average dynamic friction coefficient is within a range of ⁇ 5% to 30%.
- the configuration of the invention described in claim 3 is that when the content of inorganic particles is measured for each sample cut out from each cutout portion in the invention described in claim 1,
- the average content which is the average value of the inorganic particle content, is in the range of 0.01 to 0.5% by weight, and the variation rate of the inorganic particle content of all the samples is relative to the average content. It is within the range of ⁇ 2% to 10%.
- the configuration of the invention described in claim 4 is the configuration according to the invention described in claim 1, when the refractive index in the thickness direction is measured for each sample cut out from each cut-out portion. ,That The average refractive index, which is the average value of these refractive indexes, is 1.500 or more and 1.520 or less, and the variation rate of the refractive index of all samples is within ⁇ 2% of the average refractive index. Make it a range.
- the structure of the invention described in claim 5 is that, in the invention described in claim 1, the wound polyamide-based resinous laminated film has an average particle diameter of the inorganic particles contained in the core layer as a skin.
- the thickness is equal to or greater than the thickness of the layer.
- the structure of the invention described in claim 6 is that, in the invention described in claim 1, the main component of the polyamide constituting the polyamide-based resin-laminated laminated film roll is nylon 6. is there.
- a polyamide-based resin laminated film formed from a mixture of two or more kinds of polyamide-based resins is wound up.
- the configuration of the invention described in claim 8 is that, in the invention described in claim 1, the wound polyamide-based resin laminated film is laminated with a polyolefin-based resin film. .
- the structure of the invention described in claim 9 is the invention described in claim 1, wherein the melted polyamide-based resin is extruded with a T-die force and brought into contact with a metal roll and cooled. That is, a polyamide-based resin laminated film obtained by biaxially stretching the obtained non-oriented sheet-like material is wound up.
- the structure of the invention described in claim 10 is that in the invention described in claim 1, the polyamide-based resin laminated film stretched by the tenter stretching method is wound.
- the configuration of the invention described in claim 11 is that the polyamide-based resin laminated film sequentially biaxially stretched is wound up in the invention described in claim 1.
- the configuration of the invention described in claim 12 is the invention according to claim 1, in which a polyamide-based resin laminated film stretched biaxially in the vertical direction and the horizontal direction is wound. There is something.
- the configuration of the invention described in claim 13 is substantially the same as that of the invention described in claim 1.
- the sheet-like material made of unoriented polyamide resin is stretched in the machine direction in at least two steps so that the glass transition temperature of the polyamide resin is higher than the glass transition temperature + 20 ° C and the magnification is 3 times or more.
- the polyamide-based resin laminated film that has been stretched in the transverse direction so as to have a magnification of 3 times or more is wound.
- the configuration of the invention described in claim 15 is that, in the invention described in claim 1, the polyamide-based resin-laminated laminated film that has been subjected to relaxation treatment after heat fixing is wound up. .
- the structure of the invention described in claim 16 is the same as that of the invention described in claim 1, in which the wound polyamide-based resin laminated film includes a lubricant, an anti-blocking agent, a heat stabilizer, and an antioxidant.
- a lubricant for lubricating lubricant
- an anti-blocking agent for lubricating lubricant
- a heat stabilizer for preventing oxidative damage to the wound polyamide-based resin laminated film
- an antioxidant includes a lubricant, an anti-blocking agent, a heat stabilizer, and an antioxidant.
- the structure of the invention described in claim 17 is that, in the invention described in claim 1, inorganic particles are added to the wound polyamide based resin laminated film.
- the configuration of the invention described in claim 18 is that, in the invention described in claim 17, the inorganic particles are silica particles having an average particle size of 0.5 to 5. O / zm. .
- the structure of the invention described in claim 19 is that, in the invention described in claim 1, a higher fatty acid is added to the wound polyamide-based resin laminated film.
- the configuration of the invention described in claim 20 is a manufacturing method for manufacturing the polyamide-based resin layered film roll described in claim 1, wherein a plurality of extruder forces are produced by a co-extrusion method.
- a film-forming process for forming an unstretched laminated sheet obtained by laminating a plurality of polyamide-based resinous resins by melt extrusion of the polyamide-based resin, and an unstretched laminated sheet obtained by the film-forming process in the machine direction and the transverse direction A biaxial stretching process for biaxial stretching,
- the film forming step uses a high-concentration raw material chip to laminate a skin layer containing 0.05 to 2.0% by weight of inorganic particles on the core layer.
- the biaxial stretching step involves stretching in the longitudinal direction in two stages and then in the transverse direction, and the first-stage stretching ratio in the longitudinal two-stage stretching is determined from the second-stage stretching ratio.
- each of the chips made of the polyamide resin having the largest amount used and one or more other polyamide resin chips having a composition different from that of the polyamide resin are mixed together.
- Extruder force Melted and extruded to form an unstretched laminated sheet, and the shape of each polyamide-based resin chip used is an elliptical cylinder with an elliptical cross section having a major axis and a minor axis
- Polyamide-based resin chips other than the most used polyamide-based resin chips The most used amount of polyamide-based resin chips
- the average major axis, average minor axis, and average chip length of polyamide-based resin chips are ⁇ The average major axis, the average minor axis, and the average chip length within the range of 20% are adjusted.
- the film forming step includes a step of melting and extruding using a plurality of extruders provided with a funnel-shaped hopper as a raw material chip supply unit, and all the inclination angles of the funnel-shaped hot bar are 65. And the moisture content of the polyamide-based resin chip before being supplied to the funnel-shaped hot bar is adjusted to 800 ppm or more and lOOOppm or less, and the polyamide before being supplied to the funnel-shaped hot bar The temperature of the system resin chip is adjusted to 80 ° C or higher
- the process includes a step of cooling the melt-extruded unstretched laminated sheet by bringing it into contact with a cooling roll, and in the cooling step, the surface of the molten resin and the cooling roll is included. The contacting part is sucked in the opposite direction to the winding direction by the suction device over the entire width of the molten resin.
- the structure of the invention described in claim 21 is that, in the invention described in claim 20, the high concentration raw material chip force inorganic particles used in the film forming step is 5% by weight or more. That is, it is a polyamide-based resin chip added with less than 20% by weight.
- the structure of the invention described in claim 23 is the invention described in claim 20, wherein a preheating step performed before the longitudinal stretching step, and a heat treatment step performed after the longitudinal stretching step, Fluctuation force of the surface temperature of the film at any point in the longitudinal stretching process, preheating process and heat treatment process.
- the average temperature is adjusted within the range of 1 ° C over the entire length of the film! , To be.
- the polyamide-based resin laminated film roll of the present invention it is possible to carry out bag-making by lamination smoothly and with little trouble even under high humidity such as in summer, and packaging without S-shaped force. Things can be obtained efficiently. Further, in post-processing such as bag making processing, it becomes possible to obtain processed products with a high yield. If the polyamide-based resin laminated film roll of the present invention is used, the food packaging bag after the bag-making process by lamination becomes tough and excellent in pinhole resistance.
- the polyamide-based resin-laminated film roll of the present invention has a maximum boiling water shrinkage that is the maximum value of the boiling water shrinkage in all directions for all the samples when the samples are cut out by the method described later.
- the average boiling water shrinkage which is the average value of the maximum boiling water shrinkage, is adjusted to be 2% or more and 6% or less.
- the polyamide-based resin laminated film roll of the present invention has a boiling water contraction rate in the +45 degree direction and a longitudinal direction with respect to the longitudinal direction for all the samples when the samples are cut out by the method described later.
- the difference in boiling water shrinkage direction which is the absolute value of the difference from the boiling water shrinkage in the 45 ° direction
- the average difference in the boiling water shrinkage direction which is the average of the difference in boiling water shrinkage direction
- the first sample cutting portion is provided within 2 m from the end of winding of the film, and the final cutting portion is provided within 2 m from the beginning of winding of the film.
- the sample cut-out force of the sample will also have a sample cut-out portion every 100m Do it. “About every 100 m” means that the sample may be cut out at about 100 m ⁇ lm.
- the cutting of the above sample will be explained.
- the first sample is within 2m from the end of winding of the film. Cut out (1).
- the sample is cut out in a rectangular shape so as to have a side along the longitudinal direction of the film and a side along the direction perpendicular to the longitudinal direction (not cut diagonally).
- cut away the second sample (2) at a distance of 100 m away from the cut portion.
- the third sample (3) is separated to the winding start side of 200m
- the fourth sample (4) is separated to the winding start side of 300m
- the fifth sample is separated to the winding start side of 400m. Cut out (5).
- the sixth (final) sample (6) cuts out any part within 2m from the beginning of film winding.
- the boiling water shrinkage rate hereinafter referred to as BS
- maximum boiling water shrinkage rate hereinafter referred to as BSx
- average boiling water shrinkage rate hereinafter referred to as BSax
- boiling water shrinkage rate are as follows. Measure direction difference (hereinafter referred to as BSd) and average boiling water shrinkage direction difference (hereinafter referred to as BSad).
- the biaxially oriented polyamide-based resin laminated film cut out from each cut-out part of the polyamide-based resin-laminated film roll is cut into a square shape and left in an atmosphere of 23 ° C. and 65% RH for 2 hours or more.
- a circle (about 20cm in diameter) centered on the center of this sample is drawn, and the vertical direction (film drawing direction) is 0 °.
- the straight line passes through the center of the circle in the direction of 0 to 165 ° clockwise at 15 ° intervals. And measure the diameter in each direction to obtain the length before treatment.
- the cut sample was heat-treated in boiling water for 30 minutes, then removed, wiped off moisture adhering to the surface, air-dried, and left in an atmosphere of 23 ° C and 65% RH for 2 hours or more.
- BSad total BSd of all samples Number of Z samples.
- the BSx value of the polyamide-based resin laminated film constituting the polyamide-based resin laminated film roll is the heat resistance (lamination strength or heat resistance) when the film is formed into a bag shape and subjected to hot water treatment. It is important for ensuring the strength of the laminate and enhancing the toughness and pinhole resistance of the film itself. If the BSx value is less than 2%, the toughness and pinhole resistance will be insufficient. On the other hand, if it exceeds 6%, it is not preferable because of poor lamination or insufficient heat-resistant laminate strength during hot water treatment. Toughness' The range of BSx is more preferably 3.5 to 5.0% in terms of enhancing pinhole resistance, laminating properties and heat-resistant laminate strength.
- the BSd value of the polyamide-based resin-laminated film constituting the polyamide-based resin-laminated film roll has a great influence on the curling phenomenon that occurs during boiling water treatment.
- the variation rate of the maximum boiling water shrinkage (BSx) of all the cut out samples is 2% to 10% of the average boiling water shrinkage (BSa). It needs to be adjusted so that it is within the range of (2% or more ⁇ 10% or less).
- the variation rate of the maximum boiling water shrinkage (BSx) of all samples is the maximum / minimum of the maximum boiling water shrinkage (BSx) of all samples, and the average of the maximum and minimum This is the ratio of the difference between the average boiling water shrinkage and the difference between the average boiling water shrinkage and the difference between the boiling water shrinkage and the average boiling water shrinkage.
- the maximum value Xmax of Xn is The difference between the difference between the average boiling water shrinkage (BSax) and the difference between the minimum value Xmin and the average boiling water shrinkage (BSax) must be within 10%.
- ( (II indicates absolute value) is required to be less than or equal to io%.
- the variation rate of the maximum boiling water shrinkage rate (BSx) of all the cut out samples is within a range of 9% or less of the average boiling water shrinkage rate (BSa). It is preferable that it is within a range of ⁇ 8%, and more preferably within a range of ⁇ 7%.
- the polyamide-based resin laminated film roll of the present invention is preferably as the variation rate of the maximum boiling water shrinkage (BSx) of all cut out samples is smaller, but the lower limit of the variation rate is 2 in consideration of measurement accuracy. % Is the limit.
- the fluctuation rate of the boiling water shrinkage direction difference (BSd) of all the cut out samples is 2% to 2% of the average boiling water shrinkage direction difference (BSad). It needs to be adjusted so that it is within the range of 20% (2% or more ⁇ 20% or less).
- the fluctuation rate of the boiling water shrinkage direction difference (BSd) of all samples is the maximum / minimum of the boiling water shrinkage direction differences (BSd) of all samples, and the average of those maximum and minimum When the difference between the difference between the boiling water shrinkage direction difference and the average boiling water shrinkage direction difference is calculated, this is the ratio of the difference to the average boiling water shrinkage direction difference.
- the variation rate of the boiling water shrinkage direction difference (BSd) of all the cut out samples is within ⁇ 15% of the average boiling water shrinkage direction difference (BSad). If it is within the range of ⁇ 10%, it is more preferable if it is within the range of ⁇ 10%.
- the polyamide-based resin laminated film roll of the present invention is preferably as the variation rate of the boiling water shrinkage direction difference (BSd) of all the cut out samples is smaller, but the lower limit of the variation rate thinks that the limit is around 2% considering the measurement accuracy.
- BSd boiling water shrinkage direction difference
- the polyamide-based resin laminated film roll of the present invention has an average surface roughness (SRaa) of 0.01 to 0. 0, which is an average value of three-dimensional surface roughness (SRa) of all cut out samples. It is necessary to be in the range of 06 m, and it is more preferable to be in the range of 0.02-0.05 / zm (an example of a method for measuring the three-dimensional surface roughness will be described in Examples). If the average surface roughness is less than 0.01 m, it is not preferable because good slipperiness under high humidity cannot be obtained. Conversely, if the average surface roughness is more than 0.06 m, the laminate When processing, the adhesiveness with a film such as polyolefin is lowered, which is not preferable.
- SRaa average surface roughness
- the variation rate of the three-dimensional surface roughness (SRa) of all the cut out samples is ⁇ 5% of the average surface roughness (SRaa). It is necessary to adjust to be within the range of% (5% or more ⁇ 20% or less).
- the variation rate of the three-dimensional surface roughness (SRa) of all the samples is the maximum / minimum of the three-dimensional surface roughness (SRa) of all the samples, and is within the maximum / minimum of those. This is the ratio of the difference between the average surface roughness and the average surface roughness when the difference between the average surface roughness and the average surface roughness is calculated.
- the maximum SRn This means that both the difference between the value SRmax and the average surface roughness (SRaa) and the difference between the minimum value SRmin and the average surface roughness must be within 20%.
- I SRaa—SRn I (where II is an absolute value) must be 20% or less.
- the polyamide-based resin laminated film roll of the present invention has a variation rate of the three-dimensional surface roughness (SRa) of all cut out samples within ⁇ 15% of the average surface roughness (SRaa). Preferably, it is within the range of ⁇ 10%, and more preferably within the range of ⁇ 8%. In fact, the polyamide-based resin laminated film roll of the present invention is preferable as the variation rate of the three-dimensional surface roughness (SRa) of all the cut out samples is smaller. However, the lower limit of the variation rate considers the measurement accuracy. Then, about 5% is considered the limit.
- the polyamide-based resin-laminated laminated film roll of the present invention comprises all cut out samples.
- the average haze which is the average value of haze, needs to be in the range of 1.0 to 4.0, and more preferably in the range of 1.5 to 3.0. If the average haze is more than 4.0, it is not preferable because the appearance of the formed bag is deteriorated when the bag making process is performed. Although the average haze is preferably as small as possible, the lower limit of the average haze is considered to be about 1.0 in consideration of measurement accuracy.
- the polyamide-based resin laminated film roll of the present invention has a haze variation rate of ⁇ 2% to 15% ( ⁇ 2% or more and ⁇ 15% or less) of the average haze of all the cut out samples. It needs to be adjusted to be within the range.
- the haze variation rate of all samples is the maximum / minimum of all samples in the haze, and the difference between the average haze and the larger of the maximum / minimum average hazes The ratio of the difference in the average haze when obtained.
- the polyamide-based resin laminated film roll of the present invention preferably has a variation rate of haze of all cut out samples within a range of ⁇ 10% of the average haze. More preferably.
- the polyamide-based resin laminated film roll of the present invention has a small haze variation rate for all cut out samples! /, But is more preferable U, but the lower limit of the variation rate is 2% considering the measurement accuracy. I think the degree is the limit.
- the variation rate of the thickness over the entire length in the longitudinal direction is ⁇ 2% to 10% with respect to the average thickness ( ⁇ 2% or more ⁇ 10% or less) It is necessary to adjust so that it is within the range.
- the variation rate of the thickness over the entire length in the longitudinal direction is the maximum / minimum of the thickness over the entire length in the longitudinal direction
- the average thickness is the difference between the maximum thickness and the average thickness. This is the ratio of the difference to the average thickness when the difference is obtained.
- the difference between the maximum value Tmax of the thickness over the length and the average thickness (average thickness Ta over the entire length in the longitudinal direction) and the difference between the minimum value Tmin and the average thickness (Ta) must be within ⁇ 10%. Is needed.
- the polyamide-based resin laminated film roll of the present invention preferably has a variation rate of thickness over the entire length in the longitudinal direction within ⁇ 8% of the average thickness (Ta), preferably within ⁇ 6%. It is more preferable to be in the range of.
- the polyamide-based resin-laminated film roll of the present invention is preferably as the thickness variation rate over the entire length in the longitudinal direction is smaller.
- the lower limit of the variation rate is limited to about 2% from the performance of the film forming apparatus. I believe that.
- the average dynamic friction coefficient ( ⁇ da) which is the average value of the dynamic friction coefficients ( ⁇ d) at 23 ° CX 80% RH, of all cut out samples is 0.
- the variation rate of the dynamic friction coefficient ( ⁇ d) of all the cut out samples is ⁇ 5% to 30% ( ⁇ 5% or more) of the average dynamic friction coefficient It is preferable to adjust to be within a range of ⁇ 30% or less.
- the fluctuation rate of the dynamic friction coefficient d) of all samples is the difference between the maximum and minimum of the dynamic friction coefficients d) of all samples and the average dynamic friction coefficient of those maximum and minimum values. Is the ratio of the difference to the average dynamic friction coefficient when the difference is calculated.
- the maximum value of ⁇ The difference between the difference between max and the average dynamic friction coefficient ( ⁇ da) and the difference between the minimum value ⁇ min and the average dynamic friction coefficient is preferably within 30%, in other words , I da—n
- the polyamide-based resin-laminated laminated film roll of the present invention is made up of all the cut out samples.
- the coefficient of variation of the dynamic friction coefficient (d) is preferably within ⁇ 20% of the average dynamic friction coefficient, more preferably within ⁇ 15%, and even more preferably within ⁇ 10%. That's right. Power!
- the polyamide-based resin laminated film roll of the present invention is preferably as small as the variation rate of the dynamic friction coefficient d) of all cut out samples, but the lower limit of the variation rate is about 5% in consideration of measurement accuracy. I think it is the limit.
- the average content which is the average value of the content of inorganic particles in all cut out samples, is in the range of 0.01 to 0.5% by weight. It is more preferable to be in the range of 0.05 to 0.3% by weight (an example of a method for measuring the content of inorganic particles will be described in the examples). If the average content is less than 0.01% by weight, good slipperiness under high humidity will not be obtained. On the contrary, if the average content exceeds 0.5% by weight, it will be deleted in the manufacturing process. This is not preferable because it is difficult to recover and reuse the polyamide resin.
- the polyamide-based resin laminated film roll of the present invention has a variation rate power of the inorganic particle content of all cut out samples ⁇ 2% to 10% of average content ( ⁇ 2% or more ⁇ 10% It is preferable to adjust so that it falls within the following range.
- the variation rate of the inorganic particle content of all the samples is the maximum or minimum of the inorganic particle content of all the samples, and the difference between the average content of the maximum and minimum values is large. !, The ratio of the difference to the average content when the difference between the value and the average content is obtained.
- the maximum Cn the difference between the value Cmax and the average content (Ca) and the difference between the minimum value Cmin and the average content is preferably within 10%.
- I Ca — Cn I (where II is the absolute value) is preferably 10% or less.
- the polyamide-based resin laminated film roll of the present invention preferably has a variation rate of the inorganic particle content of all cut out samples within a range of ⁇ 8% of the average content ⁇ 6 More preferably, it is within the range of%.
- the polyamide-based resin-laminated film roll of the present invention is preferable as the variation rate of the inorganic particle content of all the cut out samples is small, but the lower limit of the variation rate is 2 in consideration of measurement accuracy. % Is the limit Yes.
- the polyamide-based resin-laminated film roll of the present invention has a refractive index (Nz) in the thickness direction for all the samples when the samples are cut out by the above method.
- the average refractive index (Nza) which is the average value of the refractive indexes, is preferably adjusted so as to be 1.500 or more and 1.520 or less.
- the Nz value of the polyamide-based resin-laminated laminated film constituting the polyamide-based resin-laminated laminated film roll has a great influence on film quality such as laminate strength and thickness unevenness. Therefore, the requirement that the average refractive index is 1.500 or more and 1.520 or less is an indispensable requirement when using a biaxially oriented polyamide resin film laminated with a polyolefin resin film. It becomes.
- Nz is less than 1.500, the laminate strength with the polyolefin resin film or the like is insufficient, and peeling between the laminate base material is likely to occur due to boiling water treatment after bag making. On the other hand, this Nz gradually decreases in the process of biaxially stretching an unstretched polyamide-based resin laminated film.
- Nz can be considered as one of the indices of stretching, and a large Nz indicates that stretching is insufficient, and if Nz exceeds 1.520, it is due to insufficient biaxial stretching. Thick spots etc. appear prominently and satisfactory film quality cannot be obtained.
- the particularly preferred Nz range is 1.507 to 1.516, taking into account both laminate strength and film quality.
- the variation rate of the refractive index (Nz) of all the cut out samples is compared with the average value of the refractive indexes (hereinafter referred to as the average refractive index). Therefore, it is preferable to adjust so as to be within a range of ⁇ 2%.
- the variation rate of the refractive index (Nz) of all the samples is the maximum or minimum of the refractive indexes (Nz) of all the samples, and the difference between the average refractive index of those maximum and minimum values. When the difference between the average and the average refractive index is obtained, the ratio of the difference to the average refractive index.
- the refractive indexes of the samples (1) to (6) are Nzl to Nz6, the maximum value Nzmax and the average refractive index of Nzl to Nz6 And the difference between the minimum value Nzmin of Nzl to Nz6 and the average refractive index is preferably less than 2%, in other words, I average refractive index—Nzl I to I average Refractive index—Nz6 I is preferably 2% or less.
- the variation rate of the refractive index (Nz) of all the cut out samples is within ⁇ 1% of the average refractive index.
- the polyamide-based resin laminated film roll of the present invention is preferably as small as the variation rate of the refractive index (Nz) of all the cut out samples, but the lower limit of the variation rate is from the viewpoint of measurement accuracy and mechanical accuracy. 0.1% is considered the limit.
- the maximum boiling water shrinkage rate, the boiling water shrinkage direction difference, the surface roughness, etc. in one polyamide-based resin-laminated laminated film roll are adjusted to values within a predetermined range, and their maximum boiling water shrinkage is adjusted.
- the rate, boiling water shrinkage direction difference, surface roughness, etc. it is possible to prevent bad appearance in bag making and laminating, and it can be processed smoothly with high yield even under high humidity. It becomes possible.
- Examples of the polyamide rosin used in the present invention include nylon 6, which uses ⁇ -force prolatatam as a main raw material.
- Examples of the other polyamide resin include polyamide resin obtained by polycondensation of ratata having three or more members, ⁇ -amino acid, dibasic acid and diamine, and the like.
- ratatas in addition to the aforementioned ⁇ -force prolatatam, enantolactam, force prilllatatam, lauryllatatam, and ⁇ -amino acids include 6 aminocaproic acid, 7 aminoheptanoic acid, 9 aminononane. And acid, 1 1-aminoundecanoic acid.
- Dibasic acids include adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecadioic acid, hexadecadionic acid, eicosandioic acid, eicosagendioic acid, 2, 2 , 4 Trimethyladipic acid, terephthalic acid, isophthalic acid, 2, 6 naphthalene dicarboxylic acid, xylylene dicarboxylic acid.
- the diamines include ethylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, pentamethylene diamine, undecamethylene diamine, 2, 2, 4 (or 2 , 4, 4) Trimethylhexamethylenediamine, cyclohexanediamine, bis (4,4'aminocyclohexyl) methane, metaxylylenediamine and the like.
- the polyamide-based greaves particularly preferred in the present invention are those having a relative viscosity in the range of 2.0 to 3.5.
- the relative viscosity of the polyamide-based resin affects the toughness and extensibility of the obtained biaxially stretched film. If the relative viscosity is less than 2.0, the impact strength tends to be insufficient. This is because, when the relative viscosity exceeds 3.5, the biaxial stretchability tends to deteriorate with increasing stretching stress.
- the relative viscosity in the present invention is a value measured at 25 ° C. using a solution in which 0.5 g of a polymer is dissolved in 50 ml of 97.5% sulfuric acid.
- the polyamide-based resin-laminated film roll of the present invention is a longitudinal direction (longitudinal direction) of an unstretched film (unstretched laminated film or unstretched laminated sheet) obtained by melting and extruding a polyamide-resin chip as a raw material. ) And the transverse method (width direction), and then rolled into a roll shape and then manufactured.
- the polyamide-based resin laminated film needs to have a configuration of AZB (two types and two layers), AZBZA (two types and three layers), or AZBZC (three types and three layers). From the viewpoint of curl, the AZBZA configuration that is a symmetric layer configuration is preferable.
- the center layer that is not located on the outermost side ie, the B layer in the case of A / B / A or AZBZC layer configuration
- the thick layer in the case of the seed two-layer structure that is, the B layer in the case of the AZB layer structure of the thin A layer and the thick B layer
- the core layer is called the thick layer in the case of the seed two-layer structure.
- the outermost layer ie, A, B layer in the case of AZB layer structure, A, C layer in the case of A / BZA or AZB / C layer structure
- the thin layer ie, the A layer in the case of the AZB layer structure of the thin A layer and the thick B layer
- the skin layer is called the skin layer.
- the thickness ratio of each layer of the polyamide-based resin laminated film is preferably 5 to 50% for the A layer, or the A layer and the C layer, more preferably 10 to 20%, and particularly preferably 12-18%.
- the thickness ratio of the A layer of the surface layer described above means the sum of the thickness ratios of both surface layers
- the thickness ratio of the A layer and the C layer of the surface layer described above means the sum of the thickness ratios of both surface layers.
- the thickness ratio of the A layer, or the A layer and the C layer is less than 5%, the variation rate of the turbidity due to the thickness unevenness becomes large, which is not preferable.
- the thickness ratio of the A layer, or the A layer and the C layer exceeds 30%, the bending fatigue resistance is deteriorated, the number of pinholes is increased, and the transparency is deteriorated. .
- each layer is formed when a substantially unoriented polyamide sheet having the layer configuration of AZB, AZBZA, or AZBZC is formed.
- a method in which a polymer is melted using a separate extruder, co-extruded, cast onto a rotating drum from a die, and rapidly cooled and solidified to obtain a substantially unoriented polyamide sheet (so-called co-extrusion method). Can be suitably employed.
- a plurality of raw material polyamide resin chips having different compositions are blended in a hopper, then melt-kneaded, extruded by an extruder, and formed into a film (
- a plurality of extruders as described above are used.
- each polyamide resin chip is supplied continuously or intermittently to three hot bales and finally passed through a buffer hopper as needed.
- the raw material chips are quantitatively supplied to the extruder according to the extrusion amount of the extruder while mixing the three types of polyamide resin chips in the hopper just before or just above the extruder (hereinafter “final hopper” t). Form a film.
- the material prayer phenomenon that is, the final A phenomenon occurs in which the composition of chips supplied from Hotsuba to the extruder is different.
- the strong segregation phenomenon appears particularly prominent when the chip shape or specific gravity is different.
- the maximum boiling water shrinkage rate, the difference in boiling water shrinkage direction, the film thickness, and the refractive index in the thickness direction vary.
- Polyamide raw material chips are usually formed in a molten state after polymerization in the form of strands from a polymerization apparatus, immediately cooled with water, and then cut with a strand cutter. For this reason, the polyamide chip has an elliptical column shape with an elliptical cross section.
- the average major axis (mm) and average minor axis (mm) of the cross-sectional ellipse of other polyamide chips mixed with the polyamide chip with the largest amount of use The average tip length (mm) is ⁇ for the average major axis (mm), average minor axis (mm), and average tip length (mm) of the cross-sectional ellipse of the polyamide raw material chip with the largest usage amount, respectively.
- the raw material segregation can be reduced by adjusting the amount to within 20%. The most used amount!
- a more preferable inclination angle is 70 ° or more.
- the inclination angle of the hot tub is an angle between the funnel-shaped hypotenuse and the horizontal line segment.
- a plurality of hoppers may be used upstream of the final hopper, and in this case, the inclination angle of each hopper needs to be 65 ° or more, and more preferably 70 ° or more.
- the ratio of the fine powder generated due to the cutting of the raw material chips used in order to suppress fluctuations in the boiling water shrinkage rate Since the fine powder facilitates the occurrence of raw material prayer, it is preferable to remove the fine powder generated in the process and reduce the ratio of the fine powder contained in the hopper.
- the ratio of the fine powder contained is until the raw material chips enter the extruder. It is preferable that the amount be within 1% by weight throughout the whole process. More preferably, the amount is within 0.5% by weight.
- the fine powder can be removed by passing a sieve at the time of chip formation with a strand cutter, or by passing a cyclone air filter when the raw material chips are fed by air. The method of doing can be mentioned.
- Hotsuba As a means for reducing raw material segregation in the hopper, it is also a preferable means to optimize the capacity of the hot bar to be used.
- the proper capacity of Hotsuba is in the range of 15 to 120% by weight with respect to the discharge amount per hour of the extruder, and 20 to the discharge amount per hour of the extruder: LOO weight % Is more preferable.
- each raw material is continuously fed quantitatively to the extruder by a hopper (final hot bar) immediately above the extruder.
- a hopper final hot bar
- the chips supplied into the hopper are usually heated by a device such as a renderer to reduce the water content.
- a device such as a renderer to reduce the water content.
- the lower the moisture content during drying the less hydrolysis in the extrusion process and the better the film roll is obtained. It is.
- the physical properties are uniform.
- a film with uniform physical properties that is appropriately plasticized without being hydrolyzed in the extrusion process by controlling the moisture content within a predetermined range and securing a certain amount of moisture.
- the moisture content of the chip is set to 800 p. It is necessary to control to pm or more and lOOOppm or less.
- the moisture content of the chip exceeds 100 Oppm, hydrolysis is promoted when melted, the viscosity decreases, the longitudinal thickness unevenness of the unstretched film worsens, and the longitudinal thickness of the biaxially stretched film It may cause an increase in spots, fluctuations in physical properties, and variations.
- the moisture content of the chip is less than 800 ppm, the viscosity when melted becomes too high, and the film-forming property (ease of stretching) deteriorates.
- the optimal moisture content of the chips supplied into the hopper is 850ppm or more and 950ppm or less.
- the temperature of the chip supplied to Hotsuba is less than 80 ° C, the stagnation of the grease will worsen, causing vertical thickness unevenness, physical property fluctuations and variations, and the film roll of the present invention cannot be obtained. .
- the chip is dried by a device such as a renderer, it is necessary to adjust the drying temperature to 150 ° C. or lower. If the drying temperature exceeds 150 ° C, hydrolysis may occur during drying, which is not preferable.
- the temperature of the chips heated and dried by the pender is below 80 ° C, it must be heated again to 80 ° C or higher and supplied to the hopper.
- an unstretched film When an unstretched film is obtained by melting and extruding the chip, it is formed into a laminated film (stacked sheet) by melting the chip at a temperature of 200 to 300 ° C with each extruder and also extruding the T-die force. (That is, after casting), it is rapidly cooled by a method of wrapping around a cooling roll such as a metal tool cooled to a predetermined temperature.
- the preferable melt extrusion temperature is 240 ° C to 290 ° C. It is.
- the air gap (that is, the outlet force of the T die lip is also the vertical distance to the chill roll surface) is adjusted to 20 to 60 mm.
- a suction device such as a vacuum box (vacuum chamber) with a wide suction port, the part that contacts the surface of the molten resin and the cooling roll is covered in the winding direction over the entire width of the molten resin. It is preferable to forcibly adhere the molten resin to the metal roll by sucking in the opposite direction. In that case, it is necessary to adjust the suction air speed at the suction port to 2.0 to 7.
- the vacuum botton may be a series of suction ports, but the suction ports are divided into a predetermined number of sections in the lateral direction in order to facilitate adjustment of the suction air speed at the suction ports. Therefore, it is preferable that the suction air speed can be adjusted for each section.
- the casting speed increases, an accompanying flow is generated as the metal roll rotates, and the adhesion of the molten resin to the metal roll is impeded.
- a shielding plate formed wide with a soft material such as Teflon (registered trademark) is installed on the upstream side adjacent to the suction device (the metal roll relative to the suction device). It is preferable to block the accompanying flow by installing it on the opposite side of the rotation direction. Furthermore, in order to obtain the film roll of the present invention, it is necessary to suppress the variation in the suction wind speed of the vacuum bot within ⁇ 20% of the average suction wind speed (set value). More preferred. It is preferable to adjust the suction force by providing a filter in the vacuum box and feeding back the differential pressure before and after the filter so that the suction wind speed of the vacuum box does not fluctuate due to oligomer dust or the like.
- the film roll of the present invention when the melted resin is wound around the cooling roll, a direct negative charge of 90 to 105 mA is applied to the melted resin sheet from the needle electrode at 2 to 15 kv. It is necessary to apply and apply the glow discharge to the metal roll continuously and rapidly cool. In this case, it is preferable to adjust the DC negative charge to be applied in the range of 7 to 14 kv because the thickness variation in the vertical direction, fluctuations in physical properties, and variations are reduced. In addition, in order to obtain the film roll of the present invention, the variation of the DC negative charge to be applied is average negative. Charge (set value) must be kept within ⁇ 20%, more preferably within ⁇ 10%.
- a longitudinal and lateral stretching method in which an unstretched film is stretched in the longitudinal direction with a roll-type stretching machine and then stretched in the transverse direction with a tenter-type stretching machine, followed by heat setting treatment and relaxation treatment. Etc. need to be adopted. Furthermore, in order to obtain the film roll of the present invention, it is necessary to employ a so-called longitudinal / horizontal stretching method as a biaxial stretching method.
- the longitudinal-longitudinal-lateral stretching method is a method in which a substantially unoriented polyamide film is longitudinally stretched by first-stage stretching, followed by second-stage stretching without cooling to Tg or less.
- the film is stretched transversely at a magnification of 3.0 times or more, preferably 3.5 times or more, and further heat-set.
- the first-stage longitudinal stretch ratio higher than the second-stage longitudinal stretch ratio when performing the longitudinal-longitudinal-lateral stretching described above. That is, by making the first-stage longitudinal draw ratio higher than the second-stage longitudinal draw ratio, it is possible to obtain a film roll with good physical properties such as boiling water shrinkage and few variations in the physical properties. It becomes.
- it is usually easier to make the first stage longitudinal stretching ratio lower than the second stage longitudinal stretching ratio without causing sticking to the roll during the first stage stretching.
- a special roll such as a Teflon (registered trademark) roll, even if the longitudinal stretch ratio of the first stage is higher than the longitudinal stretch ratio of the second stage, it causes sticking to the roll. It can be easily stretched without any problems.
- the first-stage longitudinal stretching should be approximately 2.0 to 2.4 times stretched at a temperature of 80 to 90 ° C. Is preferred. If the draw ratio in the first stage is out of the above range and becomes high, the thickness unevenness in the vertical direction becomes large, such being undesirable. It is preferable to stretch the second stage of longitudinal stretching at a temperature of 65 to 75 ° C by about 1.3 to 1.7 times.
- the longitudinal direction This is not preferable because the strength (such as strength at 5% elongation) becomes low and becomes impractical.
- hot roll stretching, infrared radiation stretching, or the like can be employed as the longitudinal stretching method.
- the polyamide-based resin-laminated laminated film roll of the present invention is manufactured by such a longitudinal-longitudinal-lateral stretching method, it is necessary to reduce the thickness variation in the vertical direction, changes in physical properties, and variations. In addition, fluctuations in physical properties and fluctuations in the lateral direction can be reduced.
- the total longitudinal stretching condition is preferably 3.0 to 4.5 times.
- the transverse stretching is performed at a temperature of 120 to 140 ° C at about 4.
- the transverse stretching ratio falls outside the above range, the transverse strength (5% elongation strength, etc.) becomes low and unpractical. If the temperature is out of the range, the heat shrinkage rate in the lateral direction increases, which is not preferable. On the other hand, when the transverse stretching temperature falls outside the above range, the boil distortion increases and becomes impractical, so on the contrary, when the transverse stretching temperature rises outside the above range, the lateral stretching temperature increases. It is preferable because strength (such as strength at 5% elongation) becomes low and becomes impractical.
- the heat setting treatment after longitudinal-longitudinal-lateral stretching is performed at a temperature of 180 to 230 ° C. If the temperature of the heat setting treatment falls outside the above range, the heat shrinkage rate in the longitudinal direction and the transverse direction becomes large. On the contrary, if the temperature of the heat setting treatment rises outside the above range, biaxial stretching will occur. It is preferable because the impact strength of the film is lowered.
- the film roll of the present invention it is preferable to relax the relaxation treatment after heat setting by 2 to 10%.
- the rate of relaxation treatment falls outside the above range, the thermal contraction rate in the vertical and horizontal directions increases, and on the contrary, when the rate of relaxation treatment rises outside the above range, the longitudinal direction and width It is preferable because the strength in the direction (strength at 5% elongation, etc.) is low and it is not practical.
- the width of the film roll is not particularly limited, but from the viewpoint of ease of handling, the lower limit of the width of the film roll is preferably 0.35 m or more, and more preferably 0.50 m or more. It is more preferable.
- the upper limit of the width of the film roll is preferably 2.5 m or less, more preferably 2.0 m or less, and even more preferably 1.5 m or less.
- film law The length of the steel sheet is not particularly limited, but from the viewpoint of easy winding and handling, the lower limit of the film roll is preferably 500 m or more, more preferably 1,000 m or more.
- the upper limit of the length of the film roll is preferably 25,000 m or less, more preferably 120,000 m or less, and further preferably 15,000 m or less.
- the film thickness is about 15 m, it is particularly preferably 12000 m or less.
- the scraping core usually paper of 3 inches, 6 inches, 8 inches, etc., plastic cores and metal cores can be used.
- the thickness of the film constituting the polyamide-based resin laminated film roll of the present invention is not particularly limited.
- a polyamide-based film for packaging 8 to 5 is preferable, and 10 to 30 is preferable. More preferably, / ⁇ ⁇ .
- the polyamide-based resin laminated film constituting the film roll of the present invention includes a lubricant, an anti-blocking agent, a heat stabilizer, an antioxidant, an anti-static agent, a light-proofing agent, and the like within a range not impairing the properties. It is also possible to include various additives such as an impact resistance improver. In particular, it is preferable to contain various inorganic particles for the purpose of improving the slipperiness of the biaxially stretched film. In addition, it is preferable to add an organic lubricant such as ethylene bis-stearic acid, which exhibits the effect of lowering the surface energy, because the slip of the film constituting the film roll becomes excellent.
- a lubricant such as ethylene bis-stearic acid
- the polyamide-based resin laminated film constituting the film roll of the present invention may be subjected to heat treatment or humidity control treatment in order to improve dimensional stability depending on the application.
- heat treatment or humidity control treatment
- corona treatment, coating treatment, flame treatment, etc., and processing such as printing and vapor deposition can be performed.
- the amount of inorganic particles added to the polyamide-based resin when producing high-concentration raw material chips, it is preferable to set the amount of inorganic particles added to the polyamide-based resin to 5 to 20% by weight, preferably 10 to 15% by weight. Is more preferable. If the added amount of the inorganic particles exceeds 20% by weight, the dispersibility of the inorganic particles is lowered, and foreign matter may be formed in the film, which is not preferable. On the other hand, if the amount of inorganic particles added exceeds the force by weight, the economic efficiency deteriorates, which is not preferable.
- the polyamide resin is previously powdered by a method such as pulverization in a cooled state and then kneaded with inorganic particles. This is preferable because the dispersibility of the resin in the resin is improved.
- the properties of the inorganic particles added to the polyamide resin that constitutes the skin layer are specified so that good slipperiness under high humidity is achieved. It becomes possible to make it. That is, the inorganic particles to be added are particularly preferably silica particles having an average particle size (that is, average particle size) of 0.5 to 5.0 m. If the average particle size is less than 0.5 m, good slipperiness cannot be obtained, and conversely, if the average particle size exceeds 5. O / zm, transparency may be poor, Since "missing" occurs, it is not preferable.
- the inorganic particles preferably have a pore volume of 0.5 to 2. OmlZg, more preferably 0.8 to 1.5 ml / g. When the pore volume is less than 0.5 ml / g, the transparency of the film is deteriorated. Therefore, when the pore volume is preferably less than 2. OmlZg, the slipping property of the film is deteriorated.
- a laminated film (laminated sheet) having a plurality of layer structures is formed by melt extrusion of a plurality of extruder forces using the coextrusion method as described above.
- the discharge amount of the resin it is preferable to adjust the discharge amount of the resin to be melt-extruded as a skin layer so that the final thickness of the skin layer after stretching is 0.5 to 4. O / zm. It is more preferable to adjust it to be 1.0 to 3.0 m.
- the above-mentioned means (1) to (4) and (7) to (9) are used, and in the stretching process of the unstretched laminated film (5), (6)
- this means it is possible to reduce the thickness unevenness of each layer constituting the laminated film, and consequently reduce the thickness unevenness of the entire laminated film.
- the physical property fluctuation of the film roll can be reduced very efficiently.
- only one of the above-mentioned means (1) to (9) is effective. It does not contribute effectively to the reduction of the physical property fluctuation of the film roll.
- the means (1) to (9) are used in combination. Therefore, it is considered possible to reduce the physical property fluctuation of the film roll very efficiently.
- Chips C and E are both Nai-Non 6 (same physical properties as Chip A) 85.00 wt%, silica particles with an average particle size of 2. and a pore volume of 1.2 mlZg 15.0 wt%
- Tip D is Nylon 6 (same physical properties as Tip A) 95.00 wt%, silica particles with an average particle size of 2.
- chips A to E are all elliptical cylinders, and chips A to D have the same cross-sectional major axis, cross-sectional minor axis, and chip length.
- melt extrusion of polyamide-based resin from three extruders (first to third extruders) (stacking and extruding in a die) and rotating at 17 ° C
- An unstretched film (polyamide-based resin-laminated sheet) having a thickness of 257 m and a two-layer / three-layer structure was obtained by winding it around a metal roll and quenching.
- the method for forming each layer of the unstretched film (the process up to melt extrusion) is as follows. In the following description, the first layer, the second layer, and the third layer are referred to in order from the surface layer of the polyamide-based resin laminated sheet (that is, the surface of the third layer is a metal roll contact surface).
- Chips A and C were separately dried using a 15 kl blender apparatus while heating to about 120 ° C. over about 8.0 hours.
- the moisture content of chips A and C were both 800 ppm.
- the moisture content was measured using a Karl Fischer moisture meter (MKC-210, manufactured by KYOTO Electronics) under the conditions of sample weight lg and sample heating temperature 230 ° C.
- chips A and C in each of the renderers were continuously and separately supplied to a hopper directly above the extruder (first extruder) with a metering screw feeder.
- the supply amount of chip A was 99.5% by weight, and the supply amount of chip C was 0.5% by weight.
- the hopper had a capacity of 150 kg of raw material chips.
- the inclination angle of Hotsuba was adjusted to 70 °.
- the drying power was supplied to the hot hopper within a short time so that the temperature of the chips in each renderer would not become too low.
- the temperatures of chips A and C immediately before being supplied to Hotsuba were both about 91 ° C.
- the supplied chips A and C were mixed in a hopper, and melt-extruded from a T die at 270 ° C using a single-screw type first extruder.
- Chips A and C in each of the blenders dried as described above were continuously and separately supplied to a hot bar immediately above the extruder (second extruder) with a metering screw feeder.
- the supply amount of chip A was 99.97 wt%, and the supply amount of chip C was 0.03 wt%.
- the hopper had a capacity of 150 kg of raw material chips.
- the inclination angle of Hotsuba was adjusted to 70 °.
- Chips A and C in each of the blenders dried as described above were continuously and separately supplied to a hot bar immediately above an extruder (third extruder) with a metering screw feeder.
- the supply amount of chip A was 99.5% by weight, and the supply amount of chip C was 0.5% by weight.
- the hopper had a capacity of 150 kg of raw material chips.
- the inclination angle of Hotsuba was adjusted to 70 °.
- the temperature of the chips in each renderer is low. Drying power was supplied to Hotsuba within a short time so as not to become too stiff. The temperatures of chips A and C immediately before being supplied to Hotsuba were both about 91 ° C. Then, the supplied chips A and C were mixed in a hopper and melt-extruded from a T die at 270 ° C by a single screw type third extruder.
- the average major axis, the average minor axis, and the average chip length of the polyamide-based resin chips (Chip C) other than the polyamide-based resin chips having the largest use amount are included within the range of ⁇ 20%.
- the discharge amount of the first to third extruders in the formation of the unstretched film was adjusted so that the thickness ratio of the first layer Z second layer Z third layer was 2Z11Z2.
- the air gap when winding molten resin around a metal roll was adjusted to 40 mm, and a negative DC charge of 100 mA was applied to the molten film at 11 ⁇ 1. lkv from the acicular electrode. From one discharge, the molten resin was electrostatically adhered to the metal roll. Further, when the melted resin is wound around the metal roll, the part where the melted resin contacts the metal roll is wound up by using the vacuum box over the entire width of the melted resin. By sucking in the opposite direction, adhesion of the molten resin to the metal roll was promoted. The suction air speed of the vacuum box was adjusted to 5.0 ⁇ 0.5 m / sec over the entire width of the suction port (that is, the total width of the molten resin).
- the obtained unstretched film was stretched about 2.1 times (first longitudinal stretching) by a Teflon (registered trademark) roll at a stretching temperature of about 85 ° C, and then made of ceramic.
- first longitudinal stretching a Teflon (registered trademark) roll at a stretching temperature of about 85 ° C, and then made of ceramic.
- second longitudinal stretching a stretching temperature of about 70 ° C.
- the longitudinally stretched sheet was continuously guided to the tenter, stretched 4.0 times at about 130 ° C, and heat-set at about 210 ° C for 5.0% transverse relaxation treatment.
- both edges were cut and removed, and a biaxially stretched film of about 15 ⁇ m was continuously formed over 2000 m to produce a mill roll.
- the thicknesses of the first layer, the second layer, and the third layer were about 2 m, respectively. It was about 11 m and about m.
- the fluctuation range of the film surface temperature when the film was continuously produced for 2000 m is the preheating temperature.
- the average temperature was ⁇ 0.8 ° C
- the average temperature was ⁇ 0.6 ° C in the stretching step
- the average temperature was ⁇ 0.5 ° C in the heat treatment step.
- the obtained mill roll was slit into a width of 400 mm and a length of 2000 m, and wound around a 3-inch paper tube to obtain two polyamide-based resin laminated film rolls (slit rolls). Then, using the obtained two slit rolls (that is, those having the same mill roll force), the characteristics were evaluated by the following methods.
- the first is within 2 m from the end of film winding.
- a sample cut-out section is provided, and the second to 20th sample cut-out section is provided every approximately 100 m, including the first sample cut-out section force, and the 21st sample cut-out section is provided within 2 m from the start of film winding.
- the sample film was also cut out for each of the first to 21st sample cutting force.
- the evaluation results are shown in Tables 4-7.
- the impact strength and the laminate strength were shown as the average value of the measured values of each sample sample and the range of fluctuation of the value of each sample sample.
- S-curl the number of sample samples at each evaluation level and the overall evaluation level of all sample samples are shown.
- a biaxially oriented polyamide-based resin laminate film (sample film) cut out from each cut-out part of one slit roll is cut into a 21cm square and left for 2 hours or more in an atmosphere of 23 ° C and 65% RH. did.
- Draw a circle with a diameter of 20cm centered on the center of this sample draw a straight line passing through the center of the circle in the direction of 0 to 165 ° clockwise at 15 ° intervals, assuming the vertical direction (film drawing direction) as 0 °.
- the diameter in the direction was measured and taken as the length before treatment.
- the cut sample is then heat-treated in boiling water for 30 minutes, then removed, wiped off moisture adhering to the surface, air-dried, and left in an atmosphere of 23 ° C and 65% RH for 2 hours or more.
- the length of the straight line drawn in each diametrical direction is measured and set as the length after treatment, and BS (boiling water shrinkage), BSx (maximum boiling water shrinkage), BSax ( Average boiling water shrinkage, BSd (boiling water shrinkage direction difference), BSad (average boiling water shrinkage direction difference) were calculated.
- the maximum 'minimum in the maximum boiling water shrinkage (BSx) of all the samples is obtained, and the difference between the average boiling water shrinkage (BSax) of the maximum and minimum is larger and the average boiling water.
- the variation rate of the maximum boiling water shrinkage (BSx) with respect to the average boiling water shrinkage (BSax) was obtained.
- the maximum and minimum values in the boiling water shrinkage direction difference (BSd) of all the samples are obtained, and the difference between the maximum boiling point and the average boiling water shrinkage direction difference (BSad) is larger.
- a stylus-type three-dimensional surface roughness meter (Kosaka Laboratory Co., Ltd.) is applied to the surface of the biaxially oriented polyamide-based resin layer film (sample film) cut out from each cut-out part of one slit roll.
- SE-3AK with a needle radius of 2 m, a load of 30 mg, and a needle speed of 0.25 mm, with a cut-off value of 0.25 mm in the longitudinal direction of the film and a measurement length of lm m.
- the three-dimensional height of each of the obtained dividing points was analyzed using a three-dimensional roughness analyzer (manufactured by Kosaka Laboratory Ltd., TDA-21), and the three-dimensional average surface roughness (nm )
- JIS-C215 Using biaxially oriented film cut out from each cutout part of the slit roll, JIS-C215
- Test piece width 130mm, length 250mm
- Each biaxially oriented film cut out from each cut-out part of the slit roll was measured using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., 300A) in accordance with JIS K7 136. The measurement was performed twice and the average value was obtained.
- a biaxially oriented film cut from each cut-out part of the slit roll is burned at 800 ° C.
- the weight of the residue was calculated, and the ratio (percentage) of the residue weight to the film weight before combustion was calculated as the content of inorganic particles.
- the weight of the residue when the biaxially oriented film cut out from each cut-out part was dissolved in a solvent such as sulfuric acid was determined, and the initial film weight of the residue was determined. It is also possible to adopt a method for calculating a ratio (percentage) to the weight.
- Respective refractive index in the thickness direction after leaving each sample film cut out from each sample cut-out part in an atmosphere of 23 ° C and 65% RH for 2 hours or more using ATAGO "Abbé refractometer type 4mm" (Nz) was measured. Also, the average average refractive index of all sample films is calculated, and the difference between the maximum or minimum Nz and the average refractive index in all samples as shown in Table 6 is calculated, and the ratio of the difference to the average refractive index is calculated. was calculated as the rate of change.
- Each sample film cut out from each cut-out section is left in an atmosphere of 23 ° C and 65% RH for 2 hours or more, and then the film impact tester TSS type manufactured by Toyo Seiki Seisakusho is used. 12. The breaking strength was measured with a 7 mm hemispherical impactor to determine the impact strength. The average impact strength of all sample films was also calculated.
- the biaxial orientation constituting the slit roll Urethane AC agent (Toyomoto "EL443" was applied, and then a 15m-thick LDPE (low density polyethylene) film was extruded at 315 ° C using a single test laminator device manufactured by Modern Machinery.
- a 40-m-thick LLDPE (linear low-density polyethylene) film was continuously laminated thereon to obtain a laminate film roll having a three-layer structure composed of polyamide-based resin ZLDPEZLLDPE.
- the processability when manufacturing a laminate film roll was evaluated in the following three stages. The temperature when the laminate processability was evaluated was about 25 ° C, and the humidity was about 75% RH.
- the laminate film cut out from the laminate film roll was cut out to a width of 15 mm and a length of 200 mm to make a test piece, and a “Tensilon UMT- ⁇ -500 type” manufactured by Toyo Baldwin was used.
- the peel strength between the polyamide-based resin layer film layer and the LDPE layer was measured at a humidity of 65%.
- the tensile rate was lOcmZ, the peel angle was 180 degrees, and water was added to the peeled portion.
- the laminate strength is measured by cutting out the first sample piece within 2m from the end of winding of the laminate film roll, and the cutting force of the first sample piece is about every 100m, and the second force is 20th.
- a sample piece was cut out, and the 21st sample piece was cut within 2 m from the beginning of winding of the film, and each of the first to 21st sample pieces was measured. The average of those measured values was also calculated.
- the laminate film wound up as a laminate film roll as described above is folded into two parallel to the winding length direction using a test sealer manufactured by Seibu Kikai Co., Ltd.
- the product was heat-sealed continuously at 10 mm in the vertical direction and intermittently heat-sealed at intervals of 150 mm to obtain a semi-finished product with a width of 200 mm.
- This is cut in the winding length direction, and both edges are cut so that the seal portion is 10 mm, then cut in the direction perpendicular to this at the boundary of the seal portion, and a three-side seal bag (seal width: 10 mm) is Produced.
- the supply amount of the chip A is 99.0 weight.
- the chip A is supplied at 1.0% by weight.
- the supply amount of 99.94% by weight and the supply amount of chip C was set to 0.06% by weight.
- a polyamide-based resin-laminated laminated film roll was obtained in the same manner as in Example 1 except that the raw material chip B was used instead of the raw material chip A (i.e., in Example 4, the first to third layers were Polymetaxylene dipamide is contained in the polyamide-based rosin that constitutes it)). And the characteristic of the obtained film roll was evaluated by the same method as Example 1. The evaluation results are shown in Tables 4-7.
- the discharge amount of the first and third extruders was adjusted so that the third layer was not formed and the thickness ratio of the first layer Z second layer was 2Z13.
- a polyamide-based resin laminated film roll was obtained in the same manner as in Example 1.
- the thickness of the first layer (outer layer) and the second layer (inner layer) was about 2 / ⁇ ⁇ , about 13 / zm.
- the properties of the obtained film roll were evaluated by the same method as in Example 1. The evaluation results are shown in Tables 4-7.
- the raw material chip D is used in place of the raw material chip C as the raw material for forming the first layer and the third layer, and the chip to the first extruder and the third extruder in the formation of the first layer and the third layer is used.
- the supply amount of A is 94.0% by weight
- the supply amount of chip D is 6.0% by weight
- the supply amount of chip A to the second extruder in the formation of the second layer is 99.6% by weight.
- the supply amount of chip C was 0.4% by weight.
- the properties of the obtained film roll were evaluated by the same method as in Example 1. The evaluation results are shown in Tables 4-7.
- An unstretched film (laminated film) obtained in the same manner as in Example 1 was stretched longitudinally (first longitudinal stretching) by about 2.2 times at a stretching temperature of about 90 ° C using a roll made of Teflon (registered trademark). Thereafter, the film was stretched longitudinally (second longitudinal stretching) by about 1.5 times at a stretching temperature of about 70 ° C. using a ceramic roll. The Further, the longitudinally stretched sheet was continuously led to a stenter in the same manner as in Example 1, stretched 4.0 times at about 130 ° C, and heat-set at about 210 ° C.
- the film was cooled after being subjected to a lateral relaxation treatment of%, and both edges were cut and removed, whereby a biaxially stretched film of about 15 m was continuously formed over 2000 m.
- the fluctuation range of the film surface temperature when the film was continuously produced was the same as in Example 1.
- the obtained biaxially stretched film was slit and wound up in the same manner as in Example 1 to obtain a polyamide-based resin laminated film roll. Then, the characteristics of the obtained film roll were evaluated by the same method as in Example 1. The evaluation results are shown in Tables 4-7.
- An unstretched film (laminated film) obtained in the same manner as in Example 1 was stretched in two stages in the same manner as in Example 1. After that, the longitudinally stretched sheet is continuously guided to the stenter, stretched 3.6 times at about 130 ° C, and heat-fixed at about 215 ° C to 3.0% lateral relaxation. After the treatment, the film was cooled, and both edges were cut and removed to continuously form a biaxially stretched film of about 15 m over 2000 m. The fluctuation range of the film surface temperature when the film was continuously produced was the same as in Example 1. The obtained biaxially stretched film was slit and wound in the same manner as in Example 1 to obtain a polyamide-based resin laminated film roll. Then, the characteristics of the obtained film roll were evaluated by the same method as in Example 1. The evaluation results are shown in Tables 4-7.
- Polyamide-based resin-laminated film roll in the same manner as in Example 1 except that the angle of inclination of each hot bar was changed to 65 ° when the raw material chips in the blender were fed to the hot bar immediately above the first to third extruders. Got.
- the properties of the obtained film roll were evaluated by the same method as in Example 1. The evaluation results are shown in Tables 4-7.
- Example 1 When forming an unstretched resin sheet, Example 1 was used except that a single-layer structure was formed without forming the second layer and the third layer, and only the raw material chip A was used as a raw material for forming the first layer. In the same manner, a polyamide-based resin film roll was obtained. The properties of the obtained film roll were evaluated by the same method as in Example 1. The evaluation results are shown in Tables 4-7. [Comparative Example 2]
- a polyamide-based resin laminated film roll was obtained in the same manner as in Example 1 except that the raw material chip E was used instead of the raw material chip C.
- the average long diameter and average tip length of the polyamide-based resin chips (chip E) other than the polyamide-based resin chips are the most used. It is not included within ⁇ 20% of the average long diameter and average chip length of the chip (chip A).
- the properties of the obtained film roll were evaluated by the same method as in Example 1. The evaluation results are shown in Tables 4-7.
- Polyamide-based resin-laminated film roll in the same manner as in Example 1 except that the angle of inclination of the hot bar was changed to 45 ° when the raw material chips in the blender were supplied to each hot bar immediately above the first to third extruders. Got.
- the properties of the obtained film roll were evaluated by the same method as in Example 1. The evaluation results are shown in Tables 4-7.
- the raw material chips A and C were pre-dried and then allowed to stand for about 5 hours in each blender before being supplied to the hot tubs immediately above the first to third extruders, as in Example 1. Thus, a polyamide-based resin laminated film roll was obtained.
- the moisture content of chips A and C immediately before being supplied to each hot bar was 800 ppm, and the temperature of chips A and C immediately before being supplied to each hot bar was about 30 ° C. .
- the properties of the obtained film roll were evaluated by the same method as in Example 1. The evaluation results are shown in Tables 4-7.
- the unstretched film obtained in the same manner as in Example 1 was stretched about 1.5 times (first longitudinal stretching) at a stretching temperature of about 90 ° C by a Teflon (registered trademark) roll, and then made of ceramic. Using the roll, the film was stretched longitudinally (second longitudinal stretching) about 2.2 times at a stretching temperature of about 70 ° C. Further, the longitudinally stretched sheet is continuously guided to a stenter, and is transversely stretched in the same manner as in Example 1. After heat-fixing and lateral relaxation treatment, the sheet is cooled and both edges are cut and removed. A biaxially stretched film of about 15 m was continuously formed over 2000 m. The fluctuation range of the film surface temperature when the film was continuously produced was the same as in Example 1. Then, the resulting film was slit and wound up in the same manner as in Example 1 to obtain a polyamide-based resin laminated film. The properties of the obtained film roll were evaluated by the same method as in Example 1. The evaluation results are shown in Tables 4-7.
- Variation rate of silica content relative to average silica content The variation rate was calculated based on the larger of the a and the minimum in the silica content of all the samples, and the larger difference from the average silica content. * Fluctuation rate of maximum boiling water shrinkage relative to average boiling water shrinkage;
- the fluctuation rate was calculated with the larger difference between ⁇ ⁇ equal boiling water shrinkage direction difference among the maximum ⁇ s small boiling water shrinkage direction difference of all samples.
- Fluctuation rate was calculated with the difference between the average thickness and the maximum / minimum thickness over the entire length.
- the variation rate was calculated from the maximum / minimum of the refractive indexes of all the samples with the larger difference from the average refractive index.
- the film roll of the comparative example has poor laminating workability due to large variations in physical properties such as vertical thickness unevenness over the entire roll, boiling water shrinkage rate, refractive index, and dynamic friction coefficient under high humidity. It can be seen that the haze is extremely strong and the S-curl phenomenon is observed.
- the polyamide-based resin-laminated laminated film roll of the present invention has excellent processing characteristics as described above, it can be suitably used for food retort processing.
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Laminated Bodies (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
Description
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Priority Applications (2)
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EP05820356A EP1889717B1 (en) | 2005-06-10 | 2005-12-21 | Polyamide resin laminate roll and process for producing the same |
US11/921,866 US8465831B2 (en) | 2005-06-10 | 2005-12-21 | Polyamide based laminated resin film roll and production process thereof |
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JP2005-171487 | 2005-06-10 | ||
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JP2005203303A JP3829863B1 (ja) | 2005-06-10 | 2005-07-12 | ポリアミド系樹脂積層フィルムロール、およびその製造方法 |
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US (1) | US8465831B2 (ja) |
EP (1) | EP1889717B1 (ja) |
JP (1) | JP3829863B1 (ja) |
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US20100221554A1 (en) * | 2007-11-08 | 2010-09-02 | Unitika Ltd. | Process for producing polyamide resin film and polyamide resin film obtained by the process |
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JP3829864B1 (ja) * | 2005-06-22 | 2006-10-04 | 東洋紡績株式会社 | ポリアミド系混合樹脂積層フィルムロール、およびその製造方法 |
JP4618228B2 (ja) * | 2006-09-25 | 2011-01-26 | 東洋紡績株式会社 | ポリアミド系混合樹脂積層フィルムロール、およびその製造方法 |
WO2008108208A1 (ja) * | 2007-02-27 | 2008-09-12 | Toyo Boseki Kabushiki Kaisha | ポリプロピレン系樹脂積層フィルムロール、およびその製造方法 |
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- 2005-07-12 JP JP2005203303A patent/JP3829863B1/ja active Active
- 2005-12-21 WO PCT/JP2005/023512 patent/WO2006132005A1/ja active Application Filing
- 2005-12-21 US US11/921,866 patent/US8465831B2/en active Active
- 2005-12-21 KR KR1020077030845A patent/KR101044165B1/ko active IP Right Grant
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Also Published As
Publication number | Publication date |
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EP1889717A1 (en) | 2008-02-20 |
TW200704512A (en) | 2007-02-01 |
JP2007015357A (ja) | 2007-01-25 |
EP1889717B1 (en) | 2012-10-10 |
JP3829863B1 (ja) | 2006-10-04 |
US20090191369A1 (en) | 2009-07-30 |
US8465831B2 (en) | 2013-06-18 |
TWI402168B (zh) | 2013-07-21 |
KR101044165B1 (ko) | 2011-06-24 |
KR20080031224A (ko) | 2008-04-08 |
EP1889717A4 (en) | 2009-07-08 |
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