WO2019093217A1 - Film de résine de polyéthylène - Google Patents

Film de résine de polyéthylène Download PDF

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Publication number
WO2019093217A1
WO2019093217A1 PCT/JP2018/040649 JP2018040649W WO2019093217A1 WO 2019093217 A1 WO2019093217 A1 WO 2019093217A1 JP 2018040649 W JP2018040649 W JP 2018040649W WO 2019093217 A1 WO2019093217 A1 WO 2019093217A1
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Prior art keywords
polyethylene resin
film
particles
polyethylene
less
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PCT/JP2018/040649
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English (en)
Japanese (ja)
Inventor
大木　祐和
忠嗣 西
松田　明
Original Assignee
東洋紡株式会社
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Application filed by 東洋紡株式会社 filed Critical 東洋紡株式会社
Priority to KR1020207015312A priority Critical patent/KR20200078598A/ko
Priority to CN201880072163.7A priority patent/CN111315805B/zh
Priority to JP2019552750A priority patent/JP7200943B2/ja
Priority to KR1020247010725A priority patent/KR20240045383A/ko
Publication of WO2019093217A1 publication Critical patent/WO2019093217A1/fr

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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
    • B32B27/06—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Definitions

  • the present invention relates to a polyethylene resin film. More specifically, the present invention relates to a polyethylene resin film which is excellent in heat sealability, stable blocking resistance and stable slip property, and also excellent in appearance and scratch resistance.
  • the sealant film is generally used by laminating with a substrate film such as a biaxially oriented nylon film, a biaxially oriented ester film, a biaxially oriented polypropylene film or the like which is inferior in thermal adhesion to a sealant film at a low temperature .
  • a substrate film such as a biaxially oriented nylon film, a biaxially oriented ester film, a biaxially oriented polypropylene film or the like which is inferior in thermal adhesion to a sealant film at a low temperature .
  • a polyethylene-based resin inflation film suitable for a shopping bag has been reported in which particles made of a polyethylene resin having a very high molecular weight are added to a high density polyethylene resin (see, for example, Patent Document 3).
  • this method has problems such as too high tear strength, poor heat seal properties at low temperature, and poor transparency, and in addition, the addition of particles made of polyethylene resin makes the slipperiness unstable. there were.
  • An object of the present invention is to provide a polyethylene resin film which is excellent in heat sealability, stable blocking resistance, stable slipperiness, appearance and scratch resistance and in which particles are less likely to come off. Moreover, it aims at providing the laminated body using this polyethylene-type resin film, and also a package body.
  • the inventors of the present invention intensively studied, as a polyethylene resin film having a density not more than a specific range, contain particles made of a polyethylene resin and control the height of protrusions on the surface of the film. It has been found that the problems can be solved by the above, and the present invention has been solved.
  • the present invention comprises a polyethylene resin composition containing particles of a polyethylene resin and a polyethylene resin having a density of 940 kg / m 3 or less, and substantially free of inorganic particles and organic crosslinked particles,
  • the polyethylene-based resin film is characterized in that the maximum peak height of the surface on one side is 2 ⁇ m or more and 15 ⁇ m or less, and the particles other than the particles made of the polyethylene-based resin.
  • Another aspect is to contain particles made of a polyethylene resin, is substantially free of inorganic particles and organic cross-linked particles, a layer density of the polyethylene resin composition is 940 kg / m 3 or less at least
  • the polyethylene resin film is characterized in that it is on one side and the maximum maximum height of the surface of the layer is 2 ⁇ m or more and 15 ⁇ m or less.
  • the particles of the polyethylene resin have a viscosity average molecular weight of not less than 1.5 million and a melting point peak temperature by DSC of not more than 150.degree.
  • erucic acid amide and / or ethylene bis oleic acid amide.
  • the blocking value of the surface layers having the maximum peak height of 2 ⁇ m or more and 15 ⁇ m or less is 200 mN / 70 mm or less.
  • the laminated body containing the polyethylene-type resin film in any one of the above-mentioned, and another film is suitable.
  • Preferred is a packaging bag comprising a laminate as described above.
  • the present invention can provide a polyethylene resin film which is excellent in heat sealability, stable blocking resistance and stable slipperiness, and also excellent in appearance and scratch resistance. Moreover, the laminated body using this polyethylene-type resin film, and also a package can be provided.
  • the polyethylene-based resin film of the present invention is composed of a polyethylene-based resin composition, but mainly contains a polyethylene-based resin.
  • the polyethylene resin is a homopolymer of ethylene monomer, a copolymer of ethylene monomer and ⁇ -olefin, and a mixture thereof, and as ⁇ -olefin, propylene, butene-1, hexene Examples thereof include -1, 4-methylpentene-1, octene-1, and decene-1.
  • the density range of the polyethylene resin composition is preferably 900 ⁇ 940kg / m 3, more preferably 910 ⁇ 940kg / m 3, more preferably 910 ⁇ 935kg / m 3, especially 915 ⁇ 935kg / m 3
  • 915 to 925 kg / m 3 is particularly preferred.
  • a polyethylene resin composition having a density of less than 900 kg / m 3 is likely to have reduced blocking resistance.
  • a polyethylene-based resin composition having a density of greater than 940 kg / m 3 has a high heat seal initiation temperature, is difficult to form into a bag, and is inferior in transparency.
  • the present inventors found that when using a polyethylene resin composition whose density is greater than 940 kg / m 3 , it is difficult to obtain stable blocking resistance or stable slip property of the polyethylene resin film.
  • the For blocking resistance a sample obtained by superimposing measurement surfaces of a film is sized by 7 cm ⁇ 7 cm, temperature 50 ° C., pressure 440 kgf / cm 2 , and time 15 minutes in a heat press (Model: SA-303 manufactured by Tester Sangyo Co., Ltd.) Perform pressure treatment.
  • the sample blocked with this pressure treatment and the bar are attached to an autograph (Shimadzu model: UA-3122) so that the bar and the peeling surface are horizontal, and the bar has a speed (100 m
  • the force at which the blocking part is peeled off is measured four times per minute, and the average value is used as an index, but when using a polyethylene resin composition whose density is greater than 940 kg / m 3
  • the heat seal start temperature tends to be high. It is preferable that the variation of each measurement value of the four measurements be at the same level as when inorganic particles are used.
  • the melt flow rate (hereinafter sometimes referred to as MFR) of the polyethylene resin composition of the present invention is preferably about 2.5 to 4.5 g / min from the viewpoint of film forming property and the like.
  • MFR was measured in accordance with ASTM D1893-67.
  • the polyethylene resin is synthesized by a method known per se.
  • the polyethylene resin composition of the present invention preferably has a melting point of 85 ° C. or more, more preferably 100 ° C. or more, particularly preferably 110 ° C. or more, from the viewpoint of heat resistance and the like.
  • the polyethylene-based resin composition in the present invention may be a single system, but it is also possible to blend two or more types of polyethylene resins having different densities in the above density range.
  • the average density and the blending ratio can be estimated by GPC measurement or density measurement.
  • particles made of a polyethylene-based resin described below can be blended.
  • particles made of polyethylene resin in which case the particles made of a polyethylene resin preferably have a viscosity average molecular weight of not less than 1,500,000, and more preferably not less than 1,600,000. More than 1.7 million are more preferable. In addition, 2.5 million or less is preferable, 240 or less is more preferable, and 2.3 million or less is more preferable. With a viscosity average molecular weight in this range, the maximum peak height of the surface layer on at least one side can be 2 ⁇ m or more and 15 ⁇ m or less.
  • the viscosity average molecular weight of the particles made of polyethylene resin is less than 1.5 million, if the temperature at the time of melt mixing is higher than the melting point peak, due to decomposition by heat or shear or fusion / flocculation or partial compatibility with the base resin As a result of changes in particle shape, the formation of projections like conventional inorganic particles and organic cross-linked polymer beads can not be performed, and the function as an antiblocking agent is not sufficient, and the appearance such as transparency, film It affects mechanical strength or heat sealability.
  • the particles made of a polyethylene resin are homopolymers of ethylene monomers, copolymers of ethylene monomers and ⁇ -olefins, and mixtures thereof, and as ⁇ -olefins, propylene And butene-1, hexene-1, 4-methylpentene-1, octene-1, decene-1 and the like.
  • a density range of particles made of polyethylene resin is preferably 930 ⁇ 950kg / m 3, more preferably 935 ⁇ 945kg / m 3, more preferably 937 ⁇ 942kg / m 3.
  • Particles made of a polyethylene resin having a density of less than 930 kg / m 3 are soft and the shape of the particles is difficult to maintain during melt extrusion, and the blocking resistance tends to decrease.
  • particles made of a polyethylene resin having a density of more than 950 kg / m 3 are likely to have a drop in dropout resistance because the particles are hard and not only the scratch resistance is easily lowered but also the affinity to the base polyethylene resin is lowered. .
  • the average particle diameter of particles made of a polyethylene resin used in the present invention is preferably 2 ⁇ m or more, more preferably 3 ⁇ m or more, and still more preferably 5 ⁇ m or more.
  • the average particle diameter is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, and still more preferably 10 ⁇ m or less.
  • the addition amount of the particles of the polyethylene resin of the present invention is preferably 0.1% by weight or more, more preferably 0.3% by weight or more, still more preferably 0.4% by weight or more, based on the whole film. preferable. Moreover, 2 weight% or less is preferable, 1.5 weight% or less is more preferable, and 1.0 weight% or less is more preferable.
  • the addition amount of particles made of polyethylene resin is less than 0.1% by weight, it becomes difficult to set the maximum peak height of the surface layer on at least one side to 2 ⁇ m or more per designated area (0.2 mm 2 ), and anti-blocking It becomes difficult to obtain the sex and slippery.
  • the addition amount of particles made of polyethylene resin is more than 2% by weight, the number of projections on the surface is large, the transparency is poor, and the low temperature sealing property is easily deteriorated.
  • polyethylene resins other than the above-mentioned "particles composed of polyethylene resin” are homopolymers of ethylene monomers, or copolymers of ethylene monomers and ⁇ -olefins, and It is a mixture, and as the ⁇ -olefin, propylene, butene-1, hexene-1, 4-methylpentene-1, octene-1, decene-1 and the like can be exemplified.
  • the density range is preferably 900 ⁇ 940kg / m 3 of the polyethylene resin other than the particles made of a polyethylene resin, more preferably 910 ⁇ 940kg / m 3, more preferably 920 ⁇ 940kg / m 3, 920 ⁇ 935 kg / m 3 is particularly preferred, and 920 to 925 kg / m 3 is more particularly preferred.
  • a polyethylene resin having a density of less than 900 kg / m 3 is likely to have reduced blocking resistance.
  • a polyethylene resin having a density of greater than 940 kg / m 3 has a high heat sealing start temperature, is difficult to form into a bag, and is inferior in transparency.
  • the present inventors have found that when using a polyethylene resin having a density greater than 940 kg / m 3 , it is difficult to obtain stable blocking resistance or stable slip of the polyethylene resin film.
  • a sample obtained by superimposing measurement surfaces of a film is sized by 7 cm ⁇ 7 cm, temperature 50 ° C., pressure 440 kgf / cm 2 , and time 15 minutes in a heat press (Model: SA-303 manufactured by Tester Sangyo Co., Ltd.) Perform pressure treatment.
  • the sample blocked with this pressure treatment and the bar are attached to an autograph (Shimadzu model: UA-3122) so that the bar and the peeling surface are horizontal, and the bar has a speed (100 m
  • the force at which the blocking part is peeled off is measured four times per minute, and the average value is used as an index, but when using a polyethylene-based resin whose density is greater than 940 kg / m 3 , Not only the variation of each of the four measurements but also the tendency to increase the heat sealing start temperature was recognized. It is preferable that the variation of each measurement value of the four measurements be at the same level as when inorganic particles are used.
  • high-pressure low-density polyethylene is transparent, flexible, and excellent in tear strength and tensile strength on average.
  • LDPE low-density polyethylene
  • butene-1, hexene-1 octene-1 are copolymerized in small amounts, and there are many short molecular chains in the molecular chain, and linear short chain branched polyethylene (LLDPE), which has excellent sealing performance and physical strength.
  • a metallocene catalyst linear short-chain branched polyethylene (LLDPE) that exhibits extremely sharp molecular weight distribution, uniform comonomer distribution, and excellent tear, tensile, puncture strength, and pinhole resistance properties is selected according to its application. be able to.
  • the melt flow rate (hereinafter sometimes referred to as MFR) is 2.5 to 4.5 g / min from the viewpoint of film forming property etc. The degree is preferred.
  • MFR was measured in accordance with JIS-K7210.
  • the polyethylene resin is synthesized by a method known per se.
  • the polyethylene resin particles when using a resin having a MFR as low as 2.5 g / 10 min or less other than the polyethylene resin particles, the polyethylene resin particles may be used in the same manner as described for the density. Since the change in particle size is apt to occur due to the decrease in viscosity average molecular weight and the entanglement of molecular chains with polyethylene resin other than particles made of polyethylene resin, it is necessary to be careful about the extrusion conditions. In the case of high-speed film formation using a large-sized film forming machine, an MFR of about 3 to 4 g / 10 min is particularly preferable because of film forming property.
  • the melting point is preferably 85 ° C. or more, more preferably 100 ° C. or more, and particularly preferably 110 ° C. or more from the viewpoint of heat resistance and the like in the present invention.
  • the polyethylene-based resin other than the particles of the polyethylene-based resin in the present invention may be a single system, but two or more polyethylene resins different in density in the above-mentioned density range may be blended.
  • the average density and the blending ratio can be estimated by GPC measurement or density measurement.
  • additives such as an antioxidant, a neutralizing agent, an organic lubricant, a non-droplet and an antistatic agent are used in combination as long as the purpose and effect of the present invention are not impaired. Also good. Blending of these additives can be appropriately blended when blending and mixing the respective components of the polyethylene resin composition.
  • organic lubricant it is preferable to add an organic lubricant.
  • the lubricity and antiblocking effect of the laminated film are improved, and the handleability of the film is improved. As the reason, it is considered that the lubricant effect and the mold release effect are expressed by the organic lubricant bleeding out and being present on the film surface.
  • organic lubricant having a melting point higher than normal temperature include fatty acid amides and fatty acid esters. Specifically, oleic acid amide, erucic acid amide, behenic acid amide, ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, ethylene bis oleic acid amide and the like. These may be used alone, but it is preferable to use two or more kinds in combination because the lubricity and antiblocking effect can be maintained even under a severe environment.
  • the lower limit of the concentration of the organic lubricant amide in the layer containing particles made of polyethylene resin is preferably 200 ppm, more preferably 400 ppm. If it is less than the above, slipperiness may be deteriorated.
  • the upper limit of the organic lubricant amide concentration is preferably 2500 ppm, more preferably 2000 ppm. If it exceeds the above, it is too slippery, which is not preferable.
  • ethylene / vinyl acetate copolymer, ethylene / acrylic ester copolymer, etc. may be mixed and used as long as the purpose and effect of the present invention are not impaired.
  • the polyethylene resin film of the present invention is required to be substantially free of inorganic particles.
  • the inorganic particles referred to here are inorganic substances generally used as an antiblocking agent such as silica, talc, calcium carbonate, diatomaceous earth, zeolite and the like, and inorganic substances in the entire polyethylene resin film of the present invention not containing substantially It means that the proportion of the amount of particles is 0.2% by weight or less. More preferably, it is 0.1% by weight or less.
  • the polyethylene resin film of the present invention it is necessary to contain substantially no crosslinked organic particles.
  • the crosslinked organic particles referred to here are organic crosslinked particles represented by polymethyl acrylate resin etc., and the content of the crosslinked organic particles in the whole of the polyethylene resin film of the present invention that the content is not substantially contained is 0.2 It means that it is not more than% by weight. More preferably, it is 0.1% by weight or less.
  • the polyethylene resin film of the present invention for example, specific ones among polyethylene resins conventionally used as polyethylene resins other than particles consisting of polyethylene resin and particles consisting of polyethylene resin It is preferable to adopt a process of melt-kneading a polyethylene-based resin composition containing the following, a process of melt-extruding the melt-kneaded resin composition to form a molten resin composition sheet, and a process of cooling and solidifying the molten resin composition sheet.
  • the polyethylene resin film of the present invention may be a single layer or a laminate.
  • the thickness of the film in the case of a single layer is preferably 3 ⁇ m or more, more preferably 10 ⁇ m or more, further preferably 15 ⁇ m or more, and particularly preferably 20 ⁇ m or more. Moreover, 200 micrometers or less are preferable, 150 micrometers or less are more preferable, and 100 micrometers or less are especially preferable. If it is less than 3 ⁇ m, the effect of particles made of polyethylene resin is reduced, and the effect of blocking resistance and slipperiness is hard to be obtained.
  • the thickness of the layer containing particles made of a polyethylene resin in the case of lamination and the maximum peak height of at least one surface layer is 2 ⁇ m or more and 15 ⁇ m or less is preferably 3 ⁇ m or more, more preferably 10 ⁇ m or more, 15 micrometers or more are further preferable, and 20 micrometers or more are especially preferable. Moreover, 200 micrometers or less are preferable, 150 micrometers or less are more preferable, and 100 micrometers or less are especially preferable. If it is less than 3 ⁇ m, the effect of particles made of polyethylene resin is reduced, and the effect of blocking resistance and slipperiness is hard to be obtained. (Raw material mixing process)
  • any method may be used as long as they are uniformly mixed, and if using master batch, ribbon blender, The method of mixing using a Henschel mixer, a tumbler mixer etc., etc. are mentioned.
  • particles made of a polyethylene resin may be attached to a resin to which an additive is attached, or may be added directly to an extruder by side feed or the like.
  • particles made of polyethylene resin are directly mixed with linear low density polyethylene, homopolymer of ethylene monomer, or copolymer of ethylene monomer and ⁇ -olefin without using masterbatch.
  • high dispersibility can be obtained, and in terms of cost, direct attachment by the side feed method or the like is preferable.
  • the lower limit of the melt mixing temperature of the polyethylene resin composition is preferably 200 ° C., more preferably 210 ° C., and still more preferably 220 ° C. If the amount is less than the above, discharge may be unstable.
  • the upper limit of the resin melting temperature is preferably 260 ° C. When the amount exceeds the above range, decomposition of the resin proceeds, and as a result of recombination, the amount of a crosslinked organic substance generated as a result of recombination, so-called foreign matter such as gel, increases.
  • the above-mentioned antioxidant is contained in the polyethylene resin composition, melt extrusion at higher temperatures is possible, but it is preferable to set the temperature to 270 ° C. or less.
  • the melting point of the polyethylene resin particles used in the present invention is about 150 ° C. or less, and it is mixed with a polyethylene resin other than the polyethylene resin particles, and it is much lower than the temperature at the time of melt-kneading
  • the polyethylene resin film extruded from the T die without being dispersed at the molecular level in polyethylene resins other than particles consisting of polyethylene resins, and made of a polyethylene resin is obtained through the cooling process.
  • the particles are present in the polyethylene resin other than the particles made of the polyethylene resin while maintaining the particle size and shape before addition.
  • the filter medium used for high precision filtration of the molten resin is not particularly limited, but in the case of a filter medium of a stainless sintered body, in addition to foreign substances such as so-called gel, Si, Ti, Sb, Ge derived from additives such as catalyst It is excellent in the removal performance of the aggregate which has Cu as a main component, and is suitable. Moreover, it is preferable that the filtration precision is 200 micrometers or less.
  • the filtration accuracy as referred to herein means the following. The nominal filtration accuracy, and the ability to capture 60 to 98% of particles (in this case, 200 ⁇ m or more) larger than the indicated filtration accuracy.
  • the pressure increase during melt-kneading of the polyethylene resin composition is preferably smaller.
  • the method of measuring the amount of pressure increase was performed by the method described in the example.
  • the molten polyethylene-based resin composition sheet is melt extruded from, for example, a T-die, cast on a cooling roll, and solidified by cooling to obtain an unstretched sheet.
  • a cooling roll it is preferable to cast on a cooling roll. Since the particles made of polyethylene resin used in the present invention are originally hydrophobic resin, the hydrophobicity of the surface of the particles does not change even after melt-kneading and extruding steps, and the particles are seen as inorganic particles whose surface is hydrophobized Thermal degradation products at the lip of the T-shaped die, so-called "stain buildup" are extremely unlikely to occur.
  • T-die method melt-extruding a molten polyethylene-based resin composition sheet and forming the film into a film by a T-die method or an inflation method, but the T-die method is particularly preferable in that the melting temperature of the resin composition can be increased. desirable.
  • the lower limit of the cooling roll temperature is preferably 10 ° C. If it is less than the above, not only the effect of crystallization suppression may be saturated but also problems such as condensation may occur, which is not preferable.
  • the upper limit of the cooling roll temperature is preferably 70 ° C. or less. If the content exceeds the above range, crystallization proceeds and the transparency deteriorates, which is not preferable. When the temperature of the cooling roll is in the above range, it is preferable to lower the humidity of the environment around the cooling roll to prevent condensation.
  • the temperature of the cooling roll surface rises because the high temperature resin contacts the surface.
  • the cooling roll is cooled by flowing cooling water through the inside of the pipe, but a sufficient amount of cooling water is secured, the arrangement of the pipe is devised, maintenance is performed to prevent sludge from adhering to the pipe, etc. It is necessary to reduce the temperature difference in the width direction of the surface.
  • the thickness of the unstretched sheet is preferably in the range of 3 to 200 ⁇ m.
  • the polyethylene resin film of the present invention may have a multilayer structure.
  • one or two or more other layers can be provided in addition to the layer made of the polyethylene resin composition described above and having a maximum peak height of 2 ⁇ m or more and 15 ⁇ m or less on the surface.
  • a general multilayering apparatus multilayer feed block, static mixer, multilayer multi manifold, etc.
  • a method of laminating thermoplastic resins delivered from different flow paths using two or more extruders in multiple layers using a field block, static mixer, multi-manifold die or the like can be used.
  • a layer consisting of a polyethylene resin composition and having a maximum peak height of 3 ⁇ m or more and 15 ⁇ m or less on the surface is used as a seal layer (A layer), and the other layers are an intermediate layer (B layer) and laminate, respectively. It is good to set it as a layer (C layer) and to contain in this order.
  • the outermost layers are the A layer and the C layer, respectively.
  • Examples of the polyethylene-based resin used for the intermediate layer (B layer) and the laminate layer (C layer) include a mixture of one or more selected from ethylene / ⁇ -olefin copolymer and high pressure polyethylene.
  • the ethylene / ⁇ -olefin copolymer is a copolymer of ethylene and an ⁇ -olefin having 4 to 18 carbon atoms, and as the ⁇ -olefin, butene-1, hexene-1, 4-methylpentene-1, Octene-1, decene-1 and the like can be mentioned.
  • the films obtained from these polyethylene resins have excellent heat seal strength, hot tack, dirt sealability, impact resistance, and the polyethylene resins are not limited to the other properties to the extent that they do not impair the properties.
  • Resins such as ethylene / vinyl acetate copolymer, ethylene / acrylic acid ester copolymer and the like may be mixed and used.
  • the polyethylene resins used for the intermediate layer (B layer) and the laminate layer (C layer) may be the same or different.
  • particles made of polyethylene resin may or may not be added. However, it does not substantially contain inorganic particles and organic crosslinked particles.
  • the term "not substantially containing" means that the proportion of the amount of the crosslinked organic particles in the entire polyethylene resin film of the present invention is 0.2% by weight or less. More preferably, it is 0.1% by weight or less.
  • the average density of the polyethylene resin of each layer of the film is preferably sealant layer (A layer) ⁇ intermediate layer (B layer) ⁇ laminate layer (C layer).
  • sealant layer A layer
  • intermediate layer B layer
  • laminate layer C layer.
  • the incorporated organic lubricant is difficult to move to the dense layer, and is effective for maintaining the slipperiness of the sealant layer after lamination.
  • the lower limit of the density of the intermediate layer (B layer) and the laminate layer (C layer) is preferably 900 kg / m 3 , more preferably 920 kg / m 3 , and still more preferably 930 kg / m 3 . If it is less than the above, the body may be weak and difficult to process.
  • the upper limit of the density of the intermediate layer (B layer) and the laminate layer (C layer) is preferably 960 kg / m 3 , more preferably 940 kg / m 3 , and still more preferably 935 kg / m 3 .
  • the above-mentioned organic lubricant may be used in the middle layer (layer B) of the film of the present invention, and the lower limit of the organic lubricant is preferably 200 ppm, more preferably 400 ppm. If it is less than the above, slipperiness may be deteriorated.
  • the upper limit of the erucic acid amide concentration of the intermediate layer (B layer) is preferably 2000 ppm, more preferably 1500 ppm. If it exceeds the above, it may slip too much, which may cause winding deviation.
  • the recovered resin may be blended in an amount of 10 to 30% by mass in the intermediate layer (layer B) of the film of the present invention.
  • actinic ray treatment such as corona treatment on the surface of the laminate layer (C layer) of the polyethylene film described above.
  • the correspondence improves the laminate strength.
  • a layer comprising particles of a polyethylene resin is contained, and a layer having a maximum peak height of 2 ⁇ m or more and 15 ⁇ m or less of at least one surface layer is a seal layer (A layer), and the other layer is a laminate layer (C Layer) is good.
  • the maximum peak height of the surface layer of at least one side of the polyethylene resin film of the present invention is required to be 2 ⁇ m or more and 15 ⁇ m or less. When the maximum peak height Rz exceeds 15 ⁇ m, it is not preferable because appearance defects occur.
  • the measurement method is carried out by the method described in the examples.
  • the polyethylene resin film of the present invention preferably has a number of projections exceeding 15 ⁇ m (number / 0.2 mm 2 ) in the surface layer having a maximum peak height of 2 ⁇ m or more and 15 ⁇ m or less on the surface of 0 or less. The smaller the number, the poorer the appearance such as flicker and haze.
  • the measurement method is carried out by the method described in the examples.
  • the upper limit of the heat sealing start temperature of the polyethylene resin film laminated with the biaxially stretched nylon film (15 ⁇ m) is preferably 130 ° C., more preferably 120 ° C. m. If the above is exceeded, sealing may be difficult.
  • the lower limit of the ultimate heat seal strength at 120 ° C. of the polyethylene resin film laminated with biaxially stretched nylon film (15 ⁇ m) is preferably 30 N / 15 mm, more preferably 35 N / 15 mm. If it is less than the above, the bag may be easily torn after making the bag.
  • the upper limit of the heat seal strength at 120 ° C. of the polyethylene resin film laminated with biaxially oriented nylon film (15 ⁇ m) is preferably 70 N / 15 mm, more preferably 65 N / 15 mm. If the above is exceeded, it may be difficult to open the bag after making the bag.
  • the measurement method is carried out by the method described in the examples.
  • the lower limit of the blocking strength of the polyethylene resin film laminated with the biaxially stretched nylon film (15 ⁇ m) is preferably 0 mN / 20 mm, more preferably 10 mN / 20 mm, and still more preferably 15 mN / 20 mm.
  • the upper limit of the blocking strength is preferably 150 mN / 20 mm, more preferably 50 mN / 20 mm, and still more preferably 40 mN / 20 mm. If the above is exceeded, the slipperiness immediately after unrolling may deteriorate.
  • the measurement method is carried out by the method described in the examples.
  • the lower limit of the coefficient of static friction after lamination of the polyethylene resin film laminated with biaxially stretched nylon film (15 ⁇ m) is preferably 0.05, and more preferably 0.08. When it is less than the above, the film may slip too much during winding, which may cause winding deviation.
  • the upper limit of the coefficient of static friction after lamination is preferably 0.50, more preferably 0.4. When it exceeds the above, the opening property after bag making is bad, and the loss at the time of processing may increase.
  • the measurement method is carried out by the method described in the examples.
  • the lower limit of the haze of the polyethylene resin film of the present invention is preferably 3%, more preferably 4%, still more preferably 5%. If it is less than the above, there may be a small amount of antiblocking agent, which may cause blocking.
  • the upper limit of the haze is preferably 15%, more preferably 12%, and still more preferably 10%. If the above is exceeded, it may be difficult to view the contents.
  • the measurement method is carried out by the method described in the examples.
  • the polyethylene resin film of the present invention hardly feels flickering or has fine flickering but is uniform and not particularly concerned.
  • the measurement method is carried out by the method described in the examples.
  • non-powder type which has blocking resistance without applying conventional starch or the like powder to the film surface
  • inorganic particles having an average particle diameter of about 10 ⁇ m have been added.
  • the lower limit of the Young's modulus (MD) of the polyethylene resin film of the present invention is preferably 100 MPa, more preferably 200 MPa. If it is less than the above, the waist may be too weak to be processed easily.
  • the upper limit of Young's modulus (MD) is preferably 800 MPa, more preferably 600 MPa.
  • the lower limit of the Young's modulus (TD) of the polyethylene resin film of the present invention is preferably 100 MPa, more preferably 200 MPa. If it is less than the above, the waist may be too weak to be processed easily.
  • the upper limit of Young's modulus (TD) is preferably 1000 MPa, more preferably 600 MPa.
  • Average particle diameter of particles made of polyethylene resin The average particle size of the polyethylene resin particles before use was measured as follows. The particles are dispersed in ion exchange water stirred at a predetermined rotation speed (about 5000 rpm) using a high-speed stirrer, and the dispersion is added to isotone (saline) and further dispersed by an ultrasonic disperser, The particle size distribution was determined by the counter method and calculated as the volume average particle size.
  • melting point Using a differential scanning calorimeter (DSC) manufactured by SII, measurement was performed at a sample amount of 10 mg and a heating rate of 10 ° C./min. The melting endothermic peak temperature detected here was taken as the melting point.
  • DSC differential scanning calorimeter
  • Heat seal start temperature (° C) An adhesive for dry lamination made by Toyo Morton (TM569, CAT-10L) is applied to the corona surface of a nylon film (Toyobo's biaxially stretched nylon film: N1100, 15 ⁇ m) so that the solid content is 3 g / m 2 and 80 ° C. After the solvent was removed by evaporation in an oven, the corona-coated surface of the polyethylene resin film and the coated surface of the adhesive were laminated by nipping on a temperature control roll at 60 ° C. The laminated laminated film was aged at 40 ° C. for 2 days.
  • the prepared laminated sample was heat sealed at a seal pressure of 0.1 MPa, at a seal time of 0.5 seconds, at a seal temperature of 90 to 160 ° C. and a pitch of 10 ° C. and a width of 10 mm.
  • the heat-sealed sample is cut into strips so that the heat seal width is 15 mm, set in an autograph (Shimadzu model: UA-3122), and the seal surface is peeled at a speed of 200 mm / min.
  • the value was measured by n number 3, and heat seal strength and heat seal temperature were plotted at each temperature.
  • the heat seal temperature which becomes 4.9 N / 15 mm from the graph which tied between each plot with a straight line was read, and it was set as the heat seal start temperature.
  • the prepared laminated sample was heat sealed at a seal pressure of 0.1 MPa, at a seal time of 0.5 seconds, at a seal temperature of 120 to 190 ° C. and a pitch of 10 ° C. and a width of 10 mm.
  • the heat-sealed sample is cut into strips so that the heat seal width is 15 mm, set in an autograph (Shimadzu model: UA-3122), and the seal surface is peeled at a speed of 200 mm / min.
  • the value was measured by n number 3, and the heat seal strength with the highest average value was taken as the ultimate seal strength.
  • Blocking Strength A laminated film with a nylon film (biaxially stretched nylon film manufactured by Toyobo Co., Ltd .: N1100, 15 ⁇ m) was prepared as follows. Apply an adhesive for dry lamination (TM569, CAT-10L) made by Toyo Morton on the corona surface of nylon film so that the solid content is 3 g / m 2 and evaporate off the solvent in an oven at 80 ° C. The corona surface of the film and the coated surface of the adhesive were nipped and laminated on a 60 ° C. temperature control roll. The laminated laminated film was aged at 40 ° C. for 2 days.
  • a sample (10 cm ⁇ 15 cm) obtained by superposing measurement surfaces on each other is positioned 1 cm inside the length direction (15 cm) at the center of the sample width (10 cm)
  • a 7 cm ⁇ 7 cm aluminum plate (2 mm thick) is placed on top so as to be aligned, and subjected to pressure treatment at a temperature of 50 ° C. and a pressure of 440 kgf / cm 2 for 15 minutes.
  • a laminated film with a nylon film (biaxially stretched nylon film made by Toyobo Co., Ltd .: N1100, 15 ⁇ m) was produced as follows.
  • An adhesive for dry lamination made by Toyo Morton (TM569, CAT-10L) is applied to the corona surface of a nylon film so that the solid content is 3 g / m 2 and the solvent is removed by evaporation in an oven at 80 ° C.
  • the corona surface of the adhesive and the coated surface of the adhesive were nipped and laminated on a temperature control roll at 60.degree.
  • the laminated laminated film was aged at 40 ° C. for 2 days.
  • the static friction coefficient between the polyethylene resin film faces of the produced laminated film was measured in an environment of 23 ° C. and 65% RH in accordance with JIS-K7125.
  • Haze (%) [Td (diffuse transmittance%) / Tt (total light transmittance%)] x 100
  • a laminated film with a nylon film (biaxially stretched nylon film made by Toyobo Co., Ltd .: N1100, 15 ⁇ m) was produced as follows. Apply an adhesive for dry lamination (TM569, CAT-10L) made by Toyo Morton on the corona surface of nylon film so that the solid content is 3 g / m 2 and evaporate off the solvent in an oven at 80 ° C. The corona surface of the film and the coated surface of the adhesive were nipped and laminated on a 60 ° C. temperature control roll. The laminated laminated film was aged at 40 ° C. for 2 days.
  • the polyethylene-based resin film of the produced laminated film was pinched with a finger and rubbed ten times so that the polyethylene resin film surfaces of the laminated film overlap each other, and visually observed. Ease of scratching was classified by the following ⁇ , ⁇ , ⁇ , x. ⁇ : There is almost no damage. ⁇ : There are thin streaks of scratches but no whitening. Fair: fine streaks and partial whitening are observed. X: The rubbed part almost whitens.
  • Miperon XM 220 Ultra-high molecular weight polyethylene particles, manufactured by Mitsui Chemicals, Inc., density 940 kg / m 3 , melting point 136 ° C., viscosity average molecular weight 2,000,000, Shore hardness 65 D, volume average particle diameter 30 ⁇ m, particles exceeding 30 ⁇ m Weight percentage of diameter 55%)
  • Miperon PM 220 modified product ultra high molecular weight polyethylene particles, manufactured by Mitsui Chemicals, Inc., density 940 kg / m 3 , melting point 135 ° C., viscosity average molecular weight 1.8 million, Shore hardness 65 D, volume average particle diameter 10 ⁇ m, 25 ⁇ m Weight percentage of particle size exceeding 1% or less
  • KMP-130-10 spherical silica particles, manufactured by Shin-Etsu Silicon Co., Ltd., average particle diameter 10 ⁇ m
  • Dicalite WF diatomaceous earth, Grefco. Inc., product, processed to an average particle diameter of 5 ⁇ m by a pin mill crusher Use
  • Ethylene bis oleic acid amide using Sumitomo Chemical's ethylene bis oleic acid amide 2% master batch EMB11
  • Erucic acid amide using Sumitomo Chemical's Erucic acid amide 4% master batch EMB10
  • Examples 1 to 5 The resins and additives shown in Table 1 were used as raw materials for the seal layer, laminate layer, and intermediate layer, respectively melted at 240 ° C. using three extruders respectively, and filtered with a sintered filter having a filtration accuracy of 120 ⁇ m. After co-extrusion from a T-die into a sheet, melt extrusion so that the thickness ratio of the seal layer, intermediate layer, and laminate layer becomes 1: 3: 1, and after cooling and solidifying with a 30 ° C.
  • the surface of the laminate layer of the sheet was subjected to corona discharge treatment, and was wound into a roll at a speed of 150 m / min to obtain a polyethylene resin film having a thickness of 50 ⁇ m and a wet tension of 45 N / m on the surface of the laminate layer.
  • the polyethylene resin films obtained in Examples 1 to 5 are excellent in heat sealability, and the blocking resistance and the friction coefficient have small fluctuations in measured values between the measurement samples, and have stable blocking resistance and slipperiness. Moreover, the appearance and the scratch resistance were also excellent. And it was excellent also in film forming processability.
  • the surface of the laminate layer of the sheet was subjected to corona discharge treatment, and was wound into a roll at a speed of 150 m / min to obtain a polyethylene resin film having a thickness of 50 ⁇ m and a wet tension of 45 N / m on the surface of the laminate layer.
  • the film obtained in Comparative Example 1 was excellent in blocking resistance and slipperiness, slightly flickering, and inferior in scratch resistance and film forming processability.
  • the film obtained in Comparative Example 2 was excellent in blocking resistance and slipperiness, it had a flickering feeling and was inferior in appearance.
  • the film obtained in Comparative Example 3 was excellent in blocking resistance and transparency, it had a flickering feeling and the appearance was remarkably inferior.
  • the film obtained in Comparative Example 4 had melting unevenness on the surface, a flickering feeling, and the appearance was significantly inferior.
  • blocking resistance, slipperiness, and scratch resistance were also inferior.
  • the blocking resistance and the friction coefficient were not stable because the variation of the measured value between the measurement samples was large.
  • the present invention is not limited to the composition indicated in the above-mentioned example, but combines the composition indicated in each example suitably
  • the configuration can be changed as appropriate without departing from the scope of the present invention.
  • the polyethylene-based resin film according to the present invention is excellent in its properties, and can be suitably used as a film for a wide range of applications such as food packaging.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Wrappers (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Materials For Medical Uses (AREA)

Abstract

L'invention concerne un film de résine polyéthylène qui présente d'excellents résultats en termes d'aptitude au thermoscellage, de résistance au blocage, de glissance, ainsi qu'en termes d'apparence et de résistance aux rayures. Ce film de résine de polyéthylène est caractérisé en ce qu'il comprend une composition de résine de polyéthylène qui contient des particules d'une résine de polyéthylène, et une résine de polyéthylène ayant une densité de 940 kg/m3 ou moins, mais ne contient sensiblement pas de particules inorganiques ou de particules organiques réticulées, la hauteur maximale de pic d'au moins une surface de celles-ci étant de 2 à 15 µm.
PCT/JP2018/040649 2017-11-08 2018-11-01 Film de résine de polyéthylène WO2019093217A1 (fr)

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JP2019552750A JP7200943B2 (ja) 2017-11-08 2018-11-01 ポリエチレン系樹脂フィルム
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JP2013245345A (ja) * 2012-05-29 2013-12-09 Mitsui Chemicals Inc オレフィン系重合体組成物および該組成物からなるフィルム
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JP2006095955A (ja) * 2004-09-30 2006-04-13 Sumitomo Chemical Co Ltd 表面保護フィルム
JP2008088248A (ja) * 2006-09-29 2008-04-17 Tamapori Kk インフレーション成形用樹脂組成物及びその成形フィルム
JP2011201983A (ja) * 2010-03-25 2011-10-13 Nitto Denko Corp 表面保護シート用基材および表面保護シート
JP2013245345A (ja) * 2012-05-29 2013-12-09 Mitsui Chemicals Inc オレフィン系重合体組成物および該組成物からなるフィルム
US20140243466A1 (en) * 2013-02-28 2014-08-28 Sabic Innovative Plastics Ip B.V. Wear and friction properties of engineering thermoplastics with ultra-high molecular weight polyethylene
WO2015182448A1 (fr) * 2014-05-30 2015-12-03 東レ株式会社 Film réfléchissant, et unité de rétroéclairage à éclairage périphérique utilisant ce film réfléchissant
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TW201922871A (zh) 2019-06-16
CN111315805B (zh) 2023-04-11
JP7200943B2 (ja) 2023-01-10
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