WO2015093448A1 - ポリオレフィン系樹脂ラップフィルム及びラップフィルム収容体 - Google Patents
ポリオレフィン系樹脂ラップフィルム及びラップフィルム収容体 Download PDFInfo
- Publication number
- WO2015093448A1 WO2015093448A1 PCT/JP2014/083166 JP2014083166W WO2015093448A1 WO 2015093448 A1 WO2015093448 A1 WO 2015093448A1 JP 2014083166 W JP2014083166 W JP 2014083166W WO 2015093448 A1 WO2015093448 A1 WO 2015093448A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- wrap film
- film
- container
- polyolefin resin
- polyolefin
- Prior art date
Links
Images
Classifications
-
- 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
- B26—HAND CUTTING TOOLS; CUTTING; SEVERING
- B26F—PERFORATING; PUNCHING; CUTTING-OUT; STAMPING-OUT; SEVERING BY MEANS OTHER THAN CUTTING
- B26F3/00—Severing by means other than cutting; Apparatus therefor
- B26F3/02—Tearing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/02—Wrappers or flexible covers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D83/00—Containers or packages with special means for dispensing contents
- B65D83/08—Containers or packages with special means for dispensing contents for dispensing thin flat articles in succession
- B65D83/0847—Containers or packages with special means for dispensing contents for dispensing thin flat articles in succession through an aperture at the junction of two walls
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D83/00—Containers or packages with special means for dispensing contents
- B65D83/08—Containers or packages with special means for dispensing contents for dispensing thin flat articles in succession
- B65D83/0847—Containers or packages with special means for dispensing contents for dispensing thin flat articles in succession through an aperture at the junction of two walls
- B65D83/0852—Containers or packages with special means for dispensing contents for dispensing thin flat articles in succession through an aperture at the junction of two walls with means for assisting dispensing
- B65D83/0882—Containers or packages with special means for dispensing contents for dispensing thin flat articles in succession through an aperture at the junction of two walls with means for assisting dispensing and for cutting interconnected articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65H—HANDLING THIN OR FILAMENTARY MATERIAL, e.g. SHEETS, WEBS, CABLES
- B65H35/00—Delivering articles from cutting or line-perforating machines; Article or web delivery apparatus incorporating cutting or line-perforating devices, e.g. adhesive tape dispensers
- B65H35/0006—Article or web delivery apparatus incorporating cutting or line-perforating devices
- B65H35/002—Hand-held or table apparatus
-
- 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
- B29C55/28—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of blown tubular films, e.g. by inflation
-
- 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
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08J2323/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
Definitions
- the present invention relates to a polyolefin resin wrap film and a wrap film container.
- Food wrap film is mainly used in general households as a simple packaging material for food, and many of them are used for the purpose of protecting food.
- Such a wrap film is required to have an adhesive property such that the container and the film or the films are closely adhered to each other when the food or the container is packaged and cannot be peeled off by itself.
- heat resistance that can withstand the use of a microwave oven, a soft hand feeling, tension, a suitable appearance of a packaged product, and hygiene are required.
- a wrap film is almost wound and accommodated in a storage box, a low pulling force from the storage box, a low cutting force when cutting the film, and a stable propagation property are required at the same time.
- it is important to produce efficiently in order to provide a good quality and inexpensive wrap film.
- a wrap film containing a vinylidene chloride resin is widely used mainly as a food packaging material for home use because it has a property of high adhesion and good cutability when using a blade (see, for example, Patent Document 1). .)
- a wrap film containing a polyolefin resin which is a non-chlorine resin is also used.
- the conventional wrap film is inferior in cutability when cut by hand, and is difficult to cut by hand. Moreover, it is more difficult to cut straight with a hand. For this reason, the container is provided with a blade for cutting the wrap film. However, if there is a blade for cutting the wrap, there is a risk that the hand may be cut during use, and care must be taken particularly when the child uses it. In addition, since the blade is made of a material different from that of the container, there is a problem when separating and discarding.
- a wrap film containing a polyethylene resin for example, when used in a microwave oven, the film shrinks, and high temperature oil adheres to the wrap film. There may be holes. Therefore, a wrap film containing a polyethylene resin is inferior in heat resistance oil resistance.
- wrap films containing conventional polymethylpentene and wrap films containing polyolefin resins are difficult to cut in a straight line in the TD or MD direction when cut by hand, and tear strength Therefore, there is a problem that it is difficult to cut because a high force is required for cutting.
- the present invention has been made in view of the above problems, and provides a polyolefin-based resin wrap film that can be easily cut in a predetermined direction by hand and has excellent heat and oil resistance, and a wrap film container that contains the wrap film.
- the purpose is to do.
- the present invention is as follows. [1] Including polyolefin resin, When tearing in the flow direction, it is torn in the flow direction, When tearing in the width direction, it tears in the width direction, and if it tears in the direction of 45 ° to the flow direction, it tears in either the flow direction or the width direction, The acute angle between the tear direction and the cutting line when tearing in the direction of flow and 45 ° is 30-60 °, A polyolefin resin wrap film having a tear strength of 10 g or less when torn in the direction of 45 ° with the flow direction.
- the elastic modulus in the film flow direction is 300 MPa or more, The puncture strength is 260 g or less,
- the shrinkage factor in the flow direction (Smd) obtained by the following formula (1) and the shrinkage factor in the width direction (Std) obtained by the following formula (2) are Smd ⁇ 2.5 times, Std ⁇ 2.5 times, Smd
- the polyolefin-based resin wrap film according to [1], wherein ⁇ Std ⁇ 10 times and Std / Smd 0.5 to 10 is satisfied.
- the azimuthal distribution profile has four scattering peaks; An interval between adjacent scattering peaks of the four scattering peaks is 90 ° ⁇ 10 °;
- the orientation component ratio R is 0.01 or more and 100 or less,
- the average area of the four scattering peaks is 1 or more and 89 or less, 4.
- the polyolefin resin wrap film according to any one of [1] to [3] above. [5] 5.
- a polyolefin-based resin wrap film that can be easily cut in a predetermined direction by hand and has excellent heat resistance oil resistance and a wrap film container that contains the wrap film.
- FIG. 1 It is a perspective view which shows an example of the wrap film container which accommodated the polyolefin resin wrap film which concerns on this embodiment. It is a figure which shows the outline of the tearability test in an Example. It is a figure which shows the azimuth distribution profile of Example 2. FIG. It is a figure which shows the azimuth distribution profile of the comparative example 2. It is a figure which shows an example of the cutting tool shape of a wrap film container. It is a perspective view which shows the other example of the wrap film container which accommodates the polyolefin resin wrap film which concerns on this embodiment.
- the present embodiment a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
- the present invention is not limited to this, and various modifications can be made without departing from the gist thereof. Is possible.
- the polyolefin-based resin wrap film according to the present embodiment (hereinafter also referred to as “wrap film”) is Including polyolefin resin, When tearing in the flow direction (hereinafter also referred to as “MD direction”), it is torn in the flow direction, When tearing in the width direction (hereinafter also referred to as the “TD direction”) and tearing in the direction of 45 ° with the flow direction, the tearing is performed in either the flow direction or the width direction.
- MD direction tearing in the flow direction
- TD direction width direction
- the acute angle between the tear direction and the cutting line when tearing in the direction of flow and 45 ° is 30-60 °
- the tear strength when tearing in the direction of 45 ° with the flow direction is 10 g or less.
- the wrap film is mainly used as a simple food packaging material that is cut by hand at homes and restaurants.
- wrap film applications if the wrap film can be easily cut linearly in a predetermined direction by hand, the blade of the container is not necessary, and can be used safely even when used by children. Furthermore, if the blade is not necessary, not only the manufacturing cost of the storage container can be reduced, but also the disposal cost can be reduced. In addition, such a subject does not become a special problem in the use for business use, such as a film for shrink wrapping, and for wrapping food by cutting the film using an apparatus or the like.
- the wrap film in addition to the above food packaging application, it may be used for the following applications.
- wrap film wrapped around the head to prevent staining liquid from transferring to other stains when hair dyeing at a beauty salon, etc., to suppress volatilization of the dyeing liquid, and to enhance the dyeing effect, skin cracks, wounds
- the use of wrap film wrapped around the part for the purpose of moisturizing and preventing the volatilization of the coating agent, ice, a cooling agent, etc.
- Use for wrapping the wrap film for the purpose of contacting and fixing the part use for wrapping the wrap film for the purpose of increasing the heat-retaining property of the abdomen during exercise and enhancing the diet effect, heat insulation for the thigh, knees, etc. during exercise
- Polyolefin resin Although it does not specifically limit as polyolefin-type resin, for example, the homopolymer of olefins, such as polyethylene, polypropylene, polybutene, poly 4-methylpentene, the copolymer of 2 or more types of olefins, or 1 or more types of olefins And copolymers of different components other than olefins. Polyolefin resin may be used individually by 1 type, or may use 2 or more types together.
- the polyolefin resin preferably includes a polyethylene resin.
- the polyethylene resin refers to a polyolefin resin containing an ethylene unit.
- Such polyethylene resins are not particularly limited, but include, for example, polyethylene; ethylene-vinyl acetate copolymers; ethylene-aliphatic unsaturated carboxylic acids such as ethylene-acrylic acid copolymers and ethylene-methacrylic acid copolymers.
- Acid copolymer ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-butyl methacrylate copolymer And ethylene-aliphatic unsaturated carboxylic acid ester copolymer such as a polymer.
- polyolefin-based resin contains the polyethylene-based resin, it tends to be more excellent in stretchability at the time of forming the wrap film, electron beam crosslinkability, strength at low temperature, and the like.
- Polyethylene resin may be used individually by 1 type, or may use 2 or more types together.
- the content of the polyethylene resin is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and further preferably 90 to 100% by mass with respect to 100% by mass of the polyolefin resin.
- the content of the polyethylene resin is within the above range, it tends to be more excellent in stretchability at the time of wrap film formation, electron beam crosslinkability, film strength at low temperature, and the like.
- ultra-low density polyethylene high-pressure method low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, low-pressure method high-density polyethylene, and ethylene-vinyl acetate copolymer are preferable, and the puncture resistance is preferred. Therefore, high pressure method low density polyethylene, linear low density polyethylene, ethylene-vinyl acetate copolymer and the like are more preferable.
- VLDPE Ultra-low density polyethylene
- the content of VLDPE is preferably 0 to 80% by mass, more preferably 0 to 60% by mass, and still more preferably 0 to 40% by mass with respect to 100% by mass of the polyolefin resin.
- Low density polyethylene refers to a polyethylene resin having a density of 0.910 g / cm 3 or more and less than 0.930 g / cm 3 .
- ethylene does not bind in a simple chain, and can have many long chain branches (LCB) and short chain branches (SCB).
- the content of LDPE is preferably 5 to 50% by mass, more preferably 8 to 40% by mass, and still more preferably 10 to 30% by mass with respect to 100% by mass of the polyolefin resin. When the content of LDPE is within the above range, the elasticity (tension and waist) and adhesion of the wrap film tend to be further improved.
- the method for producing the low density polyethylene is not particularly limited, but for example, a generally known method such as a high pressure method can be used.
- a high pressure method specifically, low density is obtained by polymerizing ethylene in an autoclave or a tube reactor in the presence of a free radical generator such as peroxide at a high temperature and high pressure of 100 to 300 ° C. and 100 to 350 MPa.
- Polyethylene can be produced.
- Linear low density polyethylene (hereinafter also referred to as “LLDPE”) is a kind of ultra-low density polyethylene and low-density polyethylene, and is generally also referred to as an ethylene- ⁇ -olefin copolymer. A copolymer of one or more ⁇ -olefins.
- the ⁇ -olefin is not particularly limited, and examples thereof include ⁇ -olefins having 3 to 20 carbon atoms such as 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and 1-otaten. At least one selected from the group consisting of: Of these, 1-butene, 1-hexene, and 1-otaten are preferable.
- the content of ⁇ -olefin in the linear low density polyethylene is preferably 6 to 30% by mass based on the charged monomer.
- the content of LLDPE is preferably 50 to 95% by mass, more preferably 55 to 90% by mass, and further preferably 60 to 85% by mass with respect to 100% by mass of the polyolefin resin.
- the density of LLDPE is preferably 0.900 ⁇ 0.940g / cm 3, more preferably 0.910 ⁇ 0.935g / cm 3, more preferably 0.920 ⁇ 0.930g / cm 3.
- the density is 0.900 g / cm 3 or more, excessive adhesion is suppressed and the pulling power is further improved, and the elasticity (tension and waist) of the film tends to be further improved.
- the production method of the linear low density polyethylene is not particularly limited.
- generally known methods such as a gas phase fluidized bed method, a gas phase stirred bed method, a liquid phase slurry method, a liquid phase solution method, a high pressure reaction kettle method, etc.
- ethylene and ⁇ -olefin are copolymerized in a gas phase or in a liquid phase at low temperature and low pressure in the presence of a transition metal catalyst.
- group catalyst, etc. are mentioned.
- Ziegler catalysts are preferable. By using a Ziegler-based catalyst, the low molecular weight component in the obtained polyethylene increases, and the adhesion tends to be moderately high.
- MDPE Medium density polyethylene
- the content of MDPE is preferably 0 to 80% by mass, more preferably 0 to 60% by mass, and further preferably 0 to 40% by mass with respect to 100% by mass of the polyolefin resin.
- High density polyethylene refers to a polyethylene resin having a density of 0.942 or more and g / cm 3 .
- HDPE is generally a linearly bonded ethylene with few branches.
- the content of HDPE is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and further preferably 0 to 9% by mass with respect to 100% by mass of the polyolefin resin.
- the content of HDPE is within the above range, the elasticity (tension and waist) of the wrap film is further improved and tends to be easily stretched during the production.
- High density polyethylene is an ethylene homopolymer or a copolymer of ethylene and ⁇ -olefin, and can be produced by a generally known method such as the Phillips method, the standard method, or the Ziegler method.
- the method for measuring the density of polyethylene can be performed by the method described in Examples.
- ultra-low density polyethylene, high pressure forensic density polyethylene, medium density polyethylene, low pressure method high density polyethylene, and linear low density polyethylene may be used alone or in combination of two or more different catalysts or constituents. May be.
- the ethylene-vinyl acetate copolymer (hereinafter also referred to as “EVA”) has a vinyl acetate component content of 5-25% by mass with respect to 100% by mass of the ethylene-vinyl acetate copolymer. Is preferred. When the vinyl acetate component is 5% by mass or more, the adhesiveness of the wrap film tends to be further improved. Moreover, when the vinyl acetate component is 25% by mass or less, the odor of the wrap film tends to be more odorless.
- the content of EVA is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and further preferably 0 to 10% by mass with respect to 100% by mass of the polyolefin resin.
- the polyolefin resin preferably contains 5 to 50% by mass of LDPE, 50 to 95% by mass of LLDPE, and 0 to 30% by mass of EVA, 8 to 40% by mass of LDPE, 55 to 90% by mass of LLDPE, and 0 to 20% of EVA. %, More preferably 10 to 30% by weight of LDPE, 60 to 85% by weight of LLDPE, and 0 to 10% by weight of EVA.
- the polyolefin resin can be polymerized using a known catalyst such as a single site catalyst or a multisite catalyst.
- the polyolefin resin is not limited to those conventionally obtained from petroleum and natural gas-derived raw materials, but may be those obtained from plant-derived raw materials such as sugar cane and corn.
- Density of the polyolefin resin is preferably 0.860 ⁇ 0.960g / cm 3, more preferably 0.900 ⁇ 0.955g / cm 3, more preferably 0.915 ⁇ 0.950g / cm 3.
- the density can be measured by the method described in the examples.
- the melt flow rate (hereinafter also referred to as “MFR”) at 190 ° C. and 2.16 kg of the polyolefin resin is preferably 0.1 to 25 g / 10 minutes, more preferably 0.2 to 10 g / 10 minutes, More preferably, it is 3 to 5 g / 10 min.
- MFR melt flow rate
- the MFR is 0.1 g / 10 min or more, the entanglement of molecular chains is moderately weakened, the force required for cutting is reduced, and the occurrence frequency of foreign substances such as decomposition products in the resin extrusion process is also reduced. Tend to be.
- MFR is 25 g / 10 min or less
- the entanglement of the molecular chain is moderately increased and the polyolefin resin is easily oriented, so that the wrap film can be prevented from being accidentally broken.
- MFR can be measured by the method as described in an Example.
- the wrap film may be a single layer or a laminate containing a polyolefin resin, or may be a laminate containing a layer containing a polyolefin resin and a layer containing another resin.
- each layer of the wrap film may be blended with another resin or various additives within a range of less than 50 wt%.
- wrap film if necessary, known additives such as plasticizers used in food packaging materials, stabilizers, weather resistance improvers, coloring agents such as dyes or pigments, antifogging agents, antibacterial agents, lubricants, and nucleating agents May be included. These may be used alone or in combination of two or more.
- the plasticizer is not particularly limited.
- citrate esters such as tributyl acetylcitrate, dimethyl phthalate, diethyl phthalate, dioctyl phthalate, glycerin, glycerin ester, wax, liquid paraffin, phosphate ester and epoxy And soy bean oil.
- the stabilizer is not particularly limited. Specifically, 2,5-t-butylhydroquinone, 2,6-di-t-butyl-p-cresol, 4,4′-thiobis- (6-t- Butylphenol), 2,2′-methylene-bis- (4-methyl-6-tert-butylphenol), octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) bropionate, and Antioxidants such as 4,4'-thiobis- (6-t-butylphenol); epoxidized vegetable oil, laurate, myristate, palmitate, stearate, isostearate, oleate, ricinoleic acid Heat stabilizers such as salts, 2-ethyl-hexylate, isodecanoate, neodecanoate, and calcium benzoate.
- the weather resistance improver is not particularly limited. Specifically, ethylene-2-cyano-3,3′-diphenyl acrylate, 2- (2′-hydroxy-5′-methylphenyl) benzolitriazole, 2 UV rays such as-(2'-hydroxy-3'-t-butyl-5'-methylphenyl) 5-chlorobenzotriazole, 2-hydroxy-4-methoxybenzophenone, and 2,2'-dihydroxy-4-methoxybenzophenone An absorbent is mentioned.
- the colorant such as a dye or pigment is not particularly limited, and specific examples include carbon black, phthalocyanine, quinacridone, indoline, azo pigment, and bengara.
- the antifogging agent is not particularly limited, and specific examples include glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene fatty acid alcohol ether, polyoxyethylene glycerin fatty acid ester, and polyoxyethylene sorbitan fatty acid ester.
- glycerin fatty acid ester derived from a fatty acid not containing a double bond such as glyceryl stearate, diglyceryl stearate, glycerin laurate, and diglycerin laurate is preferable. Thereby, the bleeding of the additive component on the film surface can be suppressed, and the film surface can be prevented from being clouded.
- the antibacterial agent is not particularly limited, and specific examples include silver-based inorganic antibacterial agents.
- the lubricant is not particularly limited. Specifically, fatty acid hydrocarbon lubricants such as ethylene bissteramide, butyl stearate, polyethylene wax, paraffin wax, carnauba wax, myristyl myristate, stearyl stearate, and higher fatty acid lubricants. , Fatty acid amide lubricants, and fatty acid ester lubricants.
- the nucleating agent is not particularly limited, and specific examples include phosphate ester metal salts.
- the acute angle between the tear direction and the cutting line when tearing in the direction of flow and 45 ° is 30 to 60 °, preferably 35 to 55 °, more preferably 40 to 50 °.
- the “cut line” refers to a tear start point and an end point (end edges of a wrap film test piece) when the wrap film is torn in a line direction drawn in the direction of 45 ° from the MD direction. And the intersection of the actual torn line).
- the wrap film concerning this embodiment is torn in MD direction or TD direction. Therefore, the tearing direction when the acute angle formed by the tearing direction and the cutting line when tearing in the MD direction of the wrap film in the direction of 45 ° is 45 ° is the MD direction or the TD direction.
- the angle between the tear direction and the cutting line can be controlled by the stretching conditions and the degree of orientation caused thereby. In biaxial stretching, the higher the stretching ratio and the lower the stretching temperature, the higher the degree of molecular orientation, and the molecular chains are strongly oriented in the MD and TD directions.
- the wrap film when the wrap film is torn, it tends to be torn in the direction in which the molecules are strongly oriented. That is, it is easy to tear in the MD and TD directions, and it is difficult to tear in the other direction, for example, 45 ° with respect to the MD direction. Therefore, even if it tears at 45 ° with the flow direction, it tears in the MD or TD direction.
- a wrapping film wound body is pulled out and cut by hand, it is possible to easily cut in the width direction by applying a tension in the flow direction and creating a cutting start point with a finger.
- the tear evaluation in the flow direction can be performed in the same manner as the tear evaluation in the direction of 45 ° with respect to the flow direction, except that the tear direction is the flow direction.
- the acute angle between the tear direction and the cutting line when tearing in the flow direction is 0 to 15 °, preferably 0 to 10 °, more preferably 0 to 5 °.
- the angle between the tearing direction and the cutting line is within the above range, it tends to be more excellent in straightness when cut by hand.
- “when tearing in the flow direction tears in the flow direction” means that the angle between the tear direction and the cutting line is within the above range.
- the tear evaluation in the width direction can be performed in the same manner as the tear evaluation in the direction of 45 ° with respect to the flow direction, except that the tear direction is the width direction.
- the acute angle between the tear direction and the cutting line when tearing in the width direction is 0 to 15 °, preferably 0 to 10 °, more preferably 0 to 5 °.
- “when tearing in the width direction is torn in the width direction” means that the angle between the tear direction and the cutting line is within the above range.
- the tear strength when the wrap film is torn in the direction of 45 ° with the MD direction is 10 g or less, preferably 1 to 8 g, more preferably 2 to 6 g.
- the tear strength in the MD direction and in the direction of 45 ° is within the above range, the cutting properties in the MD direction and the TD direction tend to be more excellent. If the tear strength is greater than 10 g, it cannot be easily cut by hand.
- the tear strength when tearing in the direction of 45 ° with the MD direction of the wrap film refers to the tear strength measured when the film is torn.
- the tear strength when the wrap film is torn in the MD direction is preferably 10 g or less, more preferably 1 to 8 g, and even more preferably 2 to 6 g.
- the tear strength in the MD direction is within the above range, it tends to be more excellent in cutability by the hand in the MD direction. If the tear strength is greater than 10 g, it cannot be easily cut by hand.
- the tear strength when the wrap film is torn in the TD direction is preferably 10 g or less, more preferably 1 to 8 g, and even more preferably 2 to 6 g.
- the tear strength in the TD direction is within the above range, it tends to be more excellent in hand cutability in the TD direction. If the tear strength is greater than 10 g, it cannot be easily cut by hand.
- the tear strength in each direction can be measured by the method described in the examples.
- the tear strength of the wrap film can be controlled by the draw ratio, the content ratio of each resin, the resin density, the thickness, and the like.
- the transmission wide-angle X-ray scattering measurement of the wrap film is performed by the following method.
- An X-ray with a wavelength of 0.154 nm is incident in the normal direction of the wrap film, and transmission wide-angle X-ray scattering measurement is performed.
- a two-dimensional detector is used.
- air scattering correction is performed.
- the scattering intensity is normalized by the following equation (3).
- I ( ⁇ ) is the actually measured scattering intensity
- I ′ ( ⁇ ) is the normalized scattering intensity.
- the azimuth distribution profile preferably has four scattering peaks.
- the interval between the four scattering peaks is preferably 90 ° ⁇ 10 °, more preferably 90 ° ⁇ 8 °, and further preferably 90 ° ⁇ 5 °.
- A, B, C, and D are sequentially set from the smaller azimuth angle side of the four scattering peaks, and these scattering peak areas are SA, SB, SC, and SD.
- SA azimuth angle
- SC SC
- SD SD
- the area S of each scattering peak is defined by the following formula (4).
- ⁇ 1 and ⁇ 2 are integral upper and lower limits ( ⁇ 1 ⁇ 2), and ⁇ where I ′ ( ⁇ ) sandwiching each scattering peak takes a minimum value is used.
- the orientation component ratio R is defined by the following formula (5).
- the orientation component ratio R is preferably 0.01 or more and 100 or less, more preferably 0.05 or more and 50 or less, and further preferably 0.1 or more and 10 or less.
- R (SA + SC) / (SB + SD) (5)
- the average area S ′ of the four scattering peaks is defined by equation (6).
- the average area S ′ is preferably from 1 to 89, more preferably from 10 to 79, and even more preferably from 20 to 69.
- S ′ (SA + SB + SC + SD) / 4 (6)
- wrap film satisfying the above four conditions is oriented in two orthogonal directions (generally MD direction and TD direction), cutting (tearing) from either direction will cause the two orthogonal directions It becomes possible to cut with good linearity preferentially.
- the melting point in differential scanning calorimetry (DSC) of the wrap film is preferably 80 ° C to 123 ° C, more preferably 85 ° C to 122 ° C, and further preferably 90 ° C to 121 ° C.
- the maximum value is the melting point peak.
- the melting point may exceed 123 ° C.
- the puncture resistance (piercing depth per unit thickness) of the wrap film is further improved, and it tends to be difficult to break against the protrusion.
- the wrap film is cross-linked by irradiation with energy rays. By being crosslinked, it can be easily cut by hand. Moreover, it exists in the tendency for the heat resistance and oil resistance which can be used on the high temperature conditions in a microwave oven to improve more by having bridged.
- the gel fraction of the wrap film is used as an index of the degree of crosslinking.
- the gel fraction of the wrap film is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, and further preferably 25 to 40% by mass.
- a gel fraction can be measured by the method as described in an Example.
- the elastic modulus of the wrap film in the present embodiment is used as an index of the difficulty in stretching the film, the drawability thereby, and the cut property.
- the elastic modulus in the MD direction is preferably 300 MPa or more, more preferably 300 to 1200 MPa, and further preferably 300 to 900 MPa.
- the elastic modulus in the TD direction is preferably 100 MPa or more, more preferably 100 to 1000 MPa, and further preferably 100 to 800 MPa.
- the elastic modulus can be measured by the method described in the examples.
- the elastic modulus can be adjusted by the density of the resin used, the degree of crosslinking, the draw ratio, and the like.
- the puncture strength of the wrap film is preferably 260 g or less, more preferably 50 to 250 g, and even more preferably 100 to 240 g.
- the puncture strength can be measured by the method described in the examples. Further, the puncture strength can be adjusted by the density of the resin, the degree of crosslinking, the draw ratio and the like.
- the wrap film is difficult to extend in the MD direction and the TD direction, Since it is easy to form the penetration trace which becomes, it exists in the tendency which cut property improves more and is excellent.
- the shrinkage ratio of the wrap film in this embodiment is a pseudo stretch ratio calculated backward from the maximum thermal shrinkage rate, and is used as an index of the degree of orientation.
- the maximum thermal shrinkage in this embodiment is the heat reached when the stretched wrap film is heated and heated, the residual stress is released, the shrinkage starts, the residual stress disappears, and the shrinkage behavior ends. It refers to the shrinkage rate.
- the heat shrinkage rate measured when heated at a temperature at which the crystal is completely melted, or in the case of an amorphous resin, at a temperature sufficiently exceeding the glass transition temperature Tg.
- the measurement heating temperature is the higher one of the following.
- the flow direction shrinkage ratio (Smd) obtained by the following formula (1) is preferably 2.5 times or more, more preferably 3.0 times or more, and further preferably 4.0 times or more.
- Smd is within the above range, the film is highly oriented in the MD direction, and therefore, the film is easily broken linearly in the MD direction from the starting point of the wrap film, and the cut property tends to be further improved.
- Shrinkage ratio in the flow direction (Smd) 100 / (100 ⁇ md) (1) (In the above formula (1), ⁇ md represents the maximum thermal contraction rate (%) in the flow direction.)
- the width direction shrinkage ratio (Std) obtained by the following formula (2) is preferably 2.5 times or more, more preferably 3.0 times or more, and further preferably 4.0 times or more.
- Std is within the above range, since the film is highly oriented in the TD direction, the film is easily broken linearly in the TD direction from the starting point of cutting the wrap film, and the cut property tends to be improved.
- Width direction shrinkage ratio (Std) 100 / (100 ⁇ td) (2) (In the above formula (2), ⁇ td represents the maximum heat shrinkage (%) in the width direction.)
- shrinkage ratio in the flow direction (Smd) and the shrinkage ratio in the width direction (Std) can be calculated by the methods described in the examples.
- the shrinkage ratio can be adjusted to a desired value depending on the degree of crosslinking, the stretching ratio, the stretching temperature, heat setting conditions, and the like.
- the area stretch ratio (Smd ⁇ Std) is preferably 10 times or more, more preferably 15 times or more, and further preferably 20 times or more.
- the polyolefin resin is highly oriented in the MD direction and the TD direction, and therefore linearly extends from the starting point of the wrap film in the MD direction or the TD direction. It tends to break the film.
- Std / Smd is preferably 0.5 to 10, more preferably 0.52 to 9, and further preferably 0.55 to 8.
- Std / Smd is within the above range, the cutting property in the width direction tends to be more excellent. Thereby, when handling a wrap film winding body, there exists a tendency for the generation
- the heat resistant temperature of the wrap film is preferably 130 ° C. or higher, more preferably 135 ° C. or higher, and further preferably 140 ° C. or higher.
- the heat-resistant temperature can be adjusted depending on the type of resin, density, degree of crosslinking, and the like. The heat-resistant temperature can be measured by the method described in the examples.
- the adhesion work of the wrap film is preferably 0.50 to 3.50 mJ, more preferably 0.80 to 3.00 mJ, and even more preferably 1.00 to 2.00 mJ.
- the adhesion work is 0.50 mJ or more, the adhesiveness tends to be high and the film can be prevented from being peeled off alone.
- the work of adhesion is 3.50 mJ or less, excessive adhesion is prevented, and the handleability tends to be further improved.
- the adhesion work is an index for evaluating the adhesion between films and containers when a container or food is covered with a wrap film, and is an important characteristic in combination with the pulling force.
- the work of adhesion can be measured by the method described in the examples.
- the adhesion work can be adjusted by the density or combination of the resins used.
- the thickness of the wrap film is preferably 5.0 to 15.0 ⁇ m, more preferably 5.0 to 12.0 ⁇ m, and even more preferably 5.0 to 8.5 ⁇ m.
- the total layer thickness is 5 ⁇ m or more, the tendency to be easily broken tends to be further suppressed.
- the total layer thickness is 15 ⁇ m or less, the cut property tends to be further improved.
- the thickness can be measured by the method described in the examples.
- the adjustment of the total layer thickness can be performed by the discharge amount or ratio of each layer extruder during production, the line speed, the draw ratio, and the like.
- the extrusion process is a process in which a polyolefin resin is melt-extruded from an extruder.
- a wrap film composed of a plurality of layers it is not particularly limited.
- the resin is melted with an extruder for each layer and co-extruded with a multilayer circular die (for example, a circular three-layer die or a circular five-layer die). To do.
- the laminating step is a step of producing a laminate by laminating extruded resins when producing a wrap film composed of multiple layers.
- the laminating method is not particularly limited, and examples thereof include a dry laminating method, an extrusion laminating method, and a coextrusion method. Among these, the above-described coextrusion method is preferable in terms of simple equipment.
- the stretching step is a step of biaxially stretching the extruded polyolefin resin and orienting the polyolefin resin in the MD direction and the TD direction.
- the stretching method is not particularly limited. For example, a casting method in which a melted polyolefin resin is drawn using a cooling roller, a double bubble inflation method in which the molten resin tube is heated and stretched after being cooled and solidified, and air is blown directly into the molten resin tube for stretching. And a direct tenter biaxial stretching method in which tenter transverse stretching is performed after roll longitudinal stretching. The wrap film is stretched to a suitable thickness. In order to improve the cutability of the wrap film, the control of the draw ratio, particularly in the MD direction and the TD direction, and the TD tear strength obtained thereby are important factors.
- biaxial stretching is preferable, sequential tenter biaxial stretching and double bubble inflation are more preferable, and double bubble inflation is more preferable. Biaxial stretching tends to improve cutability.
- simultaneous biaxial stretching that simultaneously stretches in the MD direction and the TD direction is applicable, but after stretching in the MD direction and then in the sequential biaxial stretching or stretching in the TD direction.
- Sequential biaxial stretching that stretches in the MD direction is more preferred.
- the draw ratio in the MD and TD directions is preferably 5.0 to 12 times, more preferably 5.5 to 11 times, and even more preferably 6.0 to 10 times.
- the stretching ratio in the TD direction is a ratio of (film width after stretching) / (parison width before stretching), and the stretching ratio in the MD direction is (line speed after stretching) / (line speed before stretching). Is the ratio.
- the draw area ratio is preferably 5 to 70 times, and more preferably 20 to 60 times. When the stretched area ratio is 5 times or more, the cutting property tends to be more excellent. Moreover, it exists in the tendency for a stretched area magnification to become smaller than the dimensional change of a product because it is 70 times or less.
- the stretching temperature is preferably the melting point of the polyolefin-based resin + 60 ° C. or less, more preferably the melting point + 40 ° C. or less, and still more preferably the melting point + 30 ° C. or less.
- the stretching temperature is in the above range, the degree of orientation of the polyolefin resin is increased and the cutting property by hand tends to be excellent.
- the winding step is a step of winding the stretched film with a winder to produce a film original.
- both ends of the film original fabric are cut with a slitter and peeled into two pieces, further cut into a desired width, and wound to obtain a wound body.
- the film is wound from the wound body by a desired winding length to produce a wound film.
- the winding method is not specifically limited, For example, the method of winding around a core is mentioned.
- the core is not particularly limited, and examples thereof include paper, plastic, metal, wooden, and combinations thereof.
- a winding body without a core body can be obtained by using an air shaft or the like as a winding core without using the core body. This has the advantage that no dust is generated on the core when it is discarded after use.
- the energy ray irradiation step can be performed on the parison or the stretched film.
- the electron beam used in the electron beam crosslinking treatment method is not particularly limited, and examples thereof include ionizing radiation such as ultraviolet rays, electron beams, X-rays, ⁇ rays, rays, rays, and neutron rays. Among these, an electron beam is preferable.
- Examples of the irradiation method by electron beam irradiation include a method in which an electron beam is irradiated onto the entire parison or film with an energy voltage of 100 kV to 1 MV.
- An antioxidant may be added for the purpose of preventing deterioration of additives such as resin and antifogging agent during extrusion kneading and adjusting the degree of crosslinking during electron beam crosslinking.
- the addition method is not particularly limited, a method of adding directly to the extruder together with the raw material resin, a method of adding by a master batch kneaded in advance into the raw material resin, and adding in advance to a liquid additive such as an antifogging agent. And a method of directly adding this to an extruder. Since the antioxidant has an effect of inhibiting the crosslinking reaction during electron beam crosslinking, the degree of crosslinking can be adjusted by the addition amount of the antioxidant.
- post-treatment such as heat setting for dimensional stability and lamination with other types of films may be performed.
- the double bubble inflation method will be described in more detail as an example of a wrap film manufacturing method.
- a melted polyolefin resin or a resin composition containing a polyolefin resin is extruded into a tubular shape from a die port of a circular die by an extruder, and a parison that is a tubular resin composition is formed.
- a sock solution may be injected to give releasability inside the parison.
- a sock liquid For example, water, mineral oil, alcohols; Polyhydric alcohols, such as propylene glycol and glycerol; Cellulose type and polyvinyl alcohol type aqueous solution are mentioned.
- a sock liquid may be used individually by 1 type, or may use 2 or more types together.
- the outer side of the parison which is an extrudate, is brought into contact with cold water using a cold water tank or water cooling ring, etc., and the parison is cooled and solidified from the inside and outside by injecting and storing a sock solution into the inside of the parison.
- the parison is in a state where the sock liquid is applied to the inside thereof.
- the solidified parison is folded by a first pinch roll to form a double ply sheet parison.
- the application amount of the sock liquid is controlled by the pinch pressure of the first pinch roll.
- the parison is irradiated with an energy beam such as an electron beam to crosslink the resin.
- the parison is opened again and becomes tubular.
- the parison is reheated to a temperature suitable for stretching.
- the temperature suitable for stretching is preferably 130 to 230 ° C. from the viewpoint of enabling easy stretching.
- air is injected into a tubular parison heated to an appropriate temperature, and bubbles are formed by inflation stretching to obtain a stretched film.
- the stretched film is folded with a third pinch roll to become a double-ply film.
- a heat setting process is performed as needed.
- the double ply film is wound up by a winding roll. Further, the double-ply film is slit and peeled to become a single film (single peeling). Finally, this film is wound on, for example, a core to obtain a wrap film wound body.
- wrap film manufacturing method is an example of a wrap film manufacturing method, and the wrap film may be manufactured according to various apparatus configurations and conditions other than those described above. For example, other known methods may be employed.
- the wrap film container includes a wound body of the polyethylene-based resin wrap film and a container that houses the wound body.
- the container may or may not have a cutting tool for cutting the polyethylene resin wrap film.
- FIG. 1 is a perspective view showing an example of a wrap film container that contains a polyolefin-based resin wrap film according to the present embodiment.
- the container for storing the wrap film F includes a rectangular parallelepiped storage chamber 8 formed by the upper surfaces of the front plate 1, the bottom plate 2, the rear plate 3, and the side plates 6, and an upper end edge of the rear plate 3.
- Cover plate 4 provided to be connected in a direction covering storage chamber 8, lid cover piece 5 extending from the front edge of cover plate 4 in a direction to cover front plate 1, and provided on both sides of lid cover piece 5
- a storage box including the lid 4 formed on each wall surface of the armpit lid piece 7 may be used.
- the wound body R is obtained by winding the polyethylene resin wrap film F.
- the container stores the wound body R.
- the container may have a cutting tool for cutting the polyethylene resin wrap film.
- FIG. 5 shows an example of the cutting tool shape of the wrap film container.
- the cutting tool is not particularly limited, but for example, a projection-like one provided in a part of the container is preferable. In particular, it is preferable to have a protrusion on a part of the lid of the container.
- the cutting tool refers to a polyethylene resin wrap film having a shape in which a force is locally applied to a position to be a starting point for cutting, and does not include a saw blade disposed in the entire width direction of the film. .
- the polyethylene-based resin wrap film according to the present embodiment can perform straight advance greedy cutting in the MD direction or the TD direction if a force is applied locally, so it is easier if there is a cutting tool such as a protrusion instead of the blade.
- the polyethylene resin wrap film according to the present embodiment can be cut.
- the attachment position in the case where the container used in the present embodiment has a cutting tool such as a protrusion is not particularly limited as long as it is a position where the wrap film can be easily cut, and the tip edge portion of the lid cover piece 5 is more preferable.
- the cutting tool is a tool for cutting the wrap film, and various shapes and materials can be used. Although it does not specifically limit as a shape of a cutting tool, For example, protrusion shape, mountain shape, etc. are mentioned. Among these, a mountain shape that can cut the film even lighter is preferable.
- the material of the cutting tool is not particularly limited.
- an aliphatic ester polymer such as a lactic acid polymer or an ester polymer such as an aromatic ester polymer, an ethylene polymer, a propylene polymer, a styrene polymer or an amide polymer.
- examples thereof include polymer materials such as polymers, vulcanized paper, resin-impregnated cured paper, abrasive grains, and abrasive-fixed paper.
- a lactic acid-based polymer that is recyclable and environmentally friendly is more preferable.
- a cutting tool without a cutting blade what has a file part in the lid piece is preferable.
- FIG. 6 The perspective view which shows the other example of the wrap film container which accommodates the polyolefin resin wrap film which concerns on FIG. 6 at this embodiment is represented.
- the file portion arranged on the lid piece shown in FIG. 6 makes a starting point of cutting by contacting the polyethylene resin wrap film when the polyethylene resin wrap film is cut from the end. From this cutting start point, the film is more easily cut in the width direction.
- the container does not have to have a cutting tool for cutting the polyethylene resin wrap film.
- a cutting tool for cutting the polyethylene resin wrap film For example, when the wound body is taken in and out from the side of the container and cut by hand, it is more preferable to combine it with a box that can be used only by the wound body.
- the container does not have a blade, it is possible to prevent injuries caused by the blade, and it can be used safely, and it is not necessary to separate and discard the blade and the container body, so that there are advantages in discarding.
- the material of the container is not particularly limited, and examples thereof include plastic, metal, wood, cardboard and paperboard, or a combination thereof.
- paperboard is preferable in terms of ease of use.
- This paperboard is a thick paper having a thickness of 0.35 to 1.50 mm. Generally, the thicker the thicker, the stronger and stronger the container can be obtained. However, since the bending process becomes difficult, the thickness is more preferably 0.35 to 0.80 mm.
- melt flow rate The melt flow rate (hereinafter also referred to as “MFR”) at 190 ° C. and 2.16 kg of the polyolefin resin was measured according to JISK7210.
- the acute angle between the tear direction and the tear direction was measured.
- FIG. 2 shows an outline of the oblique tear test (tearability test in the MD direction and 45 ° direction) in the examples.
- the tear strength of the wrap film in the direction of 45 ° with respect to the MD direction was torn in a direction of 45 ° from the MD direction by making a 10 mm cut on a 60 mm ⁇ 60 mm film by Elmendorf tear strength tester (manufactured by Toyo Seiki). Except for the above, measurement was performed according to JISK7128.
- the cut property of the oblique tear test was evaluated by evaluating the acute angle between the tear direction and the tear direction (MD direction and 45 ° direction) according to the following evaluation criteria.
- Evaluation criteria A The acute angle formed by the tearing direction and the tearing direction is 40 to 50 °, and the tear strength is 2 to 6 g.
- X The acute angle formed between the tearing direction and the tearing direction is more than 60 ° or less than 30 °, or the tear strength is more than 10 g.
- MD direction shrinkage (Smd) and TD direction shrinkage (Std) MD direction contraction magnification (Smd) and TD direction contraction magnification (Std) were calculated by the following formulas.
- Shrinkage ratio in the flow direction (Smd) 100 / (100 ⁇ md)
- Width direction shrinkage ratio (Std) 100 / (100 ⁇ td) (2)
- ⁇ md represents the maximum heat shrinkage rate (%) in the flow direction
- ⁇ td represents the maximum heat shrinkage rate (%) in the width direction.
- the maximum heat shrinkage rate was measured according to ASTM D-1204 (1984 version). First, a film having a size of 120 mm in length and 120 mm in width was marked with 3 points at 5 cm intervals in the MD direction (of the film). Two points were then marked at 5 cm intervals in the TD direction (of the film) at each of these points. This film was heat-treated in an oven maintained at a specific temperature for 1 minute, then taken out and the heat shrinkage rate was calculated from the length between each point.
- the specific temperature refers to the higher one of the crystal melting end temperature + 10 ° C. and the glass transition temperature + 30 ° C. in the first heating performed by the DSC method at a heating rate of 10 ° C./min.
- the heat shrinkage increases as the measurement temperature increases, but reaches an equilibrium above a certain temperature. At the specific temperature, glass transition and crystal melting occur sufficiently, the molecular orientation is sufficiently relaxed, and the maximum heat shrinkage is considered to occur. Therefore, the heat shrinkage rate at this temperature is defined as the maximum heat shrinkage rate.
- the measured data was processed by the above method, and the average area S ′ of the four scattering peaks appearing in the azimuth distribution profile and the orientation component ratio R were calculated.
- Each calculation formula used the above formulas (3) to (6).
- the melting point of the wrap film obtained below was measured by carrying out the following six-stage program using a DSC manufactured by PerkinElmer. 1) Hold at 0 ° C. for 1 minute, 2) Temperature increase from 0 ° C. to 200 ° C. at 10 ° C./min, 3) Hold at 200 ° C. for 1 minute, 4) Decrease in temperature from 200 ° C. to 0 ° C. at 10 ° C./min. 5) Hold at 0 ° C. for 1 minute, 6) The temperature was raised from 0 ° C to 200 ° C at 10 ° C / min. Among the above steps, the temperature at which the caloric peak in 6) was the maximum was defined as the melting point.
- the heat-resistant temperature of the wrap film was evaluated as follows while changing some conditions while conforming to the wrap quality display implementation guideline based on Article 11 of Tokyo Metropolitan Consumer Life Ordinance (Tomin Table No. 29).
- the wrap film is cut into a width of 3 cm and a length of 14 cm, and is adhered to both sides of the upper and lower end films with a double-sided tape so as not to remove the 3 cm wide and 2.5 cm long board. It was. Without hanging a weight at the lower end of this sample, the upper end was fixed with a jig in an oven maintained at a predetermined temperature, and the presence or absence of cutting was confirmed after 1 hour.
- the open temperature was lowered by 5 ° C. and the measurement was performed in the same manner.
- the open temperature was raised by 5 ° C. and the measurement was performed in the same manner. And the highest temperature which the sample obtained from this result has not cut
- Evaluation was performed in three stages as follows. Evaluation criteria ⁇ : 140 ° C or higher Excellent heat resistance. Fully usable. ⁇ : 100 ° C. or higher and lower than 140 ° C. No problem with heat resistance. Can be used in microwave ovens. X: Less than 100 ° C. The heat resistance is poor. Difficult to use in microwave oven.
- the adhesion work of the wrap film is a value for evaluating the adhesion between the films when the wrap film is put on a container such as tableware or food.
- the adhesion work was measured and evaluated as follows.
- Two cylinders having a bottom area of 25 cm 2 and a mass of 400 g were prepared. And the filter paper with the same area as a bottom face was previously affixed on these bottom faces. The wrap film was tensioned and fixed so that no wrinkles would enter the bottom surfaces of the two cylinders to which the filter paper was attached. Then, after aligning the two cylinders so that these film surfaces were exactly overlapped with each other, a 500 g weight was immediately placed and loaded, followed by pressure bonding for 1 minute.
- the weight was removed, and the overlapped films were immediately pulled apart in a direction perpendicular to the surface at a speed of 5 mm / min with a tensile tester, and the energy (mJ) generated at this time was defined as the work of adhesion. .
- the measurement was performed in a 23 ° C. atmosphere. The test was performed 10 times, and an average value was adopted. This evaluation was performed in four stages as follows.
- the thickness of the wrap film was measured according to ASTME-252. Specifically, the measurement was performed using TECLOCK US-26 manufactured by TECLOCK CORPORATION.
- Evaluation criteria A No generation of tears, holes, pinholes, etc. ⁇ : Only a pinhole having an outer diameter of less than 5 mm is generated. X: Perforation or tearing of the outer shape of 5 mm or more is generated.
- a surface layer is a layer used as the outermost surface of a wrap film
- middle layer is a layer which contact
- Additive 2 Diglycerol laurate
- Examples 1 to 15 A resin composition having the composition shown in Table 1 with a cyclic mixture of 2.0% by mass of a 1: 1 mixture of diglycerol oleate and glycerol monooleate (additive 1) or diglycerol laurate (additive 2). After being extruded from the die as a single layer, a three-layer original or a five-layer original, it was cooled and solidified with cold water to produce a tube-shaped original having a folding width of 120 mm and a thickness of 500 ⁇ m.
- Example 16 A wrap film of Example 16 was obtained in the same manner as described above except that the resin composition shown in Table 1 was used, and that electron beam crosslinking was not performed and that biaxial stretching was successively performed with a stretcher. Various physical properties are shown in Table 2.
- Example 17 A wrap film of Example 17 was obtained in the same manner as in Example 2 except that after the electron beam cross-linking treatment, sequential biaxial stretching was performed using a stretcher. Various physical properties are shown in Table 2.
- Comparative Example 1 As shown in Table 3, a wrap film of Comparative Example 1 was obtained in the same manner as in Example 8 except that the resin composition of the inner layer was different. Various physical properties are shown in Table 4.
- Comparative Example 2 As shown in Table 3, a wrap film of Comparative Example 2 was obtained in the same manner as in Example 11 except that the parison thickness and the draw ratio were different. Various physical properties are shown in Table 4.
- Comparative Example 3 As shown in Table 3, a wrap film of Comparative Example 3 was obtained in the same manner as in Example 12 except that the resin composition of the inner layer, the point where electron beam irradiation was not performed, and the parison thickness and the draw ratio were different. Various physical properties are shown in Table 4.
- Comparative Example 4 As shown in Table 3, a wrap film of Comparative Example 4 was obtained in the same manner as in Example 13 except that the electron beam irradiation was not performed and the parison thickness and the draw ratio were different. Various physical properties are shown in Table 4.
- Comparative Examples 5 to 6 As shown in Table 3, the wrap films of Comparative Examples 5 to 6 were obtained in the same manner as in Example 12 except that the resin composition of the inner layer and the intermediate layer, the point where no electron beam irradiation was performed, and the parison thickness and the draw ratio were different. It was. Various physical properties are shown in Table 4.
- FIG. 3 shows the azimuth distribution profile of Example 2
- FIG. 4 shows the azimuth distribution profile of Comparative Example 2.
- the polyolefin resin wrap film according to the present invention can be widely and effectively used for food packaging and cooking.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Polymers & Plastics (AREA)
- Forests & Forestry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Wrappers (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Packaging Of Machine Parts And Wound Products (AREA)
- Cartons (AREA)
- Details Of Rigid Or Semi-Rigid Containers (AREA)
Abstract
Description
〔1〕
ポリオレフィン系樹脂を含み、
流れ方向引き裂き時には流れ方向に引き裂かれ、
巾方向引き裂き時には巾方向に引き裂かれ、かつ
流れ方向と45°の方向に引き裂いた場合は、流れ方向又は巾方向のいずれかの方向に引き裂かれ、
流れ方向と45°の方向に引き裂いた場合の引き裂き方向と、切断線とのなす鋭角が30~60°であり、
流れ方向と45°の方向に引き裂いた場合の引裂強度が10g以下である、ポリオレフィン系樹脂ラップフィルム。
〔2〕
フィルム流れ方向の弾性率が300MPa以上であり、
突刺強度が260g以下であり、
下記式(1)により求められる流れ方向収縮倍率(Smd)と、下記式(2)により求められる巾方向収縮倍率(Std)とが、Smd≧2.5倍、Std≧2.5倍、Smd×Std≧10倍、かつStd/Smd=0.5~10を満たす、前項〔1〕に記載のポリオレフィン系樹脂ラップフィルム。
流れ方向収縮倍率(Smd)=100/(100-αmd) (1)
巾方向収縮倍率(Std) =100/(100-αtd) (2)
(上記式(1)及び(2)中において、αmdは流れ方向の最大熱収縮率(%)を示し、αtdは、巾方向の最大熱収縮率(%)を示す。)
〔3〕
前記ポリオレフィン系樹脂が、ポリエチレン系樹脂を含む、前項〔1〕又は〔2〕に記載のポリオレフィン系樹脂ラップフィルム。
〔4〕
波長0.154nmのX線をフィルム法線方向から入射させ、透過広角X線散乱を測定した際の、散乱角2θ=20.9°~21.8°の散乱強度の方位角分布プロフィールにおいて、
前記方位角分布プロフィールが、4つの散乱ピークを有し、
前記4つの散乱ピークの隣り合う散乱ピーク間隔が、90°±10°であり、
配向成分比Rが、0.01以上100以下であり、
前記4つの散乱ピークの平均面積が、1以上89以下である、
前項〔1〕~〔3〕のいずれか1項に記載のポリオレフィン系樹脂ラップフィルム。
〔5〕
示差走査熱量測定における融点が、80~123℃である、前項〔1〕~〔4〕のいずれか1項に記載のポリオレフィン系樹脂ラップフィルム。
〔6〕
ゲル分率が、10~60質量%である、前項〔1〕~〔5〕のいずれか1項に記載のポリオレフィン系樹脂ラップフィルム。
〔7〕
耐熱温度が、130℃以上である、前項〔1〕~〔6〕のいずれか1項に記載のポリオレフィン系樹脂ラップフィルム。
〔8〕
前項〔1〕~〔7〕のいずれか1項に記載のポリオレフィン系樹脂ラップフィルムが巻回された、巻回体。
〔9〕
前項〔8〕に記載のポリエチレン系樹脂ラップフィルムの巻回体と、該巻回体を収納する容器と、を有し、
該容器が、前記ポリエチレン系樹脂ラップフィルムを切断するための切断具を有する、ラップフィルム収容体。
〔10〕
前記切断具が、前記容器の一部に具備された突起状のものである、前項〔8〕に記載のラップフィルム収容体。
〔11〕
前項〔8〕に記載のポリエチレン系樹脂ラップフィルムの巻回体と、該巻回体を収納する容器と、を有し、
該容器が、前記ポリエチレン系樹脂ラップフィルムを切断するための切断具を有さない、ラップフィルム収容体。
本実施形態に係るポリオレフィン系樹脂ラップフィルム(以下、「ラップフィルム」ともいう。)は、
ポリオレフィン系樹脂を含み、
流れ方向(以下、「MD方向」ともいう。)引き裂き時には流れ方向に引き裂かれ、
巾方向(以下、「TD方向」ともいう。)引き裂き時には巾方向に引き裂かれ、かつ
流れ方向と45°の方向に引き裂いた場合は、流れ方向又は巾方向のいずれかの方向に、引き裂かれ、
流れ方向と45°の方向に引き裂いた場合の引き裂き方向と、切断線とのなす鋭角が30~60°であり、
流れ方向と45°の方向に引き裂いた場合の引裂強度が10g以下である。
ポリオレフィン系樹脂としては、特に限定されないが、例えば、ポリエチレン、ポリプロピレン、ポリブテン、ポリ4メチルペンテンなどのオレフィン類の単独重合体若しくは2種以上のオレフィン類の共重合体、又は1種以上のオレフィン類とオレフィン類以外の異種成分との共重合体が挙げられる。ポリオレフィン系樹脂は、1種単独で用いても、2種以上を併用してもよい。
このなかでも、ポリオレフィン系樹脂は、ポリエチレン系樹脂を含むことが好ましい。ポリエチレン系樹脂とは、エチレン単位を含むポリオレフィン樹脂をいう。このようなポリエチレン系樹脂としては、特に限定されないが、例えば、ポリエチレン;エチレン-酢酸ビニル共重合体;エチレン-アクリル酸共重合体、エチレン-メタクリル酸共重合体等のエチレン-脂肪族不飽和カルボン酸共重合体;エチレン-メチルアクリレート共重合体、エチレン-メチルメタクリレート共重合体、エチレン-エチルアクリレート共重合体、エチレン-エチルメタクリレート共重合体、エチレン-ブチルアクリレート共重合体、エチレン-ブチルメタクリレート共重合体等のエチレン-脂肪族不飽和カルボン酸エステル共重合体等が挙げられる。ポリオレフィン系樹脂がポリエチレン系樹脂を含むことにより、ラップフィルム製膜時の延伸性、電子線架橋性、低温下における強度等により優れる傾向にある。ポリエチレン系樹脂は、1種単独で用いても、2種以上を併用してもよい。
ラップフィルムは、必要に応じて、食品包装材料に用いられる可塑剤、安定剤、耐候性向上剤、染料又は顔料などの着色剤、防曇剤、抗菌剤、滑剤、核剤など公知の添加剤を含んでいてもよい。これらは1種単独で用いても又は2種以上を併用してもよい。
流れ方向と45°の方向への引き裂き評価では、JIS K 7128の引裂試験B法(エルメンドルフ法)と同様にして、引き裂き試験を行い、引裂強度と切断方向、すなわち流れ方向と45°の方向に引き裂いた場合の引き裂き方向と切断線とのなす鋭角を測定する。ここで、試験片はラップフィルムから流れ方向と45°の方向で採取し、試験片の大きさは60×60mm、スリット長さは10mmとする。
流れ方向への引き裂き評価は、引き裂き方向が流れ方向であること以外は、流れ方向と45°の方向への引き裂き評価と同様に行うことができる。流れ方向に引き裂いた場合の引き裂き方向と切断線とのなす鋭角は、0~15°であり、0~10°が好ましく、0~5°がより好ましい。引き裂き方向と切断線の角度が上記範囲内であることにより、手でカットした場合の直進性により優れる傾向にある。本実施形態において、「流れ方向引き裂き時には流れ方向に引き裂かれる」とは、引き裂き方向と切断線の角度が上記範囲内であることをいう。
巾方向への引き裂き評価は、引き裂き方向が巾方向であること以外は、流れ方向と45°の方向への引き裂き評価と同様に行うことができる。巾方向に引き裂いた場合の引き裂き方向と切断線とのなす鋭角は、0~15°であり、0~10°が好ましく、0~5°がより好ましい。引き裂き方向と切断線の角度が上記範囲内であることにより、手でカットした場合の直進性により優れる傾向にある。本実施形態において、「巾方向引き裂き時には巾方向に引き裂かれる」とは、引き裂き方向と切断線の角度が上記範囲内であることをいう。
ラップフィルムのMD方向と45°の方向に引き裂いた場合の引裂強度は、10g以下であり、1~8gが好ましく、2~6gがより好ましい。MD方向と45°の方向の引裂強度が上記範囲内であることにより、MD方向及びTD方向のカット性により優れる傾向にある。なお、引裂強度が10gより大きいと、手により容易にカットすることができない。ラップフィルムのMD方向と45°の方向に引き裂いた場合の引裂強度は、その引き裂かれた際に測定される引裂強度をいう。
波長0.154nmのX線をフィルム法線方向から入射させ、透過広角X線散乱を測定した際の、散乱角2θ=20.9°~21.8°の散乱強度の方位角分布プロフィールにおいて、方位角分布プロフィールが、4つの散乱ピークを有し、4つの散乱ピークの隣り合う散乱ピーク間隔が、90°±10°であり、配向成分比Rが、0.01以上100以下であり、4つの散乱ピークの平均面積が、1以上89以下であることが好ましい。なお、「フィルムの法線方向」とは、フィルム面の1点を通り、その点における接平面に垂直な方向をいう。
R=(SA+SC)/(SB+SD) (5)
S’=(SA+SB+SC+SD)/4 (6)
ラップフィルムの示差走査熱量測定(DSC)における融点は、80℃~123℃が好ましく、85℃~122℃がより好ましく、90℃~121℃がさらに好ましい。なお、ラップフィルムのDSCで測定におけるピークが複数ある場合には、最大値を融点ピークとする。融点の高いHDPEや特定のMDPE等を含む場合、融点は123℃を超えることがある。融点が上記範囲内であることにより、ラップフィルムの耐突刺性(単位厚み当たりの突刺深度)がより向上し、突起物に対して破れにくくなる傾向にある。
ラップフィルムはエネルギー線照射により架橋処理されたものであることが好ましい。架橋処理したものであることにより、より容易に手で切ることができる。また、架橋処理したものであることにより、電子レンジでの高温条件下で使用可能な耐熱性、耐油性がより向上する傾向にある。
本実施形態におけるラップフィルムの弾性率は、フィルムの伸び難さ、それによる引き出し性、カット性の指標として用いられる。MD方向の弾性率は、300MPa以上が好ましく、300~1200MPaがより好ましく、300~900MPaがさらに好ましい。また、TD方向の弾性率は、100MPa以上が好ましく、100~1000MPaがより好ましく、100~800MPaがさらに好ましい。MD方向弾性率又はTD方向弾性率が上記範囲内にあることにより、ラップフィルムの引き出し性がより向上する方向にあり、カットする際に伸び難く、よりカット性が優れる傾向にある。
ラップフィルムの突刺強度は、260g以下が好ましく、50~250gがより好ましく、100~240gがさらに好ましい。なお、突刺強度は実施例に記載の方法により測定することができる。また、突刺強度は樹脂の密度、架橋度、延伸倍率などにより調整することができる。
本実施形態におけるラップフィルムの収縮倍率は、最大熱収縮率から逆算した擬似的な延伸倍率であり、配向度の指標として用いている。本実施形態における最大熱収縮率とは、延伸されたラップフィルムが昇温加熱され、残留応力が開放されて、収縮を開始した後、残留応力が消失し、収縮挙動が終了した時点で達する熱収縮率のことをいう。つまり結晶性樹脂の場合は、完全に結晶が融解したとみなされる温度、非晶性樹脂であれば、ガラス転移温度Tgを十分に超える温度で加熱した際に測定される熱収縮率のことをいう。測定加熱温度は、以下のうち、高温の方とする。
(A):DSC法における結晶融解終了温度+10℃
(B):DSC法におけるTg+30℃。
流れ方向収縮倍率(Smd)=100/(100-αmd) (1)
(上記式(1)中において、αmdは流れ方向の最大熱収縮率(%)を示す。)
巾方向収縮倍率(Std) =100/(100-αtd) (2)
(上記式(2)中において、αtdは、巾方向の最大熱収縮率(%)を示す。)
ラップフィルムの耐熱温度は、130℃以上が好ましく、135℃以上がより好ましく、140℃以上がさらに好ましい。耐熱温度が上記範囲内であることにより、例えば電子レンジで使用した際に高温の油がラップフィルムに付着することにより穴が開くことなどをより抑制できる傾向にある。耐熱温度は、樹脂の種類、密度、架橋度などによって、調整することができる。なお、耐熱温度は実施例に記載の方法により測定することができる。
ラップフィルムの密着仕事量は、0.50~3.50mJが好ましく、0.80~3.00mJがより好ましく、1.00~2.00mJがさらに好ましい。密着仕事量が0.50mJ以上であることにより、密着性が高くフィルムが独りでに剥がれることを抑制できる傾向にある。また、密着仕事量が3.50mJ以下であることにより、過剰密着を防ぎ、取り扱い性がより向上する傾向にある。密着仕事量は、容器や食品にラップフィルムを被せたときのフィルム同士や容器との密着性を評価する指標であり、引出力と併せて重要な特性である。
ラップフィルムの厚みは、5.0~15.0μmが好ましく、5.0~12.0μmがより好ましく、5.0~8.5μmがさらに好ましい。全層厚みが5μm以上であることにより、破れやすくなることをより抑制できる傾向にある。また、全層厚みが15μm以下であることにより、カット性がより向上する傾向にある。
本実施形態に係るラップフィルムの製造方法は、一般に公知の方法であれば特に限定されないが、例えば、押出工程、延伸(成膜)工程及び巻き取り工程などからなる方法が挙げられ、必要に応じて、積層工程、エネルギー線照射工程、及びヒートセット工程などの処理を行うこともできる。
まず、溶融したポリオレフィン系樹脂又はポリオレフィン系樹脂を含む樹脂組成物を押出機により、円形のダイのダイ口から管状に押し出し、管状の樹脂組成物であるパリソンが形成される。
本実施形態に係るラップフィルム収容体は、上記ポリエチレン系樹脂ラップフィルムの巻回体と、該巻回体を収納する容器と、を有する。容器は、ポリエチレン系樹脂ラップフィルムを切断するための切断具を有していても、有していなくてもよい。
巻回体Rは、上記ポリエチレン系樹脂ラップフィルムFが巻回されたものである。
容器は、巻回体Rを収納するものである。容器は、ポリエチレン系樹脂ラップフィルムを切断するための切断具を有していてもよい。図5にラップフィルム容器の切断具形状の一例を示す。図5に示すように、切断具としては、特に制限されないが、例えば、容器の一部に具備された突起状のものが好ましい。特に、容器のフタ部の一部に、突起部を有することが好ましい。ここで、切断具とは、ポリエチレン系樹脂ラップフィルムに対し、切断する始点となる箇所に局所的に力を加える形状のものをいい、フィルムの幅方向全体に配されるノコ刃は含まれない。本実施形態にかかるポリエチレン系樹脂ラップフィルムは、局所的に力を加えればMD方向又はTD方向に直進***切断することができるため、刃の代わりに突起部等の切断具があれば、より容易に本実施形態に係るポリエチレン系樹脂ラップフィルムを切ることができる。
〔密度〕
ポリオレフィン系樹脂の密度は、JISK7112に準じて測定した。
ポリオレフィン系樹脂の190℃、2.16kgにおけるメルトフローレート(以下、「MFR」ともいう。)は、JISK7210に準じて測定した。
ラップフィルムのMD方向の引裂強度、及びTD方向の引裂強度は、エルメンドルフ引裂強度試験機(東洋精機製)により、60mm×60mmのフィルムに10mmの切れ目を入れてMD方向から45°の方向に引き裂いたこと以外は、JISK7128に準じて測定した。
図2に実施例における斜め引裂試験(MD方向と45°の方向の引き裂き性試験)の概略を示す。ラップフィルムのMD方向と45°の方向の引裂強度は、エルメンドルフ引裂強度試験機(東洋精機製)により、60mm×60mmのフィルムに10mmの切れ目を入れてMD方向から45°の方向に引き裂いたこと以外は、JISK7128に準じて測定した。
◎:引き裂かれた方向と引き裂き方向とのなす鋭角が40以上50°以下であり、かつ引裂強度が2~6gである。
○:引き裂かれた方向と引き裂き方向とのなす鋭角が30°以上40°未満、又は50°超過60°以下かつ引裂強度が10g以下である。
×:引き裂かれた方向と引き裂き方向とのなす鋭角が60°超過又は30°未満である、又は引裂強度が10g超過である。
刃なしカット性評価では、まずラップフィルム巻回体を片手に持ち、ラップフィルムを上出しで30cm引き出し、ラップフィルム巻回体を持っている手の親指を、巾方向中央部に押し当てた。次いで、引き出したラップフィルムに対して、引き出し方向に張力を掛けながら、親指を強くラップフィルムに押し当てた。親指の押し当てによりラップフィルムに切断の切っ掛けを作ったのち、引き出し方向張力により、ラップフィルムが巾方向に切断した。この時の切断状況を下記評価基準により評価した。
評価基準
◎ : あまり力を掛けずに、巾方向に真っ直ぐに、綺麗な切断面で切断された。
○ : やや強めに力を掛けることで、概ね巾方向に真っ直ぐ、綺麗な切断面で切断された。
△ : 切断されたが、巾方向に真っ直ぐではない、または切断面が綺麗でない。
× : うまく巾方向に切断されなかった。
フィルム流れ方向の弾性率は、ASTMD-882に準じて測定した。測定条件は、引張速度は5mm/min、初期試料長(つかみ具間隔)は100mm、試料幅は10mmであり、2%伸長時の応力から算出した。評価基準を以下に示す。
評価基準
×:700MPa超過 張り、腰及び手触り感が落ちる
△:600MPa超過700MPa以下 実用上、張り、腰及び手触り感に問題なし
◎:400MPa以上600MPa以下 最適な弾性率である。張り、腰及び手触り感に優れる。
○:300MPa以上400MPa未満 適度な弾性率である。
×:300MPa未満 弾性率が不適である。
農林規格第10条に準じて、フィルムを内寸法で125mm×125mmの木枠に固定し、その中心部に直径1.0mm、先端形状0.5mmRの針を50±5mm/分の速度で突き刺し、針が貫通するまでの最大荷重を測定し、その値を突刺強度とした。
上記突刺強度と同様に試験をした際に、針が貫通するまでの移動距離を測定し、その値を突刺深度とした。
MD方向収縮倍率(Smd)及びTD方向収縮倍率(Std)は下記式により算出した。
流れ方向収縮倍率(Smd)=100/(100-αmd) (1)
巾方向収縮倍率(Std) =100/(100-αtd) (2)
(上記式(1)及び(2)中において、αmdは流れ方向の最大熱収縮率(%)を示し、αtdは、巾方向の最大熱収縮率(%)を示す。)
最大熱収縮率の測定は、ASTMD-1204(1984年度版)に準じて行った。まず、縦120mm×横120mmの大きさのフィルムに(フィルムの)MD方向に5cm間隔で3点の印を付けた。次いでこれらの各点の(フィルムの)TD方向に5cm間隔で2点の印を付けた。このフィルムを特定温度に保たれたオーブン中で1分間熱処理後、取り出して各点間の長さから熱収縮率を計算した。
下記で得られたラップフィルムから、縦1cm、横1cmの正方形の試料を切り取り、試料のMD方向(巻き取り方向)を縦に、TD方向(MD方向に垂直する方向)を横になるよう、試料ホルダーにセットした。測定は、RIGAKU社製X線散乱装置(Nano-Viewer)を用いて行った。測定条件は、入射X線波長0.154nm、カメラ長79.1mm、出力45kV/60mA、測定時間15分とした。検出器には、イメージングプレートを用いた。上記の測定では、空気散乱補正を実施した。
下記で得られたラップフィルムの融点は、パーキンエルマー社製DSCを用いて下記の6段階のプログラムを実施することにより測定した。
1)0℃にて1分保持、
2)0℃から200℃まで10℃/分で昇温、
3)200℃で1分保持、
4)200℃から0℃まで10℃/分で降温、
5)0℃で1分保持、
6)0℃から200℃まで10℃/分で昇温。
上記段階のうち6)における熱量ピークが最大の温度を融点と規定した。
ラップフィルムのゲル分率は、ASTM-D2765に準拠し以下のように測定した。沸騰パラキシレン中、12時間抽出した後の不溶分の質量分率を次式により表示したものをゲル分率とした。尚、試料は、延伸されたフィルムを140℃で熱収縮させてパリソン状に戻したものを使用した。なお、ゲル分率の測定においては、適宜フィルム融点以上の沸点を持つ溶媒を使用することができる。
ゲル分率(質量%)=(抽出後の試料重量/抽出前の試料重量)×100
ラップフィルムの耐熱温度は、東京都消費生活条例11条に基づくラップ品質表示実施要領(都民表第29号)に準拠しつつ、一部条件を変更して、次の通り評価した。
評価基準
〇:140℃以上 耐熱性が優れている。十分使用可能。
△:100℃以上140℃未満 耐熱性は問題なし。電子レンジで使用可能。
×:100℃未満 耐熱性が悪い。電子レンジで使用しづらい。
ラップフィルムの密着仕事量は、この方法は、食器などの容器や食品にラップフィルムを被せたときのフィルム同士の密着性を評価するための値である。密着仕事量は、以下の通り、測定し、評価した。
×:3.50mJ超過 過剰密着である。
△:3.00mJ超過3.50mJ以下 過剰密着が殆どない。実用上、密着性は問題ない。
〇:2.00mJ超過3.00mJ以下 独りでに剥がれない。過剰密着がない。密着性が優れている。
◎:1.00mJ以上2.00mJ以下 最適な密着仕事量である。
密着性が非常に優れている。
〇:0.80mJ以上1.00mJ未満 独りでに剥がれない。過剰密着がない。密着性が優れている
△:0.50mJ以上0.80mJ未満 独りでに剥がれることが殆どない。過剰密着が殆どない。実用上、密着性は問題ない。
×:0.50mJ未満 独りでに剥がれる。実用上、密着性に問題がある。
ラップフィルムの厚みは、ASTME-252に準じて測定した。具体的には、TECLOCKCORPORATION製 TECLOCK US-26を使用して測定を行った。
実際に料理をラップ包装し、電子レンジ加熱する際の実用的な耐熱油性を評価する実包耐熱油性は、以下のように測定した。お皿にカレーライスを盛り、その上からラップフィルムで包装した後、電子レンジで、750W×1分加熱した後、ラップフィルムに破れ、穴あき、ピンホール等の有無を目視確認し、下記評価基準により評価した。
◎:破れ、穴あき、ピンホール等の生成なし。
○:外径5mm未満のピンホールのみ生成。
×:外形5mm以上の穴あき、破れなどが生成。
以下の樹脂を表面層、中間層、および内部層の材料として用いた。なお、表面層とは、ラップフィルムの最表面となる層であり、中間層とは、ラップフィルムの表面層に接する層であって、内部層がある場合には、内部層を挟むように接する層であり、内部層とは、ラップフィルムの中間層に挟まれるように接する層である。
・LL1:エチレン-1-オクテン共重合体、密度=0.926g/cm3、MFR=2.0g/10分
・LL2:エチレン-1-へキセン共重合体、密度=0.913g/cm3、MFR=2.0g/10分
・LL3:エチレン-1-ヘキセン共重合体、密度=0.926g/cm3、MFR=2.5g/10分
・LL4:エチレン-1-ヘキセン共重合体、密度=0.916g/cm3、MFR=2.3g/10分
・LL5:エチレン-1-ヘキセン共重合体、密度=0.912g/cm3、MFR=1.0g/10分
・VL1:エチレン-1-ヘキセン共重合体、密度=0.900g/cm3、MFR=2.0g/10分
・VL2:エチレン-1-ヘキセン共重合体、密度=0.905g/cm3、MFR=4.0g/10分
・ML1:エチレン-オクテン共重合体、密度=0.939g/cm3、MFR=2.1g/10分
・LD1:高圧法低密度ポリエチレン、密度=0.921g/cm3、MFR=0.4g/10分
・LD2:高圧法低密度ポリエチレン、密度=0.922g/cm3、MFR=0.2g/10分
・LD3:高圧法低密度ポリエチレン、密度=0.924g/cm3、MFR=3.0g/10分
・HD1:高密度ポリエチレン、密度=0.954g/cm3、MFR=1.1g/10分
・EL1:エチレン-1-オクテン共重合エラストマー、密度=0.877g/cm3、MFR=0.5g/10分
・EL2:エチレン-1-オクテン共重合エラストマー、密度=0.868g/cm3、MFR=0.5g/10分
・EVA1:エチレン-酢酸ビニル共重合体、酢酸ビニル成分=15%、密度=0.940g/cm3、MFR=2.0g/10分
・EVA2:エチレン-酢酸ビニル共重合体、酢酸ビニル成分=15%、密度=0.940g/cm3、MFR=1.0g/10分
・PP1:ホモポリプロピレン、密度=0.900g/cm3、MFR=3.3g/10分
・PB1:プロピレン-ブテン共重合体、密度=0.890g/cm3、MFR=2.0g/10分
・PMP1: ポリメチルペンテン、密度=0.834g/cm3、MFR=21g/10分(260℃)
・添加剤1:ジグリセリンオレートとグリセリンモノオレートの1:1混合物
・添加剤2:ジグリセリンラウレート
表1に示す組成の樹脂組成物に、ジグリセリンオレートとグリセリンモノオレートの1:1の混合物(添加剤1)またはジグリセリンラウレート(添加剤2)を2.0質量%添加したものを環状ダイより単層または3層原反または5層原反として押出した後、冷水にて冷却固化して、折り巾120mm、厚さ500μmのチューブ状原反を作製した。これを電子線照射装置に誘導し、500kVに加速した電子線を照射し、吸収線量として80kGyになるように架橋処理を行った。これを延伸機内に誘導して再加熱を行い、2対の差動ニップロール間に通して、エアー注入によりバブルを形成し、表1に示す延伸条件でそれぞれ延伸を行い、実施例1~15のラップフィルムを得た。各種物性を表2に示す。
表1に記載の樹脂組成とし、電子線架橋をしない点、ストレッチャーにて逐次二軸延伸をした点が異なる以外は上記と同様にして実施例16のラップフィルムを得た。各種物性を表2に示す。
電子線架橋処理を行った後に、ストレッチャーにて逐次二軸延伸をした点が異なる以外は実施例2と同様にして実施例17のラップフィルムを得た。各種物性を表2に示す。
表3のように、内部層の樹脂組成が異なる以外は、実施例8と同様にして比較例1のラップフィルムを得た。各種物性を表4に示す。
表3のように、パリソン厚みと延伸倍率が異なる以外は、実施例11と同様にして比較例2のラップフィルムを得た。各種物性を表4に示す。
表3のように、内部層の樹脂組成、電子線照射をしない点、パリソン厚みと延伸倍率が異なる以外は、実施例12と同様にして比較例3のラップフィルムを得た。各種物性を表4に示す。
表3のように、電子線照射をしない点、パリソン厚みと延伸倍率が異なる以外は、実施例13と同様にして比較例4のラップフィルムを得た。各種物性を表4に示す。
表3のように、内部層及び中間層の樹脂組成、電子線照射をしない点、パリソン厚みと延伸倍率が異なる以外は、実施例12と同様にして、比較例5~6のラップフィルムを得た。各種物性を表4に示す。
表3のように、ポリエチレンを用いた市販のラップフィルムを比較例7のラップフィルムとして用いた。各種物性を表4に示す。
表3のように、ポリプロピレンを用いた市販のラップフィルムを比較例8のラップフィルムとして用いた。各種物性を表4に示す。
表3のように、ポリメチルペンテンを用いた市販のラップフィルムを比較例9のラップフィルムとして用いた。各種物性を表4に示す。
◎:耐熱性、密着性が良好でカット性が非常に優れる。
刃なしカット性◎、実包耐熱油性○以上、密着仕事量○以上
○:耐熱性、密着性、刃なしカット性が良好。
刃なしカット性○、実包耐熱油性○以上、密着仕事量○以上
△:刃なしカット性がやや劣る。
刃なしカット性△、実包耐熱油性○以上、密着仕事量△以上
×:刃なしカット性が劣る。
刃なしカット性×、実包耐熱油性○以上、密着仕事量△以上
Claims (11)
- ポリオレフィン系樹脂を含み、
流れ方向引き裂き時には流れ方向に引き裂かれ、
巾方向引き裂き時には巾方向に引き裂かれ、かつ
流れ方向と45°の方向に引き裂いた場合は、流れ方向又は巾方向のいずれかの方向に引き裂かれ、
流れ方向と45°の方向に引き裂いた場合の引き裂き方向と、切断線とのなす鋭角が30~60°であり、
流れ方向と45°の方向に引き裂いた場合の引裂強度が10g以下である、ポリオレフィン系樹脂ラップフィルム。 - フィルム流れ方向の弾性率が300MPa以上であり、
突刺強度が260g以下であり、
下記式(1)により求められる流れ方向収縮倍率(Smd)と、下記式(2)により求められる巾方向収縮倍率(Std)とが、Smd≧2.5倍、Std≧2.5倍、Smd×Std≧10倍、かつStd/Smd=0.5~10を満たす、請求項1に記載のポリオレフィン系樹脂ラップフィルム。
流れ方向収縮倍率(Smd)=100/(100-αmd) (1)
巾方向収縮倍率(Std) =100/(100-αtd) (2)
(上記式(1)及び(2)中において、αmdは流れ方向の最大熱収縮率(%)を示し、αtdは、巾方向の最大熱収縮率(%)を示す。) - 前記ポリオレフィン系樹脂が、ポリエチレン系樹脂を含む、請求項1又は2に記載のポリオレフィン系樹脂ラップフィルム。
- 波長0.154nmのX線をフィルム法線方向から入射させ、透過広角X線散乱を測定した際の、散乱角2θ=20.9°~21.8°の散乱強度の方位角分布プロフィールにおいて、
前記方位角分布プロフィールが、4つの散乱ピークを有し、
前記4つの散乱ピークの隣り合う散乱ピーク間隔が、90°±10°であり、
配向成分比Rが、0.01以上100以下であり、
前記4つの散乱ピークの平均面積が、1以上89以下である、
請求項1~3のいずれか1項に記載のポリオレフィン系樹脂ラップフィルム。 - 示差走査熱量測定における融点が、80~123℃である、請求項1~4のいずれか1項に記載のポリオレフィン系樹脂ラップフィルム。
- ゲル分率が、10~60質量%である、請求項1~5のいずれか1項に記載のポリオレフィン系樹脂ラップフィルム。
- 耐熱温度が、130℃以上である、請求項1~6のいずれか1項に記載のポリオレフィン系樹脂ラップフィルム。
- 請求項1~7のいずれか1項に記載のポリオレフィン系樹脂ラップフィルムが巻回された、巻回体。
- 請求項8に記載のポリエチレン系樹脂ラップフィルムの巻回体と、該巻回体を収納する容器と、を有し、
該容器が、前記ポリエチレン系樹脂ラップフィルムを切断するための切断具を有する、ラップフィルム収容体。 - 前記切断具が、前記容器の一部に具備された突起状のものである、請求項8に記載のラップフィルム収容体。
- 請求項8に記載のポリエチレン系樹脂ラップフィルムの巻回体と、該巻回体を収納する容器と、を有し、
該容器が、前記ポリエチレン系樹脂ラップフィルムを切断するための切断具を有さない、ラップフィルム収容体。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15/103,061 US10017616B2 (en) | 2013-12-16 | 2014-12-15 | Polyolefin-based resin wrap film and wrap film-encasing body |
CN201480067830.4A CN105813952B (zh) | 2013-12-16 | 2014-12-15 | 聚烯烃系树脂保鲜膜和保鲜膜容纳体 |
JP2015553535A JP6209225B2 (ja) | 2013-12-16 | 2014-12-15 | ポリオレフィン系樹脂ラップフィルム及びラップフィルム収容体 |
EP14872297.8A EP3085637B1 (en) | 2013-12-16 | 2014-12-15 | Polyolefin-based resin wrap film, and wrap film-encasing body |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013259453 | 2013-12-16 | ||
JP2013-259453 | 2013-12-16 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015093448A1 true WO2015093448A1 (ja) | 2015-06-25 |
Family
ID=53402794
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/083166 WO2015093448A1 (ja) | 2013-12-16 | 2014-12-15 | ポリオレフィン系樹脂ラップフィルム及びラップフィルム収容体 |
Country Status (6)
Country | Link |
---|---|
US (1) | US10017616B2 (ja) |
EP (1) | EP3085637B1 (ja) |
JP (1) | JP6209225B2 (ja) |
CN (1) | CN105813952B (ja) |
HK (1) | HK1226039A1 (ja) |
WO (1) | WO2015093448A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019049750A1 (ja) * | 2017-09-06 | 2019-03-14 | 旭化成株式会社 | ラップフィルム及びラップフィルム巻回体 |
JP2022500274A (ja) * | 2018-08-23 | 2022-01-04 | コンスタンティア・ピルク・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング・ウント・コンパニー・コマンディトゲゼルシャフト | 良好なバリア性を有するリサイクル可能な易裂き性包装用ラミネートおよびその製造方法 |
JP7060295B1 (ja) | 2021-06-10 | 2022-04-26 | 友哉 木村 | 保冷シート収納ケース |
JP7474158B2 (ja) | 2019-09-10 | 2024-04-24 | 旭化成株式会社 | 塩化ビニリデン系樹脂ラップフィルム |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB201205243D0 (en) | 2012-03-26 | 2012-05-09 | Kraft Foods R & D Inc | Packaging and method of opening |
GB2511559B (en) | 2013-03-07 | 2018-11-14 | Mondelez Uk R&D Ltd | Improved Packaging and Method of Forming Packaging |
GB2511560B (en) | 2013-03-07 | 2018-11-14 | Mondelez Uk R&D Ltd | Improved Packaging and Method of Forming Packaging |
USD861477S1 (en) * | 2017-10-02 | 2019-10-01 | Reynolds Consumer Products LLC | Container |
CN108016100A (zh) * | 2017-12-06 | 2018-05-11 | 广州融盛包装材料有限公司 | 一种生鲜蔬菜包装用防雾膜 |
USD873129S1 (en) * | 2017-12-07 | 2020-01-21 | The Procter & Gamble Company | Container |
JP6641539B2 (ja) * | 2018-02-07 | 2020-02-05 | オカモト株式会社 | 食品包装用ラップフィルム |
TWI735147B (zh) * | 2019-09-27 | 2021-08-01 | 順昶塑膠股份有限公司 | 保鮮膜及其保鮮膜盒組 |
CN112923861B (zh) * | 2021-01-23 | 2022-05-06 | 长沙理工大学 | 表征掺杂物在复合材料中取向程度的方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06143516A (ja) * | 1992-11-06 | 1994-05-24 | Mitsubishi Petrochem Co Ltd | 積層樹脂フィルム |
JP2004216825A (ja) * | 2003-01-17 | 2004-08-05 | Asahi Kasei Life & Living Corp | ポリオレフィン系樹脂防曇・熱収縮性多層フィルム |
JP2008031380A (ja) * | 2006-07-31 | 2008-02-14 | Mitsui Chemicals Inc | 易引裂き性フィルムおよびその製造方法ならびにその用途 |
JP2011168750A (ja) | 2010-02-22 | 2011-09-01 | Asahi Kasei Home Products Kk | ポリ塩化ビニリデン系樹脂ラップフィルム及びラップフィルム巻回体 |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5243880A (en) | 1975-10-03 | 1977-04-06 | Asahi Dow Ltd | Lapping films and its method of manufacturing |
EP0544098B1 (en) * | 1991-11-27 | 1998-08-12 | Mitsubishi Chemical Corporation | Polyolefin-based wrapping film |
US5492767A (en) | 1992-07-07 | 1996-02-20 | Mitsubishi Chemical Corporation | Laminated resin film |
JP2001246708A (ja) | 2000-03-07 | 2001-09-11 | Asahi Kasei Corp | 架橋積層のラップフィルム |
US6479137B1 (en) * | 2000-05-09 | 2002-11-12 | Exxon Mobil Oil Corporation | Controlled directional tear laminates |
US6482532B1 (en) * | 2000-06-07 | 2002-11-19 | Dow Global Technologies Inc. | Easy tear non-halogenic food wrap |
EP1207120A3 (en) * | 2000-11-08 | 2003-07-02 | Oji Paper Co., Ltd. | Wrap film |
CN1265962C (zh) * | 2001-03-14 | 2006-07-26 | 旭化成株式会社 | 交联层压包装薄膜和用于该薄膜的分配盒 |
US6682808B2 (en) * | 2001-04-20 | 2004-01-27 | Asahi Kasei Kabushiki Kaisha | Crosslinked laminated wrap film and dispenser box therefor |
DE10236502B4 (de) * | 2002-08-09 | 2004-10-14 | Nordenia Deutschland Gronau Gmbh | Siegelfähige Folie für Aufreißverpackungen |
KR101342748B1 (ko) * | 2005-06-27 | 2013-12-19 | 이데미쓰 유니테크 가부시키가이샤 | 이열성 연신 필름, 이열성 라미네이트 필름, 이열성 자루,및 이열성 연신 필름의 제조 방법 |
CA2794604C (en) * | 2010-04-16 | 2018-01-09 | Liqui-Box Corporation | Multi-layer, ethylene polymer-based films with high-density polyethylene based stiffening layer |
JP5877943B2 (ja) | 2010-09-03 | 2016-03-08 | リケンテクノス株式会社 | 包装用フィルム製品 |
JP5945138B2 (ja) * | 2012-03-23 | 2016-07-05 | リケンテクノス株式会社 | ラップフィルム収納箱 |
JP6026140B2 (ja) * | 2012-05-29 | 2016-11-16 | 株式会社クレハ | 包装容器 |
-
2014
- 2014-12-15 CN CN201480067830.4A patent/CN105813952B/zh active Active
- 2014-12-15 EP EP14872297.8A patent/EP3085637B1/en active Active
- 2014-12-15 WO PCT/JP2014/083166 patent/WO2015093448A1/ja active Application Filing
- 2014-12-15 US US15/103,061 patent/US10017616B2/en active Active
- 2014-12-15 JP JP2015553535A patent/JP6209225B2/ja active Active
-
2016
- 2016-12-20 HK HK16114458A patent/HK1226039A1/zh unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06143516A (ja) * | 1992-11-06 | 1994-05-24 | Mitsubishi Petrochem Co Ltd | 積層樹脂フィルム |
JP2004216825A (ja) * | 2003-01-17 | 2004-08-05 | Asahi Kasei Life & Living Corp | ポリオレフィン系樹脂防曇・熱収縮性多層フィルム |
JP2008031380A (ja) * | 2006-07-31 | 2008-02-14 | Mitsui Chemicals Inc | 易引裂き性フィルムおよびその製造方法ならびにその用途 |
JP2011168750A (ja) | 2010-02-22 | 2011-09-01 | Asahi Kasei Home Products Kk | ポリ塩化ビニリデン系樹脂ラップフィルム及びラップフィルム巻回体 |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019049750A1 (ja) * | 2017-09-06 | 2019-03-14 | 旭化成株式会社 | ラップフィルム及びラップフィルム巻回体 |
JP2022500274A (ja) * | 2018-08-23 | 2022-01-04 | コンスタンティア・ピルク・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング・ウント・コンパニー・コマンディトゲゼルシャフト | 良好なバリア性を有するリサイクル可能な易裂き性包装用ラミネートおよびその製造方法 |
JP7181382B2 (ja) | 2018-08-23 | 2022-11-30 | コンスタンティア・ピルク・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング・ウント・コンパニー・コマンディトゲゼルシャフト | 良好なバリア性を有するリサイクル可能な易裂き性包装用ラミネートおよびその製造方法 |
JP7474158B2 (ja) | 2019-09-10 | 2024-04-24 | 旭化成株式会社 | 塩化ビニリデン系樹脂ラップフィルム |
JP7060295B1 (ja) | 2021-06-10 | 2022-04-26 | 友哉 木村 | 保冷シート収納ケース |
JP2022189667A (ja) * | 2021-06-10 | 2022-12-22 | 友哉 木村 | 保冷シート収納ケース |
Also Published As
Publication number | Publication date |
---|---|
HK1226039A1 (zh) | 2017-09-22 |
EP3085637A1 (en) | 2016-10-26 |
JPWO2015093448A1 (ja) | 2017-03-16 |
US10017616B2 (en) | 2018-07-10 |
EP3085637A4 (en) | 2016-11-30 |
CN105813952A (zh) | 2016-07-27 |
US20160355647A1 (en) | 2016-12-08 |
JP6209225B2 (ja) | 2017-10-04 |
EP3085637B1 (en) | 2020-03-25 |
CN105813952B (zh) | 2018-04-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6209225B2 (ja) | ポリオレフィン系樹脂ラップフィルム及びラップフィルム収容体 | |
AU689239B2 (en) | Polyolefin stretch film | |
US5300353A (en) | Shrinkable, stretchable multi-layered film | |
JP5328464B2 (ja) | 熱収縮多層フィルム | |
WO1999046325A1 (fr) | Composition de copolymere d'ethylene et utilisation de cette derniere | |
JP3838978B2 (ja) | 架橋積層ラップフィルムとその収納箱 | |
JP4205258B2 (ja) | 熱収縮性多層フィルム | |
JP2015147302A (ja) | 熱収縮多層フィルム及びそれを用いた包装袋 | |
JP5997591B2 (ja) | 低温収縮性オーバーラップ包装用フィルム | |
JP2007045855A (ja) | ポリオレフィン系樹脂組成物 | |
JP2016117517A (ja) | ポリオレフィン系樹脂ラップフィルム、巻回体、及びラップフィルム収容体 | |
JP4919620B2 (ja) | 3層架橋フィルム | |
JP6948785B2 (ja) | 穿孔フィルム | |
JPS58175635A (ja) | 高延伸多層フイルム及びその製造方法 | |
JP6510331B2 (ja) | 架橋ポリオレフィン系樹脂フィルム | |
JP4818169B2 (ja) | 熱収縮性多層フィルム | |
JP2000094604A (ja) | 包装用多層フイルム | |
JP2023012618A (ja) | ラップフィルム及びそれを用いたラップフィルム巻回体 | |
JP2001246708A (ja) | 架橋積層のラップフィルム | |
JP3748639B2 (ja) | ポリオレフィン系樹脂組成物 | |
JP3989926B2 (ja) | 印刷適性が優れた防曇性を有する収縮包装用フィルム | |
JPH05177784A (ja) | 熱収縮性多層フィルム | |
JP3140198B2 (ja) | ストレッチシュリンク包装用フィルム | |
JPH06143519A (ja) | 積層ストレッチシュリンクフィルム | |
JP2017088194A (ja) | トップシール用多層フィルム |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14872297 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2015553535 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15103061 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REEP | Request for entry into the european phase |
Ref document number: 2014872297 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2014872297 Country of ref document: EP |