Classifications

• • 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
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
• • 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
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • 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
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • 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
  • B32B2323/00—Polyalkenes
  • B32B2323/04—Polyethylene
  • B32B2323/046—LDPE, i.e. low density polyethylene
• • 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
  • B32B2323/00—Polyalkenes
  • B32B2323/10—Polypropylene
• • 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
  • B32B2325/00—Polymers of vinyl-aromatic compounds, e.g. polystyrene
• • 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
  • B32B2439/00—Containers; Receptacles
  • B32B2439/40—Closed containers
  • B32B2439/46—Bags
• • 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
  • B32B2457/00—Electrical equipment
  • B32B2457/10—Batteries
• • 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
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present invention relates to a polypropylene-based composite film having high heat seal strength from a low temperature, easy slipping, low temperature impact resistance, and bending whitening resistance, and a packaging material using the same.
• a polypropylene film is used as a packaging film.
• a polypropylene film and a polyethylene terephthalate (PET) film or a nylon (Ny) film, particularly a stretched PET film or a stretched nylon film (ONy) A packaging material in which aluminum foil is laminated is widely known.
• an organic lubricant is added to a polypropylene film used for a packaging film, and the lubricant oozes out to the surface of the film after film formation, thereby exhibiting good slipperiness.
• a conventional polypropylene film it sticks to a film such as a stretched PET film, ONy, or aluminum foil via an adhesive, and bleeds onto the film surface when aged at a certain temperature to cure the adhesive. Since the organic lubricant (particularly fatty acid amide-based lubricant) that came out re-transferred into the film, there was a tendency for slipping to become worse.
• the film surface has good slipperiness, particularly a static friction coefficient of a certain level or less, for example, a static friction coefficient of 0.3 or less.
• Patent Document 1 discloses that an unsaturated fatty acid amide having a melting point of 70 to 90 ° C. is 0.02 to 0.2% by weight, and an unsaturated fatty acid bisamide having a melting point of 115 to 135 ° C. is 0.01 to 0.12% by weight.
• unsaturated fatty acid amide and unsaturated fatty acid bisamide are Although the amount needs to be increased and the coefficient of friction can be kept low, the amount of lubricant on the film surface becomes too large after the aging treatment, causing deposits on the rolls and the like, resulting in problems in the working environment.
• a lubricant having an optimum aging temperature of less than 40 ° C such as erucamide is added to both outer layers, and a lubricant having an optimum aging temperature of 40 ° C or more such as behenamide or ethylenebisamide is added to the intermediate layer.
• a polypropylene multilayer film and a composite film having a three-layer structure using a propylene / ethylene random copolymer for an intermediate layer and a propylene / ethylene random copolymer for at least one outer layer are provided. It is disclosed.
• the polypropylene film when used as a packaging film, has excellent properties such as bending whitening resistance, low temperature impact resistance, and slipperiness in a well-balanced manner in addition to the heat sealability described above.
• conventional films have not always been able to satisfy high demands in recent years.
• bag breaking strength under severe conditions that can not be torn even when repeatedly dropped from a relatively high position in a bag containing contents may be required ( Especially in retort applications, there is a need for bag breaking strength under such severe conditions), but a polypropylene film designed for low temperature impact resistance based on the criteria for bag breaking strength under such severe conditions. Is not found.
• JP-A-9-77881 Japanese Patent Laid-Open No. 11-334004 JP-A-10-87744
• the problem of the present invention is that the heat sealing force is high from low temperature to high temperature, excellent in low temperature impact resistance and bending whitening resistance, and even if the film is aged at 60 ° C., the amount of lubricant on the film surface is within an appropriate range. It is to provide a polypropylene-based composite film that can be maintained and achieve a desirable value as a coefficient of static friction on the film surface, and a packaging material using the same.
• the polypropylene composite film of the present invention has the following configuration.
• the A layer is mainly composed of a propylene random copolymer having a melt flow rate at 230 ° C. of 2 to 10 g / 10 minutes and a melting point of 130 to 150 ° C.
• the layer has a ratio ([ ⁇ ] Cxs / [ ⁇ ] Cxis) of the intrinsic viscosity [ ⁇ ] Cxs of the soluble part of 20 ° C. xylene to the intrinsic viscosity [ ⁇ ] Cxis of the insoluble part of 1.6 or more.
• the main component is a resin composition in which 10 to 90 parts by weight of a low density polyethylene polymer (b) is blended with 100 parts by weight of the ethylene block copolymer (a), and the A layer contains 200 to 200 fatty acid amide lubricants.
• the polypropylene layer is a polypropylene composite film containing 2000 ppm, and the B layer contains 500 to 5000 ppm of a fatty acid amide lubricant.
• the amount of lubricant on the film surface at normal temperature (23 ° C.) can be maintained within an appropriate range, and the amount of lubricant on the film surface can be maintained within an appropriate range even after aging at 60 ° C.
• the static friction coefficient of the surface can be suppressed to 0.3 or less, and a polypropylene composite film suitable for battery packaging materials requiring slipperiness and a packaging material including the same can be realized.
• a polypropylene composite film suitable for a packaging material for packaging, and a packaging material including the same can be realized.
• the polypropylene composite film of the present invention comprises at least two layers of A layer / B layer, and the A layer contains a propylene random copolymer as a main component.
• a block copolymer having an olefin block more preferably, a B layer containing a propylene random copolymer (d) is provided.
• the layer A of the polypropylene composite film of the present invention is mainly composed of a propylene random copolymer having a melt flow rate at 230 ° C. (hereinafter abbreviated as MFR) of 2 to 10 g / 10 min and a melting point of 130 to 150 ° C.
• MFR melt flow rate at 230 ° C.
• the main component in the A layer means a component exceeding 50% by weight in the A layer.
• the heat seal strength at 130 ° C. and 160 ° C. decreases.
• the MFR at 230 ° C. of the propylene random copolymer of the A layer is less than 2 g / 10 minutes, the uniform lamination property with the B layer may be deteriorated, and the low temperature heat seal strength at 130 ° C. may be deteriorated. If it exceeds 10 g / 10 minutes, the bleed-out property of the lubricant may deteriorate and the slip property may decrease.
• the propylene random copolymer of layer A is a copolymer of propylene and at least one ⁇ -olefin, and examples of the ⁇ -olefin include ethylene, butene, and octene. From the viewpoint of heat sealability, a propylene / ethylene random copolymer of ethylene is preferable.
• the layer A of the polypropylene composite film of the present invention preferably contains the propylene random copolymer as a main component and 200 to 2000 ppm of a fatty acid amide lubricant. If the content of the fatty acid amide-based lubricant is less than 200 ppm, the slipperiness may be deteriorated. If it exceeds 2000 ppm, heat scattering may increase during melt extrusion, and the film-forming property may deteriorate due to contamination of the process. The low-temperature heat seal strength may also be reduced.
• fatty acid amide-based lubricant examples include oleic acid amide, erucic acid amide, stearic acid amide, palmitic acid amide, behenic acid amide and the like, and particularly, resin composition in which erucic acid amide is used in the polypropylene-based composite film of the present invention. It is preferable from the viewpoint of dispersibility in water and expression of slipperiness.
• the slipping property is improved even if the content of the fatty acid amide-based lubricant is reduced.
• the polypropylene composite film is wound up in a long length, defects due to defects such as wrinkles and air loss are reduced. If the content is 300 ppm or less, the effect of imparting slipperiness is not observed, and if it exceeds 5000 ppm, the heat sealability may be lowered.
• Preferred examples of the inorganic particles include silica, zeolite, and calcium carbonate, and preferred examples of the organic particles include crosslinked PS and crosslinked PMMA.
• Their average particle size is preferably in the range of 1 to 5 ⁇ m. If the average particle size is less than 1 ⁇ m, the effect of addition is not observed, and if it exceeds 5 ⁇ m, the heat sealing force may be reduced.
• the B layer of the polypropylene composite film of the present invention is the ratio of the intrinsic viscosity [ ⁇ ] Cxs of the soluble part of xylene at 20 ° C. to the intrinsic viscosity [ ⁇ ] Cxis of the insoluble part ([ ⁇ ] Cxs / [ ⁇ ] Cxis).
• the main component is a resin composition comprising a propylene / ethylene block copolymer (a) having a molecular weight of 1.6 or more and a low density polyethylene polymer (b).
• the main component in the B layer means a component exceeding 50% by weight in the B layer.
• the propylene / ethylene block copolymer (a) of the B layer of the polypropylene-based composite film of the present invention is a ratio of the intrinsic viscosity [ ⁇ ] Cxs of the soluble part of xylene and the intrinsic viscosity [ ⁇ ] Cxis of the insoluble part at 20 ° C. ([ ⁇ ] Cxs / [ ⁇ ] Cxis) is 1.6 or more, preferably in the range of 1.6 to 2.0. If [ ⁇ ] Cxs / [ ⁇ ] Cxis is less than 1.6, the resin is reduced due to a decrease in heat seal strength due to film crushing when heat-sealed at 160 ° C. or higher, and pressure is applied during heat sealing or drawing.
• the propylene / ethylene block copolymer (a) of the B layer has a proportion of a polypropylene portion of 20 ° C. xylene insoluble part of 70 to 85% by weight, and the intrinsic viscosity [ ⁇ ] Cxis of the xylene insoluble part is 1.5 to 2.0 dl / g, and the intrinsic viscosity [ ⁇ ] Cxs of the 20 ° C. xylene-soluble part indicating the ratio of the ethylene / propylene copolymer rubber component is 2.4 to 4.0 dl / g.
• the film may be thinned due to crushing of the film during heat sealing or drawing, and if it exceeds 2.0 dl / g, the film becomes too hard. As a result, the drawability may deteriorate.
• the intrinsic viscosity [ ⁇ ] Cxs of the xylene soluble part is less than 2.4 dl / g, the seal strength may be lowered.
• the intrinsic viscosity exceeds 4.0 dl / g the particle size of the rubber component is very large. Cracks may occur at the sea-island structure interface, resulting in low-temperature impact resistance and reduced heat sealability.
• the 20 ° C. xylene insoluble part and the soluble part are the above-mentioned propylene / ethylene block copolymer pellets completely dissolved in boiling xylene, then cooled to 20 ° C. and allowed to stand for 4 hours or more. When this was separated into a precipitate and a solution, the precipitate was called a 20 ° C. xylene insoluble part, and the part obtained by drying the solution part (filtrate) at 70 ° C. under reduced pressure was the xylene soluble part. Called.
• the propylene / ethylene block copolymer has an intrinsic viscosity of xylene-insoluble and soluble components, and a method for adjusting the melt flow rate includes hydrogen gas in each step during the polymerization of the propylene / ethylene block copolymer.
• a method of adding a molecular weight adjusting agent such as a metal compound, a method of adding an additive when melt-kneading and pelletizing a polymer obtained in powder form, a melt-kneading of a polymer obtained in powder form, and pelletizing A method for adjusting the kneading conditions during the process can be mentioned.
• a method of polymerizing propylene, ethylene or the like as a raw material using a catalyst can be mentioned.
• a Ziegler-Natta type or metallocene catalyst can be used as the catalyst, and for example, those described in JP-A-07-216017 can be preferably used.
• a trivalent titanium compound-containing solid catalyst obtained by treating with a mixture of an ether compound and titanium tetrachloride or a mixture of an ether compound, titanium tetrachloride and an ester compound, (2) an organoaluminum compound, (3 And a catalyst system comprising an electron donating compound (dialkyldimethoxysilane or the like is preferably used).
• a polymer part mainly composed of propylene is polymerized in the first step substantially in the absence of an inert agent, It is preferable to use a method in which the ethylene / propylene copolymer portion is polymerized in the gas phase in the second step.
• the polymer part mainly composed of propylene is preferably a propylene homopolymer having a melting point of 160 ° C. or higher from the viewpoint of heat resistance, rigidity, etc. It may be a copolymer with a small amount of ⁇ -olefin such as ethylene and 1-butene.
• a low density polyethylene polymer (b) is blended with the propylene / ethylene block copolymer (a).
• the polypropylene composite film of the present invention is cracked (whitened) at the interface of the sea-island structure of the film, for example, during deformation of drawing for battery exterior use, There is a concern that some electrolyte will leak. Therefore, it is necessary to design the dispersion of the rubber component at the island portion in the propylene / ethylene block copolymer to be extremely small, and the dispersion can be extremely small by containing the low density polyethylene polymer.
• the low temperature impact resistance and the bending whitening resistance are improved by increasing the glass transition point component lower than that of the propylene / ethylene block copolymer.
• the rubber component in the B layer when used for packaging materials for retort, the occurrence of unevenness (swelling skin) due to swelling of the film by the oily food of the contents is suppressed (anti-resistance) Yuzu skin properties can be improved).
• the low-density polyethylene resin (b) is preferably a low-density polyethylene, a linear low-density polyethylene, or the like, but the linear low-density polyethylene is a rubber component in the propylene / ethylene block copolymer. This is preferable because the dispersion effect is high, and the resistance to bending whitening and the skin resistance is improved.
• the density of the linear low-density polyethylene is in the range of 0.900 to 0.935 g / cm 3 and the MFR is in the range of 0.5 to 20 g / 10 min. It is preferable because the dispersibility is good and the effect of dispersing the rubber component of the propylene / ethylene block copolymer is high.
• the method for producing the linear low density polyethylene is not particularly limited, and those produced using a conventional Ziegler-Natta catalyst or a metallocene catalyst can be used.
• the above propylene / ethylene block copolymer does not impair the required physical properties of high-performance ethylene-based or styrene-based elastomers that are produced by combining a catalyst technology that achieves a high rubber content and a polymerization process technology. To the extent, that is, 5 to 30% by weight can be contained. Thereby, the dispersion of the sea-island structure can be reduced as in the case of the low-density polyethylene-based polymer.
• the layer B in the polypropylene composite film of the present invention is a resin composition in which 15 to 90 parts by weight of the low density polyethylene polymer (b) is blended with 100 parts by weight of the propylene / ethylene block copolymer (a). It has a main component.
• the low density polyethylene polymer (b) is less than 15 parts by weight with respect to 100 parts by weight of the propylene / ethylene block copolymer (a)
• whitening due to cracks at the time of drawing using, for example, a battery packaging material May occur, and there is a concern that the electrolyte as the content may leak.
• a yuzu skin may become large and an external appearance defect may arise.
• the low-density polyethylene polymer (b) exceeds 90 parts by weight with respect to 100 parts by weight of the propylene / ethylene block copolymer (a), the shift of the lubricant to the film surface layer is reduced and the slipperiness is poor.
• the low temperature impact resistance may be deteriorated.
• the dispersibility may be deteriorated, and a streak-like defect may be generated at the time of melt extrusion to deteriorate the film forming property.
• the polypropylene composite film of the present invention is aged at 60 ° C. or higher for curing the adhesive after lamination with other materials.
• the fatty acid amide-based lubricant in the B layer moves to the B layer surface side, and further from there to the A layer.
• the lubricant contained in the A layer tends to be transferred in the A layer, whereas it is transferred from the B layer to the A layer.
• the range of the amount of lubricant can be maintained in the range of 3 to 20 mg / m 2 , preferably 5 to 15 mg / m 2 , and a static friction coefficient of 0.3 or less between the surfaces of the A layers is achieved.
• B layer is a block copolymer having a styrene block with respect to 100 parts by weight of the propylene / ethylene block copolymer (a) and 10 to 90 parts by weight of the low density polyethylene polymer (b), or
• a resin composition in which 5 to 20 parts by weight of the polymer (c), which is a block copolymer having a crystalline olefin block, is blended, the rubber component in the portion to be islands in the propylene / ethylene block copolymer is further dispersed. Can be small.
• the block copolymer having a styrene block or the block copolymer having a crystalline olefin block as the polymer (c) has a block copolymer (c1) having a styrene block or a crystalline olefin block. It is a block copolymer (c2).
• Examples of the block copolymer (c1) having a styrene block used in the present invention include those provided in JP-A-3-128957.
• the polymer block is composed of a styrene monomer (c3) and a conjugated diene monomer (c4).
• the styrene monomer (c3) is not particularly limited, and specific examples include styrene, ⁇ -methyl styrene, paramethyl styrene, etc. Among these, styrene and ⁇ -methyl styrene are preferable, and the polymerization point is high. In particular, styrene is preferable.
• Examples of the conjugated diene monomer (c4) include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, Examples include 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene and the like.
• a polybutadiene block is preferable because it is excellent in rubber elasticity expressed by the polymer block and can impart excellent impact resistance to the finally obtained polypropylene-based composite film of the present invention.
• a commercially available product that can be particularly preferably used as such a block copolymer (c1) having a styrene block includes a styrene / ethylene butylene / styrene triblock copolymer (hereinafter abbreviated as SEBS). .
• SEBS styrene / ethylene butylene / styrene triblock copolymer
• the ethylene butylene block portion is easily compatible with the polypropylene-based resin, and the effect of increasing the compatibility with the propylene / ethylene block copolymer (a) is high.
• the content of polystyrene block in SEBS is preferably 12 to 67% by weight.
• the blocking resistance is good, and when it is 67% by weight or less, the low-temperature impact resistance is good.
• an MFR at 230 ° C. of 0.5 to 10 g / 10 min is preferable.
• the MFR is 0.5 g / 10 min or more, the dispersibility of the mixed resin is good, and when the MFR is 10 g / 10 min or less, the low temperature impact resistance is good.
• the block copolymer (c2) having a crystalline olefin block used in the present invention is a copolymer having a block (c5) made of crystalline polyolefin and another block (c6) not having crystallinity, Preferably, the other block (c6) has a block made of a role diene polymer.
• Examples of the block copolymer (c2) having such a crystalline olefin block include those provided in JP-A-3-128957. Specifically, a polybutadiene polymer block having a low 1,2-vinyl bond content (for example, 25% or less) and a polymer mainly composed of a conjugated diene compound, which contains 1,2- and 3,4-bonds. A copolymer composed of a polymer block having a high rate (for example, 50% or more) is synthesized, and the polybutadiene portion is made to have a structure similar to polyethylene by hydrogenating the copolymer to form a crystalline polymer block. And the like.
• conjugated diene compound examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl. 1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene, and the like. From the viewpoint of industrial availability, 1,3-butadiene and isoprene are preferably used.
• a block copolymer having a configuration of polyethylene, ethylene butylene, and polyethylene (hereinafter abbreviated as CEBC) can be mentioned. Since the ethylene butylene block portion is easily compatible with the polypropylene resin and the polyethylene block portion is easily compatible with the polyethylene resin, the propylene / ethylene block copolymer (a) and the low density polyethylene polymer (b ) Is highly effective in increasing compatibility.
• the polyethylene block content in CEBC is preferably 15 to 40% by weight.
• the blocking resistance is good, and when it is 40% by weight or less, the low-temperature impact resistance is good.
• an MFR at 230 ° C. of 0.5 to 10 g / 10 min is preferable.
• the MFR is 0.5 g / 10 min or more, the dispersibility of the mixed resin is good, and when the MFR is 10 g / 10 min or less, the low temperature impact resistance is good.
• the B layer has a melt flow rate of 2 to 10 g at 230 ° C. with respect to 100 parts by weight of the propylene / ethylene block copolymer (a) and 10 to 90 parts by weight of the low density polyethylene polymer (b). / 10 minutes, by forming a resin composition containing 10 to 50 parts by weight of the propylene random copolymer (d) having a melting point of 130 to 150 ° C., the interfacial adhesive force with the A layer is increased. As a result, the heat seal strength is increased, which is preferable.
• the addition amount of the propylene random copolymer (d) is less than 10 parts by weight, the effect of improving the heat seal strength is not observed, and when it exceeds 50 parts by weight, the low temperature impact resistance may be lowered.
• the propylene random copolymer (d) is preferably a random copolymer with an ⁇ -olefin such as ethylene, butene, octene, etc., and a propylene / ethylene random copolymer of a copolymer with ethylene is a heat. This is preferable because the range in which both the sealing force and the sliding property can be compatible is wide.
• the layer thickness may be reduced depending on the temperature and pressure at the time of heat sealing, and if the melting point exceeds 150 ° C., the low temperature impact resistance is lowered. Sometimes.
• the polypropylene-based composite film of the present invention comprises at least a two-layer structure of A layer / B layer, but the MFR at 230 ° C. is 2 to 10 g / m on the other surface of the B layer in the present invention.
• a three-layer laminate of layer A / layer B / layer C comprising a main component of a propylene random copolymer having a melting point of 130 to 150 ° C. for 10 minutes and a layer C containing 200 to 2000 ppm of a fatty acid amide lubricant. This is preferable because the laminate strength with other base materials is increased.
• the static friction coefficient after aging at 23 ° C. for 3 days between the A layer surfaces is preferably 0.3 or less, and more preferably in the range of 0.1 to 0.3.
• the coefficient of static friction after aging at 60 ° C. for 3 days between the A layer surfaces is preferably 0.3 or less, and more preferably in the range of 0.1 to 0.3. If the static friction coefficient between the A layer surfaces exceeds 0.3, battery packaging materials that require slipperiness by drawing, film breakage occurs during molding, resulting in poor product yield, and packaging materials for retort foods.
• the opening of the bag may be poor and the content filling property may be deteriorated. If the static friction coefficient between the A layer surfaces is less than 0.1, a shift may occur when stacking bag-fabricated products.
• the static friction coefficient when the A layer surface and the B layer surface or the C layer surface are overlapped is 0.3 or less, so that the polypropylene composite film of the present invention is wound up in a long length. Occasionally, traps and air pockets are reduced and productivity is improved.
• the content of the fatty acid amide-based lubricant in the B layer is less than 500 ppm, the amount of the fatty acid amide-based lubricant on the surface of the A layer is small, the coefficient of static friction between the A layer surfaces exceeds 0.3, and slipperiness may be deteriorated. It may not be satisfactorily used in battery packaging applications where slipperiness is required by drawing. In addition, if it exceeds 5000 ppm, the friction coefficient can be kept low, but the amount of lubricant on the film surface becomes too large, and the lubricant may adhere to the roll or the like in the film forming or laminating process, which may cause problems in the working environment. . Moreover, when heat-sealing, a lubricant may accumulate at the film interface, and the heat-sealing strength may be reduced.
• the thickness of the A layer or C layer of the polypropylene composite film of the present invention is preferably 1 ⁇ m or more, and the total thickness is preferably in the range of 20 to 200 ⁇ m.
• the thickness of the A layer or the C layer is less than 1 ⁇ m, sufficient heat seal strength at 130 ° C. and 160 ° C. may not be obtained, and the range of 2 to 30 ⁇ m is preferable. Further, if the total thickness is less than 20 ⁇ m, the low temperature impact resistance may not be sufficiently obtained, and there is a concern that the electrolyte solution of the battery, which is the contents, or the retort food may leak. On the other hand, when the total thickness exceeds 200 ⁇ m, the laminate processability is lowered and the production cost is increased, which is not preferable.
• the volume resistivity of the polypropylene composite film of the present invention is preferably in the range of 1 ⁇ 10 11 to 1 ⁇ 10 14 ⁇ ⁇ m.
• the battery packaging material required electrical insulation, the volume resistivity is less than 1 ⁇ 10 11 ⁇ ⁇ m poor insulating properties, there is the battery performance decreases, and when it exceeds 1 ⁇ 10 14 ⁇ ⁇ m electrostatic May cause problems in laminating properties and battery performance.
• the A layer and the C layer contain 200 to 2000 ppm of fatty acid amide lubricant, and the B layer contains a fatty acid amide lubricant. This can be achieved by adding 500 to 5000 ppm.
• the polypropylene composite film of the present invention has a heat seal strength at 130 ° C. of the A layer surfaces of 30 N / 15 mm or more, and a heat seal strength at 160 ° C. or more of 55 N / 15 mm or more.
• a heat seal strength at 130 ° C. of the A layer surfaces of 30 N / 15 mm or more
• a heat seal strength at 160 ° C. or more of 55 N / 15 mm or more When used as a packaging material, it is preferable in protecting contents.
• the packaging material for retort foods requires low-temperature sealing properties, and if the heat seal strength at 130 ° C. between the A layer surfaces is less than 30 N / 15 mm, the contents of the food may leak after retort processing.
• the heat seal strength at 160 ° C. or higher is less than 55 N / 15 mm, when used as a battery packaging material, leakage of electrolyte due to an increase in internal pressure due to heat during charging and discharging, or when used as a retort food packaging material, Liquid leakage may occur from the heat seal part in the bag drop test.
• the present invention also provides a battery outer packaging bag and a retort packaging bag made of the laminate as described above.
• the laminate is formed by laminating at least one selected from a biaxially stretched polyethylene terephthalate film, a biaxially stretched polypropylene film, a biaxially stretched nylon film, and an aluminum foil on the opposite side of the A layer.
• a biaxially stretched polyethylene terephthalate film a biaxially stretched polypropylene film
• a biaxially stretched nylon film a biaxially stretched nylon film
• aluminum foil on the opposite side of the A layer.
• a normal dry laminating method in which an adhesive is attached to the constituent film of the laminate can be suitably employed.
• the polypropylene composite film of the present invention and the base material layer can be attached.
• a method of extruding and laminating a directly-adhesive polyolefin resin can also be adopted.
• the dry laminating adhesive is not particularly limited.
• a polyol selected from the group consisting of polyurethane polyols, polyester polyols and polyether polyols.
• a two-component reactive adhesive composed of a first liquid composed of one or more of the above and a second liquid (curing agent) composed of isocyanate.
• an adhesive layer formed of a polyurethane adhesive, an acrylic adhesive, an epoxy adhesive, a polyolefin adhesive, an elastomer adhesive, a fluorine adhesive, etc. can be mentioned.
• it is preferable to use an acrylic adhesive or a polyolefin-based adhesive when used as a battery packaging material, the electrolytic solution resistance and the water vapor barrier property can be improved.
• These laminates are used after being processed into packaging materials such as molded sheets, flat bags, standing pouches, etc., using the polypropylene composite film of the present invention as a sealing layer.
• the laminated structure of these laminates is required for packaging materials, for example, sealing performance to satisfy the quality retention period of the food to be packaged, size that can handle the weight of the contents, low-temperature impact resistance, electrolyte resistance, etc. It is appropriately selected depending on.
• Heat seal strength For battery packaging materials, a biaxially stretched PET film (PET-BO) with a thickness of 12 ⁇ m, a nylon 6 stretched film (ONy) with a thickness of 15 ⁇ m, and aluminum with a thickness of 40 ⁇ m formed on both sides.
• PET-BO biaxially stretched PET film
• ONy nylon 6 stretched film
• the foil and the B layer or C layer of the polypropylene composite film of the present invention are bonded together by an ordinary dry laminating method using a urethane adhesive, and aged at 60 ° C. for 3 days, and then PET-BO / adhesive / ONy.
• Adhesive / Aluminum foil / Adhesive / A laminate (A) of the polypropylene composite film of the present invention (outermost layer A layer surface) was obtained.
• a stretched PET film having a thickness of 12 ⁇ m, an ONy film having a thickness of 15 ⁇ m, and the polypropylene composite film of the present invention are bonded together by a normal dry laminating method using a urethane-based adhesive, and 40 ° C. Was aged for 3 days to obtain a laminate (B) of PET-BO / adhesive / ONy / adhesive / polypropylene composite film of the present invention (outermost layer A layer surface).
• a flat plate heat sealer was used, and the A layer surfaces were overlapped with each other under the conditions of a seal temperature of 160 ° C., a seal pressure of 0.2 MPa, and a soot seal time of 2 seconds. After heat sealing, it was cut into strips with a width of 15 mm, and the heat seal strength was measured by a T-type peeling method at a tensile speed of 300 mm / min using Tensilon manufactured by Orientec. When the heat seal strength was 55 N / 15 mm or more, ( ⁇ ), and less than 55 N / 15 mm were ( ⁇ ).
• a flat plate heat sealer is used, A layer surface is piled up, seal temperature 130 degreeC and 160 degreeC, seal pressure 0.2 MPa, seal time After heat-sealing under conditions of 1 second, after cutting into a strip of 15 mm width and performing a retort treatment at 130 ° C. for 30 minutes, using a Tensilon manufactured by Orientec Corporation at a tensile speed of 300 mm / min, The heat seal strength was measured by a mold peeling method. If the heat seal strength at 130 ° C.
• the heat seal strength at 160 ° C. was evaluated as ( ⁇ ) when the heat seal strength was 55 N / 15 mm or more, and (x) when less than 55 N / 15 mm.
• the laminate (B) for retort packaging material prepared by the above heat seal strength measurement two of the laminates are made of the polypropylene composite film (layer A surface) of the present invention on the inner surface of the bag.
• a standing pouch having a bag size of 150 mm ⁇ 285 mm was prepared using a CA-450-10 type heat sealer manufactured by Fuji Impulse Co., Ltd., with a heating time of 1.4 seconds and a cooling time of 3.0 seconds.
• This bag is filled with 1 L of 0.1% by weight saline and then retorted at 135 ° C. for 30 minutes. After the retort-treated bag is stored in a refrigerator at 0 ° C.
• the average number of n times of 20 times until the bag breaks is 30 times or more as good low temperature impact resistance ( ⁇ ), and less than 30 times as low temperature impact resistance failure ( ⁇ ). evaluated.
• Rank 1 was rated as excellent scratch skin resistance ( ⁇ )
• Rank 2 as excellent scratch skin resistance ( ⁇ )
• Ranks 4 and 5 as poor scratch skin resistance ( ⁇ ).
• each layer in the case of a laminated film is determined by embedding the laminated film in an epoxy resin, cutting out the film cross section with a microtome, observing the cross section with a scanning electron microscope at a magnification of 3,000 times, The thickness was calculated.
• Propylene random copolymer-1 Propylene / ethylene random copolymer (denoted as “EPC-1”) having an MFR of 3.3 g / 10 min and a melting point of 142 ° C.
• Propylene random copolymer-2 Propylene-ethylene random copolymer (denoted as “EPC-2”) having a melting point of 138 ° C. with an MFR of 6.0 g / 10 min.
• Propylene random copolymer-3 Propylene-ethylene random copolymer (denoted as “EPC-3”) having a melting point of 127 ° C.
• Propylene random copolymer-4 A propylene / ethylene random copolymer (denoted as “EPC-4”) having an MFR of 1.5 g / 10 min and a melting point of 132 ° C.
• Propylene random copolymer-5 Propylene / ethylene random copolymer having a melting point of 156 ° C. (denoted as “EPC-5”), MFR 5.0 g / 10 min.
• Propylene / ethylene block copolymer-1 20 ° C. xylene soluble part 10% by weight, intrinsic viscosity [ ⁇ ] Cxs 3.2 dl / g of the soluble part, 20 ° C.
• BPP-2 propylene / ethylene block copolymer
• Propylene / ethylene block copolymer-3 20 ° C.
• xylene soluble part 20% by weight, intrinsic viscosity [ ⁇ ] Cxs 2.5 dl / g of the soluble part, 20 ° C.
• BPP-4 propylene / ethylene block copolymer
• LLDPE Linear low density polyethylene
• Fatty acid amide lubricant As the fatty acid amide lubricant, erucic acid amide was used.
• erucic acid amide was mixed with the propylene random copolymers EPC-1 to EPC-5 as the A layer composition.
• the composition of the B layer is a propylene / ethylene block copolymer (BPP-) having a ratio of xylene soluble part [ ⁇ ] Cxs and insoluble part [ ⁇ ] Cxis at 20 ° C. of [ ⁇ ] Cxs / [ ⁇ ] Cxis of 1.68. 1), linear low density polyethylene (LLDPE) as a low density polyethylene polymer, and erucic acid amide were mixed.
• BPP- propylene / ethylene block copolymer
• LLDPE linear low density polyethylene
• Each of the A layer and the B layer was supplied to separate extruders to prepare a non-stretched polypropylene composite film composed of a two-layer coextrusion of A layer / B layer.
• the thickness of each layer was set to 40 ⁇ m in total of 5 ⁇ m / 35 ⁇ m.
• erucic acid amide was mixed with propylene random copolymer EPC-1 as the composition of layer A and layer C.
• B layer composition erucic acid amide was mixed with a resin composition in which BPP-1 or BPP-2 of propylene / ethylene block copolymer, LLDPE, and EPC-1 of propylene random copolymer were mixed.
• BPP-1 or BPP-2 of propylene / ethylene block copolymer, LLDPE, and EPC-1 of propylene random copolymer were mixed.
• Each of the A layer, the B layer, and the C layer was supplied to separate extruders to prepare a non-stretched polypropylene-based composite film composed of a three-layer coextrusion of A layer / B layer / C layer.
• the thickness of each layer was set to 40 ⁇ m in total of 5 ⁇ m / 30 ⁇ m / 5 ⁇ m.
• Example 10 A layer / B layer / C layer were made to have the same raw material composition as Example 6, and the thickness of each layer was 80 ⁇ m in total of 10 ⁇ m / 60 ⁇ m / 10 ⁇ m.
• Example 11 the same formulation as in Example 6 was used except that a propylene / ethylene block copolymer (BPP-2) having [ ⁇ ] Cxs / [ ⁇ ] Cxis of 1.98 was used as the B layer composition.
• BPP-2 propylene / ethylene block copolymer
• Examples 1 to 5 are excellent in process passability, low-temperature impact resistance, resistance to bending whitening, and scratch resistance, and have sufficient seal strength at 130 ° C and 160 ° C.
• the static friction coefficient was 0.3 or less and good slipping property, and the volume resistivity was in the range of 1 ⁇ 10 11 to 1 ⁇ 10 14 ⁇ ⁇ m.
• an unstretched polypropylene-based composite film composed of a three-layer coextrusion of A layer / B layer / C layer was used, but the process passability, drawability, low temperature impact resistance, and bending whitening resistance It has excellent scratch resistance, has sufficient seal strength at 130 ° C. and 160 ° C., has a static friction coefficient of 0.3 or less, has good slipperiness, and has a volume resistivity of 1 ⁇ 10 11 to 1 It was in the range of ⁇ 10 14 ⁇ ⁇ m.
• Example 10 the total thickness was 80 ⁇ m, but it was excellent in process passability, drawability, low temperature impact resistance, bending whitening resistance, and scratch skin resistance, and seal strengths of 130 ° C. and 160 ° C. In addition, the coefficient of static friction was 0.3 or less and good slipping property, and the volume resistivity was 3.2 ⁇ 10 12 ⁇ ⁇ m.
• Example 11 a propylene / ethylene block copolymer (BPP-2) having [ ⁇ ] Cxs / [ ⁇ ] Cxis of 1.98 was used as the B layer composition. It has excellent low-temperature impact resistance, anti-bending whitening resistance, and scratch-proof skin resistance, sufficient seal strength at 130 ° C and 160 ° C, a static friction coefficient of 0.3 or less, and good slipperiness.
• the resistivity was 7.0 ⁇ 10 12 ⁇ ⁇ m.
• Comparative Example 6 was inferior in low-temperature impact resistance due to a large amount of LLDPE, inferior in slipperiness due to a small amount of lubricant bleed on the surface layer A, and inferior in process passability.
• Comparative Example 10 was the same as Example 6 except that the propylene / ethylene block copolymer (BPP-3) having [ ⁇ ] Cxs / [ ⁇ ] Cxis of 1.39 was used as the main component for the B layer.
• BPP-3 propylene / ethylene block copolymer having [ ⁇ ] Cxs / [ ⁇ ] Cxis of 1.39
• BPP-3 propylene / ethylene block copolymer having [ ⁇ ] Cxs / [ ⁇ ] Cxis of 1.39
• BPP-3 propylene / ethylene block copolymer having [ ⁇ ] Cxs / [ ⁇ ] Cxis of 1.39
• Comparative Example 11 was the same as Example 6 except that the propylene / ethylene block copolymer (BPP-4) having [ ⁇ ] Cxs / [ ⁇ ] Cxis of 1.52 was used as the main component for the B layer.
• BPP-4 propylene / ethylene block copolymer
• [ ⁇ ] Cxs / [ ⁇ ] Cxis was close to 1.6, the resin was protruded by pressurization during drawing, and the heat seal strength was low due to thinning during heat sealing.
• erucic acid amide was mixed with the propylene random copolymers EPC-1 to EPC-5 as the A layer composition.
• the composition of the B layer is a propylene / ethylene block copolymer (BPP-) having a ratio of xylene soluble part [ ⁇ ] Cxs and insoluble part [ ⁇ ] Cxis at 20 ° C. of [ ⁇ ] Cxs / [ ⁇ ] Cxis of 1.68.
• LLDPE linear low density polyethylene
• SEBS styrene / ethylene butylene / styrene triblock copolymer
• SEBS polyethylene / ethylene butylene / polyethylene triblock copolymer
• CEBC polyethylene / ethylene butylene / polyethylene triblock copolymer
• erucic acid amide was mixed with propylene random copolymer EPC-1 as the composition of the A layer and the C layer.
• B layer composition is BPP-1 or BPP-2 of propylene / ethylene block copolymer and LLDPE and SEBS or CEBC, and EPC-1 of propylene random copolymer is mixed with erucic acid amide.
• EPC-1 propylene random copolymer is mixed with erucic acid amide.
• Each of the A layer, the B layer, and the C layer was supplied to separate extruders to prepare a non-stretched polypropylene-based composite film composed of a three-layer coextrusion of A layer / B layer / C layer. The thickness of each layer was set to 40 ⁇ m in total of 5 ⁇ m / 30 ⁇ m / 5 ⁇ m.
• Example 30 A layer / B layer / C layer were made to have the same raw material composition as Example 22, and the thickness of each layer was 80 ⁇ m in total of 10 ⁇ m / 60 ⁇ m / 10 ⁇ m.
• the slip resistance was 0.3 or less and the volume resistivity was in the range of 1 ⁇ 10 11 to 1 ⁇ 10 14 ⁇ ⁇ m.
• Example 22 to 29 a non-stretched polypropylene-based composite film composed of a three-layer coextrusion of A layer / B layer / C layer was used, but the process passability, drawability, low temperature impact resistance, and bending whitening resistance With excellent seal strength at 130 ° C and 160 ° C, a coefficient of static friction of 0.3 or less and good slipperiness, and a volume resistivity of 1 ⁇ 10 11 to 1 ⁇ 10 14 ⁇ ⁇ m.
• Example 30 the total thickness was 80 ⁇ m, but it was excellent in process passability, drawability, low temperature impact resistance, and bending whitening resistance, and had sufficient seal strength at 130 ° C. and 160 ° C. Yes, the coefficient of static friction was 0.3 or less and good slipping property, and the volume resistivity was 3.2 ⁇ 10 12 ⁇ ⁇ m.
• Comparative Example 18 was inferior in low-temperature impact resistance due to the large amount of LDPE blended in layer B, inferior in slipperiness due to a small amount of lubricant bleed in the surface layer A and inferior in process passability.
• the polypropylene-based composite film of the present invention and a packaging material using the polypropylene-based composite film have high heat-sealing power, excellent slipperiness, and can be suitably used for battery exterior applications.
• the polypropylene composite film of the present invention and a packaging material using the same are packaging materials for retort foods that are excellent in slipperiness, low-temperature impact resistance, and skin-resistant properties, and that require heat seal strength at low temperatures. Can be suitably used.

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• 2019
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