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WO2008004510A1 - film d'emballage - Google Patents

film d'emballage Download PDF

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Publication number
WO2008004510A1
WO2008004510A1 PCT/JP2007/063212 JP2007063212W WO2008004510A1 WO 2008004510 A1 WO2008004510 A1 WO 2008004510A1 JP 2007063212 W JP2007063212 W JP 2007063212W WO 2008004510 A1 WO2008004510 A1 WO 2008004510A1
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WO
WIPO (PCT)
Prior art keywords
film
layer
lactic acid
polymer
intermediate layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2007/063212
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English (en)
Japanese (ja)
Inventor
Maiko Suzuki
Tomoyuki Nemoto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Chemical Corp
Original Assignee
Mitsubishi Plastics Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Plastics Inc filed Critical Mitsubishi Plastics Inc
Publication of WO2008004510A1 publication Critical patent/WO2008004510A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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

Definitions

  • the present invention is a packaging film mainly containing a lactic acid-based polymer, which is a rosin derived from a natural plant, and can be suitably used as a small wrinkle wrap film particularly used in homes.
  • the present invention relates to a packaging film that can be produced.
  • a so-called “wrap film” (in the present invention, "small film” is used as a packaging film in which cooked food can be easily packaged on a ceramic plate. (Also called “wrap film”).
  • Such a small wrap film is stored in a paper box with a cutter blade wound in a cylinder.
  • the film is drawn out from the paper box to cover the food, and the film is covered. Is pressed against the cutter blade provided in the paper box, the perforated hole is opened in the film with this cutter blade, and the film is cut to cut the film so that the bow I crack propagates in the width direction.
  • the film is generally used so that the end of the film is in close contact with the container. For this reason, in addition to transparency, the small wrap film requires various properties such as adhesion to the container, drawability that allows the film to be pulled out smoothly from the paper box, and cutability when the drawn film is cut. It is said.
  • wrapping films currently on the market in addition to a film mainly composed of a stretched polysalt-vinylidene-based resin, an extruded cast polyethylene-based resin, a plasticized poly-sulphated resin-based resin Examples thereof include films mainly composed of fat and poly 4-methylpentene 1-1 series.
  • Patent Document 1 describes the dynamic viscoelasticity measurement of the JIS K-7198 A method as a biodegradable wrap film that simultaneously has the characteristics of cuts, packaging, and heat resistance, which are the characteristics of household wrap films.
  • the value of the storage elastic modulus at 40 ° C measured at a frequency of 10 Hz and strain of 0.1% is in the range of 100 MPa to 3 GPa, and the value of the storage elastic modulus at 100 ° C is in the range of S30 MPa to 500 MPa.
  • a biodegradable wrap film containing a lactic acid-based rosin composition contained in a proportion as a main component is disclosed.
  • Patent Document 2 discloses that an outermost layer for providing a shrinkable sheet-like material capable of obtaining a high shrinkage rate at a relatively low temperature by an inflation method excellent in productivity is a layer mainly composed of polyolefin-based resin. And a shrinkable sheet-like material having at least one layer mainly composed of polylactic acid (lactic acid-based polymer) between the layers mainly composed of the polyolefin-based resin is disclosed. It is also disclosed that an adhesive layer made of an acrylic-modified polyethylene-based resin can be interposed between a layer mainly composed of a system resin and a layer composed mainly of a polylactic acid.
  • Patent Document 1 WOZ2005Z082981
  • Patent Document 2 JP 2002-19053 A
  • the present invention is a laminated film composed of at least three layers, wherein both surface layers contain a polyolefin-based polymer (A) as a main component, and the intermediate layer is a lactic acid-based resin. It contains composition (B) as the main component, storage elastic modulus') measured by dynamic viscoelasticity measurement at a frequency of 10 Hz and a temperature of 20 ° C is lGPa to 4 GPa, and the peak temperature of loss tangent (tan ⁇ ) is A packaging film having a peak value in the range of 0.1 to 0.8 at 20 to 70 ° C (preferably 20 to 60 ° C) is proposed.
  • the present invention also provides an adhesive resin between the layer containing the polyolefin polymer (A) as a main component and the layer containing the lactic acid resin composition (B) as a main component.
  • F) is a packaging film having a laminated structure in which a layer containing a main component is present, wherein the adhesive resin (F) is a modified polyolefin resin (fl), soft aromatic carbonization Copolymers of hydrogen and conjugate hydrogen carbonate or hydrogenated derivatives of these copolymers (f 2), ethylene vinyl acetate copolymers (f3) having a vinyl acetate content of 30 to 80% by mass, lactic acid series Lactic acid / acrylic mixed resin (f4) having a polymer and an acrylic block copolymer having a polymer block mainly composed of acrylate units and a polymer block mainly composed of methacrylate units
  • This is a resin that has one or two or more combined forces.
  • film is a thin flat product whose thickness is extremely small compared to the length and width and whose maximum thickness is arbitrarily limited, and is usually supplied in the form of a roll.
  • Japanese Industrial Standards JISK6900 Japanese Industrial Standards JISK6900
  • sheet is defined as a JIS definition. It usually refers to a flat product whose thickness is small instead of length and width.
  • sheet is included. Even when the term “sheet” is used, it includes “film”.
  • the expression "main component” includes the meaning of allowing other components to be contained within a range that does not hinder the function of the main component unless otherwise specified.
  • the content ratio of the main component is not specified, but the main component (when two or more components are main components, the total amount thereof) is 50% by mass or more, preferably 7%. Including the meaning of occupying 0% by mass or more, particularly preferably 80% by mass or more (including 100%).
  • ⁇ ⁇ ⁇ ⁇ '' (X, ⁇ is any number), unless otherwise stated, it means ⁇ X is greater than or equal to ⁇ , '' and ⁇ It is preferably greater than X and smaller than ⁇ '' It also includes meanings.
  • the packaging film as an example of an embodiment of the present invention (hereinafter referred to as “the packaging film”) will be described.
  • the scope of the present invention is not limited to the embodiments described below.
  • the packaging film includes a ⁇ surface layer> containing a polyolefin polymer ( ⁇ ) as a main component and a ⁇ intermediate layer> containing a lactic acid resin composition ( ⁇ ) as a main component. It is a film.
  • the surface layer and the intermediate layer may be directly laminated, or an adhesive layer may be interposed between the surface layer and the intermediate layer. Further, a regeneration layer may be interposed between the surface layer and the adhesive layer or between the intermediate layer and the adhesive layer.
  • the main component of the surface layer on either the inside or outside, or both inside and outside is a polyolefin polymer.
  • polyolefin polymers examples include ethylene polymers, butylene polymers, propylene, propylene polymers such as ethylene propylene copolymers, poly-4-methylpentene, polybutene, ethylene-vinyl acetate copolymers, and the like. Can do. These resins may be one type of the resins listed above, or may be a mixed resin composed of two or more types of resins.
  • Polyolefin thermoplastic elastomers in which ethylene / propylene rubber or the like is dispersed and composited with these polyolefin polymers can also be used.
  • the role of the surface layer that is, blocking of the packaging film, an appropriate balance between slip property and surface adhesiveness, surface properties such as antifogging property, stability of molding process during film formation, Furthermore, considering the role of suppressing the decrease in the molecular weight of the lactic acid-based polymer (C) over time due to hydrolysis, the main component of the surface layer is preferably an ethylene-based polymer.
  • the ethylene polymer may be one ethylene polymer selected from low density polyethylene, linear low density polyethylene, linear ultra low density polyethylene, medium density polyethylene and high density polyethylene, or these 2 polymers.
  • a mixed resin having a combination force of more than one kind or a copolymer mainly composed of ethylene can be mentioned.
  • the ethylene unit content preferably exceeds 50% by mass.
  • low-density polyethylene linear low-density polyethylene, linear ultra-low-density polyethylene, ethylene acetate butyl copolymer, ethylene acrylate copolymer and ethylene-methacrylate copolymer
  • Ethylene polymer or Particularly preferred is a mixed resin having a combination of two or more of these.
  • Examples of the acrylic ester of the ethylene acrylic ester copolymer include methyl acrylate and ethyl acrylate.
  • Examples of the methacrylate ester of the ethylene-methacrylic ester copolymer include methyl methacrylate, Examples thereof include ethyl methacrylate.
  • the content of acetic acid bull is 10 to 60 mass. %, Melt flow rate (hereinafter sometimes abbreviated as “MFR”. MFR measurement conditions are 190 ° C and load 21.18 N based on JIS K 7210, and the same applies to other MFRs.) An ethylene-butyl acetate copolymer having a content of 0.2 to 20 gZlO is particularly preferred.
  • the ethylene acetate butyl copolymer has a butyl acetate content of preferably 10 to 58% by mass, more preferably 12% by mass or more. Further, it is more preferable that it is 56% by mass or less, particularly less than 30% by mass.
  • the MFR of the ethylene acetate butyl copolymer is 0.2 gZlO or more, the extrusion processability is stable. On the other hand, if it is 20 gZlO or less, stable film formation at the time of molding becomes possible, and thickness unevenness, decrease in mechanical strength, variation and the like are reduced, which is preferable. From this point of view, the MFR of the ethylene acetate butyl copolymer is more preferably 0.5 to 18 gZlO, but more preferably 1 to 15 gZlO.
  • the density is 0.
  • linear low density polyethylene having a 90 to 0.95 g / cm 3 and an MFR of 0.2 to 20 g / 10 min.
  • the density of the ethylene-based polymer is within such a range, it has moderate crystallinity. Therefore, the film does not become hard, the flexibility and the elastic recovery are good, and the melting point of the ethylene polymer is higher than the actual use temperature range of the wrap, specifically the ambient temperature when heated in a microwave oven etc. Therefore, when the food is packaged with this packaging film and heated in a microwave oven or the like, there is no problem that the film melts and sticks to the food container or the like.
  • the MFR of the ethylene polymer is 0.2 gZlO or more, the extrusion processability is stable, and if it is 20 gZlO or less, stable film formation is possible at the time of molding, and thickness irregularities and mechanical strength are improved. This is preferable because reduction, variation and the like are reduced. From such a viewpoint, the MFR of the ethylene polymer is preferably 0.5 to 18 gZlO, more preferably 1 to 15 gZl0.
  • the method for producing the ethylene polymer is not particularly limited, and is a known polymerization method using a known polyolefin polymerization catalyst, such as a multi-site catalyst represented by a Ziegler or Natta type catalyst or a meta-site catalyst.
  • a known polyolefin polymerization catalyst such as a multi-site catalyst represented by a Ziegler or Natta type catalyst or a meta-site catalyst. Examples include a slurry polymerization method, a solution polymerization method, a bulk polymerization method, a gas phase polymerization method, a bulk polymerization method using a radical initiator, and a bulk polymerization method using a single site catalyst typified by a mouth-opening catalyst.
  • the lactic acid-based resin composition (B), which is the main component of the intermediate layer, may contain any lactic acid-based polymer (C).
  • lactic acid-based polymer (C) and glycerin fatty acid ester Particularly preferred is a mixture with (D).
  • the lactic acid polymer (C) includes poly (L lactic acid) whose structural unit is L-lactic acid, poly (D lactic acid) whose structural unit is 3 ⁇ 4-lactic acid, poly (DL lactic acid) whose structural unit is SL lactic acid and D-lactic acid. Lactic acid), a mixture thereof, or a copolymer containing these can be used.
  • poly (L-lactic acid) or poly (D lactic acid) here is ideally L-lactic acid or Is a polymer composed of 100% D-lactic acid, and inevitably different lactic acid may be included in the force polymerization, so it contains 98% or more of L-lactic acid or D-lactic acid.
  • the lactic acid-based polymer has low crystallinity. Therefore, polylactic acid having a lower crystallinity than poly (L lactic acid), such as poly (D-D-).
  • the main component is preferably lactic acid), poly (DL lactic acid), or a mixture thereof.
  • the crystallinity of the lactic acid polymer is low, so that bleeding out of a plasticizer or the like can be suppressed.
  • the lactic acid polymer may contain other hydroxycarboxylic acid or the like as a small amount of a copolymer component, or may contain a small amount of a chain extender residue.
  • the polymerization method of the lactic acid-based polymer includes a condensation polymerization method, a ring-opening polymerization method, and other known polymerization methods. The law can be adopted.
  • L-lactic acid or D-lactic acid, or a mixture thereof can be directly subjected to dehydration condensation polymerization to obtain a lactic acid polymer having an arbitrary composition.
  • lactide which is a cyclic dimer of lactic acid
  • lactide which is a cyclic dimer of lactic acid
  • a lactic acid polymer can be obtained.
  • Lactide includes L-lactide, which is a dimer of L-lactic acid, D-lactide, which is a dimer of D-lactic acid, or DL-lactide, which is L-lactic acid and D-lactic acid, and these are mixed as necessary.
  • L-lactide which is a dimer of L-lactic acid
  • D-lactide which is a dimer of D-lactic acid
  • DL-lactide which is L-lactic acid and D-lactic acid
  • the weight average molecular weight of the lactic acid polymer is preferably in the range of 50,000 to 400,000, and more preferably in the range of 100,000 to 250,000. If the weight average molecular weight of the lactic acid-based polymer is 50,000 or more, practical properties such as mechanical properties and heat resistance can be secured, and if it is 400,000 or less, the melt viscosity is too high and the molding processability may be inferior. Absent.
  • the lactic acid polymer used in the packaging film is commercially available!
  • a lactic acid polymer can be used.
  • the product name “Lacia” series (made by Mitsui Engineering Co., Ltd.), the product name “Nature WorksJ series (made by NatureWorks)”, the product name “U'z series” (made by Toyota Motor Corporation), etc. I'll do it.
  • the glycerin fatty acid ester (D) can play a role in plasticizing the lactic acid polymer (C).
  • the type of glycerin fatty acid ester is not particularly limited, and examples thereof include monoglyceride, diglyceride, triglyceride, acetylenic monoglyceride, and polyglycerin fatty acid esters such as diglycerin, triglycerin, and tetraglycerin. Examples include stealth. Among them, acetylene monoglyceride having a molecular structure represented by the following chemical formula (1) is particularly preferable from the viewpoint of good compatibility with a lactic acid polymer and high plasticizing ability.
  • Rl represents an alkyl group
  • R2 and R3 each represent a acetyl group or hydrogen.
  • the number of carbon atoms in these alkyl groups may be appropriately selected so as to achieve the purpose of improving adhesion and flexibility without any particular limitation. In general, 6 to 20 is preferred.
  • the molecular weight of the glycerin fatty acid ester (D) is preferably 2,000 or less, particularly 1,500 or less. It is more preferable.
  • the blending amount of glycerin fatty acid ester (D) is small. Even though it is preferable, glycerin fatty acid ester (D) is added to 100 parts by mass of lactic acid polymer (C). It is even more preferable to mix so as to include 1 to 20 parts by mass, especially 1 to L0 parts by mass, particularly 2 to L0 parts by mass.
  • the amount of glycerin fatty acid ester (D) is not excessively reduced, and The difference in elastic modulus can be reduced along with the fluidity.
  • the processability when coextruding with the front and back layers is improved, and a film having an excellent appearance without striped pattern or whitening can be obtained.
  • the processability when coextruding with the front and back layers is improved, and a film having an excellent appearance without striped pattern or whitening can be obtained.
  • the surface layer for example, the polyolefin polymer ()
  • a wide range of stretching conditions can be set. Therefore, the workability during stretching is also good.
  • the intermediate layer of the packaging film may contain a polyolefin polymer (E) in addition to the lactic acid resin composition (B).
  • the polyolefin polymer (E) may be the same polyolefin polymer as the polyolefin polymer (A) constituting the surface layer or a different polyolefin polymer, but is preferably The same polyolefin polymer should be used.
  • Polyolefin polymer (E) force If it is the same polyolefin polymer as the polyolefin polymer (A) constituting the surface layer, the adhesion between the intermediate layer and the surface layer can be further improved, and the entire film
  • the trimming loss that occurs when trimming the film after cutting both ends of the film can be added as a constituent material of the intermediate layer. It is possible to reduce material costs by eliminating waste.
  • polystyrene resin As the most preferred polyolefin polymer (E), an ethylene polymer can be mentioned, and among them, an ethylene acetate butyl copolymer having a butyl acetate content of 10 to 60% by mass can be mentioned.
  • This ethylene-vinyl acetate copolymer can be suitably used as the polyolefin polymer (A), which is the main component of the surface layer, and is transparent when added with recycled resin that generates trimming loss and other forces.
  • A polyolefin polymer
  • a heat stabilizer In the intermediate layer of the packaging film, a heat stabilizer, an antioxidant, a UV absorber, an anti-blocking agent, a light stabilizer, a nucleating agent, and a hydrolysis inhibitor are provided as long as the effects of the present invention are not impaired. Additives such as deodorants can be added.
  • the calpositimide compound is preferably 0.1 to 3 parts by mass, more preferably 0 to 100 parts by mass of the lactic acid resin composition (B). It is better to increase the weight average molecular weight by blending 5 to 1 parts by mass. Below this range, the effect of increasing the weight average molecular weight is often insignificant. If the range is exceeded, fish eyes and gel may be formed during film formation, which is not preferable.
  • the adhesive layer is composed of modified polyolefin resin (f 1), a copolymer of a soft aromatic hydrocarbon and a conjugated gene hydrocarbon, or a hydrogenated derivative of these copolymers (f 2), Ethylene acetate copolymer (f3) with a vinyl acetate content of 30-80% by mass, lactic acid polymer, polymer block mainly composed of acrylate units and methacrylate unit Lactic acid-acrylic mixed resin (f4) having an acrylic block copolymer having a polymer block, a layer containing adhesive resin (F) as a main component, which has one or two or more combined forces I prefer to be.
  • an adhesive layer by mixing the above-mentioned adhesive resin (F) with another thermoplastic resin.
  • the type and mixing ratio of the resin to be mixed are appropriately determined according to the resin constituting both surface layers and the intermediate layer.
  • the modified polyolefin resin is a resin mainly composed of a polyolefin modified with an unsaturated carboxylic acid or an anhydride thereof, or a modified monomer such as a silane coupling agent.
  • Examples of unsaturated carboxylic acids or anhydrides include acrylic acid, methacrylic acid, and maleic acid. , Maleic anhydride, citraconic acid, citraconic anhydride, itaconic acid, itaconic anhydride, or monoepoxy compounds of these derivatives and ester compounds of the above acids, react with these acids in the molecule And a reaction product of a polymer having a group capable of forming an acid, or a metal salt thereof, each of which can be used alone, or a mixture of two or more of these. Can also be used.
  • maleic anhydride is more preferable among the above.
  • silane coupling agent examples include butyltriethoxysilane and methacryloyloxytrime, which can be used alone or in combination of two or more of them. You can also
  • these modified monomers can be copolymerized in the stage of polymerizing in advance, or these modified monomers can be grafted to the polymer once polymerized. It can also be copolymerized. Of these, graft-modified ones are particularly suitable.
  • these modifying monomers can be used alone or in combination.
  • the content of the modifying monomer is preferably 0.1 to 5% by mass.
  • Copolymers of soft aromatic hydrocarbons and conjugated gen hydrocarbons, or hydrogenated derivatives of these copolymers (f 2) contain rubber components (conjugated gen hydrocarbons), and therefore buffer against stress. Can be imparted, and delamination can be suppressed. In addition, since it contains aromatic hydrocarbons (especially styrene), it has good compatibility with the intermediate layer and can suppress the clouding of the film.
  • the soft aromatic hydrocarbon styrene is preferably used, and styrene analogues such as ⁇ -methylstyrene can also be used.
  • Conjugated hydrocarbons include 1,3 butadiene, 1,2 isoprene, 1,4 isoprene, 1,3 pentagen, etc., which may be hydrogenated derivatives. These may be used alone or in combination of two or more. Can be mixed and used.
  • the content of the soft aromatic hydrocarbon is the mass of the entire copolymer. the 100%, preferably from 5 to 40 mass 0/0, more preferably 7 to 35 mass 0/0, more preferably 10 to 30 mass%. If the content of the soft aromatic hydrocarbon is 5% by mass or more, a good compatibility can be obtained when the recycled film of this packaging film is added to any of the layers. Can be suppressed. On the other hand, if the content of aromatic hydrocarbons is 40% by mass or less, the flexibility is not lowered, and therefore stress generated between the surface layer and the intermediate layer when stress is applied to the film. Because of this buffering action, delamination can be suppressed.
  • a copolymer of a soft aromatic hydrocarbon and a conjugated-gen hydrocarbon or a hydrogenated derivative thereof (f2) a styrene-conjugated conjugated random copolymer, and a styrene-conjugated-conjugated system
  • a hydrogenated derivative of a random copolymer can be preferably used.
  • These copolymers can be used alone or in admixture of two or more.
  • one or more other thermoplastic rosins can be mixed and used.
  • a copolymer of a soft aromatic hydrocarbon and a conjugated gen hydrocarbon or a hydrogenated derivative (f2) thereof can be selected from those having a polar group introduced.
  • the polar groups to be introduced include acid anhydride groups, carboxylic acid groups, carboxylic acid ester groups, strong rubonic acid chloride groups, carboxylic acid amide groups, carboxylic acid groups, sulfonic acid groups, sulfonic acid ester groups, and sulfonic acid chlorides.
  • Copolymers of styrenic compounds introduced with polar groups and conjugation or their hydrogenated caro derivatives include maleic anhydride modified SEBS, maleic anhydride modified SEPS, epoxy Typical examples include modified SEBS and epoxy-modified SEPS.
  • copolymers can be used alone or in admixture of two or more.
  • MFR JISK7210, 190.C, load 21.18N
  • Extrusion processability is stable when the MFR of the conjugated-gene hydrocarbon is 0.8 gZlO or more, and stable film formation is possible at the time of molding if the MFR is 30 gZ10 min or less. This is preferable because there is less down and variation. Therefore, the MFR is preferably 1 to 2 OgZlO.
  • the ethylene acetate butyl copolymer (f3) can further improve the transparency of the packaging film having high transparency among the above-mentioned adhesive resin (F).
  • the ethylene acetate butyl copolymer (f3) preferably has a butyl acetate content of 30 to 80%. If the vinyl acetate content is 30% by mass or more, the crystallinity is low, so the elastic modulus at room temperature is low, surface tackiness is manifested, and the refractive index of the film approaches the middle layer (B) component immediately. Therefore, it is preferable because the transparency is improved. On the other hand, if it is 80% by mass or less, blocking of raw materials does not occur, and handling is not problematic. For these reasons, it is preferred that the butyl acetate content is 30 to 80%, especially 40 to 70%, especially 45 to 60%!
  • the content of the ethylene acetate butyl copolymer in the surface layer is larger than the butyl acetate content. It is preferable to increase the vinyl acetate content of the ethylene acetate butyl copolymer in the adhesive layer.
  • the ethylene acetate butyl copolymer in the surface layer has a vinyl acetate content of 10% by mass or more and less than 30% by mass, and the vinyl acetate content of the ethylene vinyl acetate copolymer in the adhesive layer is 30 to 80% by mass.
  • the film properties such as heat resistance, film strength, bleed-out suppression, film unwinding property, and appearance are kept good. While holding, it is possible to improve the adhesion (delamination at the time of changing) and transparency of each layer, and it is possible to design an advantageous especially as a small wrap film.
  • Lactic acid / acrylic mixed resin (f4) is a lactic acid polymer (C), an acrylic block copolymer having a polymer block mainly composed of acrylate units and a polymer block mainly composed of methacrylate units. It is a mixed resin with the polymer (G).
  • Lactic acid / acrylic mixed resin (f4) contains a lactic acid polymer (C), so it has excellent affinity with the intermediate layer, and also contains an acrylic ester-methacrylic ester copolymer.
  • the viscosity can be adjusted by changing the mixing ratio of the lactic acid polymer (C) and the acrylic block copolymer (G), and the difference in melt viscosity of each layer can be reduced. If the moldability can be improved by reducing the size, it has the characteristics.
  • the lactic acid-based polymer (C) in the lactic acid / acrylic mixed resin (f4) can be used by selecting the same kind of force as the lactic acid-based polymer (C) in the intermediate layer.
  • the lactic acid polymer used in the adhesive layer and the lactic acid polymer in the intermediate layer may be the same or different, and may be different depending on the suitability of each layer. It is recommended to select a lactic acid polymer having a proper composition.
  • the lactic acid-based polymer (C) used for the adhesive layer may contain a copolymer other than lactic acid of any one of L-form, D-form, and DL (racemic) -form.
  • copolymer components include ethylene glycol, propylene glycol, butanediol, decanediol, 1,4-cyclohexanthyl alcohol, neopentyl glycol, glycerin, pentaerythritol, bisphenolanol A, polyethylene glycol, polyethylene glycol, Glycol compounds such as propylene glycol and polytetramethylene glycol, oxalic acid, adipic acid, malonic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, phthalic acid, cyclohexanedicarboxylic acid, Dodecanedioic acid, naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 5-sodium s
  • the acrylic block copolymer (G) has at least one polymer block (gl) mainly composed of acrylate units and at least 1 mainly composed of methacrylate units.
  • the content of the acrylate unit in the polymer block (gl) and the content of the methacrylic acid ester unit in the polymer block ( g 2) are not particularly limited as long as they are the main components. Are preferably in the range of 60 to: LOO% by mass, more preferably in the range of 80 to: LOO% by mass.
  • the polymer block (gl) mainly composed of an acrylate unit is a polymer block mainly composed of an acrylate unit unit, and the acrylate ester that forms the polymer block includes: For example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec butyl acrylate, tert butyl acrylate, amyl acrylate, isoamyl acrylate, acrylic acid n xylyl, cyclohexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, isoborn acrylate, acrylic acid benzyl, benzyl acrylate, phenoloxyl acrylate, acrylic acid 2- Hydrochetyl, 2-methoxyacrylic acid One or a combination of two or more such as
  • the polymer block (g2) mainly composed of the methacrylic acid ester unit is a polymer block mainly composed of a methacrylic acid ester unit, and is a methacrylic acid ester forming the polymer block.
  • the acrylic block copolymer (G) has a polymer block (gl) mainly composed of acrylate units and a polymer block (g2) mainly composed of methacrylic ester units.
  • a triblock copolymer in which the polymer block (g2) is bonded to both ends of the polymer block (gl) is preferable in terms of improving heat resistance and the like.
  • the form of the bond between the polymer block ( g 3) and the polymer block (gl) or the polymer block (g2) is not particularly limited.
  • Examples of monomers constituting the polymer block ( g 3) include olefins such as ethylene, propylene, 1-butene, isobutylene and 1-octene, 1,3 butadiene, isoprene, myrcene and other conjugated genes, styrene, ⁇ -methyl Aromatic butyl compounds such as styrene, ⁇ -methylstyrene, m-methylstyrene, butyl acetate, butylpyridine, acrylo-tolyl, methacrylic tolyl, butyl ketone, butyl chloride, vinylidene fluoride, vinylidene fluoride, acrylamide Methacrylamide, ⁇ -force prolatatone, valerolatatone, and the like.
  • olefins such as ethylene, propylene, 1-butene, isobutylene and 1-octene, 1,3 butadiene, isoprene, myr
  • MFR lactic acid'acrylic mixed resin
  • the effect of the lactic acid / acrylic mixed resin (f4) is not impaired! / In the range, in addition to the lactic acid polymer (C) and the acrylic block copolymer (G), if necessary Other polymers and additives may be included in the adhesive layer.
  • Examples of other polymers that can be blended include polyacrylic rubber, polybutene rubber, polyisobutylene rubber, synthetic rubbers such as EPR and EPDM.
  • Examples of additives include mineral oil softeners such as paraffinic oils and naphthenic oils for improving fluidity at the time of molding; improvement or increase in heat resistance, weather resistance, etc.
  • Inorganic fillers such as calcium carbonate, talc, carbon black, titanium oxide, silica, clay, barium sulfate, magnesium carbonate for purposes such as glass fiber for reinforcement, inorganic fiber or organic fiber such as carbon fiber; heat Stabilizers; antioxidants; light stabilizers; adhesives; tackifiers; plasticizers; antistatic agents; Among these additives, in order to further improve the heat resistance and weather resistance, it is practically preferable to add a thermal stability, an anti-oxidation agent and the like.
  • the method for preparing lactic acid 'acrylic mixed rosin (f4) is not particularly limited.
  • a lactic acid polymer (C) and an acrylic block copolymer (G) may be mixed together with other polymers and additives as described above as necessary.
  • the mixing operation can be carried out using a known mixing or kneading apparatus such as a kneader rudder, an extruder, a mixing roll, a banolly mixer.
  • the temperature during mixing or kneading should be appropriately adjusted according to the melting temperature of the lactic acid polymer (C) or acrylic block copolymer (G), and is usually 110 ° C to 300 ° C. Mix at a temperature within the range.
  • the thickness of the adhesive layer is preferably 0.3 ⁇ m to 5 ⁇ m because of its function. As long as the thickness of the adhesive layer is within the range, the adhesion between the surface layer and the intermediate layer can be expressed. It is preferable because film forming stability is obtained during film forming. When it is desired to further secure the thickness ratio of the intermediate layer, the thickness is more preferably 0.5 ⁇ m to 3 ⁇ m.
  • the following various additives are appropriately added to the surface layer, adhesive layer, and Z or intermediate layer of this packaging film in order to impart performance such as antifogging properties, antistatic properties, slipperiness, and tackiness. Can be combined.
  • an aliphatic alcohol fatty acid ester which is a compound of an aliphatic alcohol having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms and a fatty acid having 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms, specifically
  • Polyethylene glycol At least one of the selected compounds such as sorbitololate, polyethylene glycol sorbitan laurate, and the like, and polyalkylene ether polyols, specifically polyethylene glycol, polypropylene glycol, and also paraffinic oil.
  • One type can be blended in an amount of 0.1 to 12 parts by mass, preferably 1 to 8 parts by mass, based on 100 parts by mass of the resin component constituting each type.
  • the packaging film of the present invention includes the polyolefin polymer (A), the lactic acid resin composition (B), and the adhesive composition (F).
  • a reproduction layer containing can be provided.
  • the reproduction layer can be formed, for example, by using a trimming loss that occurs when the film is trimmed by cutting both ends of the film. Therefore, waste of material can be eliminated and material cost can be reduced.
  • the reproduction layer can be provided between the surface layer and the adhesive layer, or between the intermediate layer and the adhesive layer.
  • a reproduction layer can be provided between the surface layer and the adhesive layer, or between the intermediate layer and the adhesive layer.
  • the layer force to which trimming loss is added is determined depending on whether the surface layer, intermediate layer, or adhesive layer is the surface layer, intermediate layer, or adhesive layer. The mixing ratio of the components can be adjusted.
  • the packaging film may be a laminated film having a surface layer mainly composed of a polyolefin-based polymer (A) and an intermediate layer mainly composed of a lactic acid-based resin composition (B).
  • Other layers hereinafter may be abbreviated as “P layer” as needed, such as improvements in properties and interlayer adhesion, may be introduced as appropriate.
  • P layer a layer having the same composition as that of the surface layer
  • S layer a layer having the same composition as that of the surface layer
  • M layer Layer (hereinafter sometimes abbreviated as “M layer”) force Even if two or more layers are interposed between both surface layers, the force does not matter.
  • a three-layer configuration consisting of (S layer) Z (M layer) Z (S layer), a four-layer configuration consisting of (S layer) Z (P layer) Z (M layer) Z (S layer), (S layer) Z (P layer) Z (M layer) / (P layer) / (S layer), (S layer) / (M layer) / (M layer) / (S layer), etc.
  • a five-layer structure consisting of can be exemplified. In this case, the composition and thickness ratio of each layer may be the same or different! / ⁇ .
  • a laminated film of 5 or more layers having the surface layer Z adhesive layer Z intermediate layer Z adhesive layer Z surface layer in this order can be exemplified.
  • other layers may be appropriately introduced as needed to improve mechanical properties and interlayer adhesion.
  • a reproducing layer can be provided between the surface layer and the adhesive layer, or between the intermediate layer and the adhesive layer.
  • a layer force that has the same compositional power as the surface layer can be applied even if it is interposed other than both surface layers, and two or more layers having the same composition as the intermediate layer are interposed between the two surface layers. It doesn't matter.
  • the surface layer Z adhesive layer Z intermediate layer Z adhesive layer Z surface layer, the surface layer Z adhesive layer Z intermediate layer Z intermediate layer Z adhesive layer Z surface layer, surface layer Z regeneration Layer Z adhesive layer Z intermediate layer Z adhesive layer Z surface layer, surface layer Z adhesive layer Z regeneration layer Z intermediate layer Z adhesive layer 6 layer structure consisting of Z surface layer, surface layer Z adhesive layer Z intermediate layer Z surface layer Z intermediate layer Z adhesive layer Z surface layer, surface layer Z adhesive layer Z intermediate layer Z adhesive layer Z intermediate layer Z adhesive layer Z surface Layer, surface layer Z recycled layer Z adhesive layer Z intermediate layer Z adhesive layer Z recycled layer Z surface layer, surface layer Z adhesive layer Z recycled layer Z intermediate layer Z recycled layer Z adhesive layer Z surface layer, etc. Etc. can be illustrated.
  • the resin composition and thickness consisting of the surface layer Z adhesive layer Z intermediate layer Z adhesive layer Z
  • the thickness ratio of the intermediate layer to the total thickness of the film is 35.
  • the thickness ratio of the intermediate layer is within the effective range, it is easy to design a film that satisfies the above characteristic values (E ', tan ⁇ ) due to the dynamic viscoelasticity. When molding, stable film forming stability is easily obtained. In addition, it is possible to relatively easily impart mechanical properties for expressing a cut property suitable for a wrapping film for food packaging and relaxation properties for expressing adhesiveness of containers. In addition, even when the film formed is stored in a rolled state, blocking does not occur, antifogging properties and container adhesion are improved, and hydrolysis does not easily cause a decrease in molecular weight over time. In addition, a packaging film having good adhesion between the layers can be obtained. Furthermore, when more importance is attached to stable film forming workability and flexibility, the thickness ratio of the intermediate layer to the total film thickness is preferably 35 to 65%, particularly 35 to 60%. Is more preferable.
  • the ratio of the thickness of the intermediate layer to the total film thickness is preferably 60 to 90%, more preferably 65 to 90%.
  • the above thickness ratio should be calculated using the total thickness of all intermediate layers.
  • the thickness (total) of the packaging film is within the range used as a food packaging wrap film, specifically 6 ⁇ m to 30 ⁇ m, and preferably 8 ⁇ m to 20 ⁇ m. m, particularly preferably 10 m to 20 ⁇ m.
  • This packaging film has (1) a storage elastic modulus ( ⁇ ') measured by dynamic viscoelasticity measurement at a frequency of 10 Hz and a temperature of 20 ° C of 1.0 to 4. OGPa, and (2) loss tangent ( The peak temperature of tan ⁇ ) is 0 to 70, preferably 20 to 60, and (3) the peak value is 0.10 to 0.8. It is preferable that the film can be prepared so as to be in the range of 0 and is prepared so as to satisfy all of these conditions (1), (2), and (3).
  • the storage elastic modulus ( ⁇ ') is less than 1. OGPa, the film will be too soft and the stress against deformation will be too small. There is. On the other hand, if E 'exceeds 4. OGPa, the film becomes hard and difficult to stretch, and the pullability when pulled out from the paper box may deteriorate.
  • the peak temperature of tan ⁇ is 70 ° C or less (preferably 20 ° C to 60 ° C) and the peak value is 0.10 or more, the restoring behavior against deformation of the film occurs instantaneously. Therefore, when the film is packaged in a container, the film is not restored in a short time, and the adhesion to the container is preferable. Also, if the peak temperature of tan 8 is 20 ° C or higher and the peak value is 0.80 or lower, plastic deformation will not be exhibited, and this will not cause a problem in normal usage. U, because, preferred.
  • both surface layers are formed with a polyolefin-based polymer (A) as a main component, while an intermediate layer is formed with a lactic acid-based resin composition (B) as a main component.
  • the storage elastic modulus ( ⁇ ') measured by dynamic viscoelasticity measurement at a frequency of 10 Hz and a temperature of 20 ° C is 1.0 GPa to 4.
  • the peak temperature of loss tangent (tan ⁇ ) is 20 to 70 ° C (preferably 20 to 60 o C) in the, to be in the range of the peak value power from 0.10 to 0.80, packaging Finore
  • the conditions required for a small wrap film i.e., transparency, adhesion to the container, paper box strength, the ability to pull out the film smoothly, and the ability to cut the drawn film It is possible to provide a packaging film that can satisfy various conditions such as cut suitability, and can function suitably as a small wrap film.
  • the molecular weight of the lactic acid-based resin composition can be reduced even if the film-formed film is stored in a wound state. It is possible to suppress the blocking of the film, and the problem of the films sticking to each other can be solved.
  • an antifogging agent and the like can be included in both surface layers, so that the antifogging property of the film can be improved.
  • the constituent material of each layer is a mixed composition
  • it is preferable to mix the constituent materials of each layer in advance and, if necessary, pelletize.
  • a mixing method at this time for example, it may be pre-compounded in advance using a twin-screw extruder in the same direction, a kneader, a Hayshell mixer, or the like. You may make it throw into the machine.
  • it is necessary to consider a decrease in molecular weight due to the decomposition of the raw materials, but pre-compounding is preferable for uniform mixing.
  • a lactic acid polymer and additives as necessary are sufficiently dried to remove moisture, and then melt-mixed using a twin-screw extruder and plasticized from a vent port.
  • a pellet may be produced by extruding into a strand shape while adding a predetermined amount of the agent.
  • constituent materials for each layer may be separately put into an extruder, melt extruded, and coextruded by T-die molding or inflation molding to be laminated.
  • the melt-extruded sheet is used as a cooling roll. Therefore, after cooling and solidification, it is heated below the crystallization temperature of the resin, and using the speed difference between the nip rolls, the film is stretched 1.2 to 5.0 times in the machine direction, or the film is stretched. It is preferable to adopt a flat stretching method in which biaxial stretching and Z or simultaneous biaxial stretching are performed in the longitudinal and lateral directions by 1.2 to 5.0 times.
  • the temperature of the extruded sheet is preferably set in the range of 30 to 90 ° C, and more preferably in the range of 40 to 60 ° C.
  • both the lactic acid resin composition (B) of the intermediate layer and the polyolefin polymer (A) of the surface layer can be made close to the elastic modulus suitable for stretching.
  • the draw ratio is preferably in the range of 1.2 to 5.0 times, and more preferably in the range of 1.5 to 4.0 times. As long as the draw ratio is within the effective range, the cut property can be improved without causing troubles such as breakage and whitening of the extruded sheet.
  • the film thus obtained can be subjected to longitudinal stretching between heating rolls as necessary, in accordance with the purposes such as reduction of heat shrinkage rate and natural shrinkage rate, suppression of occurrence of width shrinkage, and the like. Even heat treatment such as heat setting and aging.
  • the heat treatment temperature in the range of 40 to 100 ° C, and even more preferably in the range of 60 to 90 ° C. If the heat treatment temperature is 40 ° C or higher, the effect of the heat treatment can be sufficiently obtained, and if it is 100 ° C or lower, there will be no formability problems such as stickiness of the film on the roll.
  • MD longitudinal direction
  • TD lateral direction
  • the film was measured from 50 ° C to 150 ° C in the transverse direction (TD) at a vibration frequency of 10Hz, a strain of 0.1%, and a heating rate of 1 ° CZ.
  • the obtained storage modulus ( ⁇ ′) at a temperature of 20 ° C., the peak temperature of the loss tangent (tan ⁇ ) and its peak value were determined.
  • the obtained film was allowed to stand for 1 month in a constant temperature and humidity machine LH-112 manufactured by Tabay Espec adjusted to 40 ° C. ⁇ 90% by weight.
  • the weight average molecular weight of the film before and after the test was measured using a gel permeation chromatography HLS-8120GPC manufactured by Tosoh Corporation and a Shim-Pack series GPC-800CP chromatographic column manufactured by Shimadzu Corporation.
  • Solvent chloroform, solution concentration 0.2 wtZvol wt%, solution injection amount 2001, solvent flow rate 1.0 mlZ min, solvent temperature 40 ° C, weight average molecular weight was calculated in terms of polystyrene.
  • the weight average molecular weight of standard positive styrene is 2000000, 670000, 110000, 35 000, 10000, 4000, 600.
  • the molecular weight retention rate (% by weight) was calculated, and the following judgment was made.
  • the molecular weight retention is 60 to: L00% by weight, and the molecular weight after aging is 100,000 or more.
  • the film was formed by the T-die forming method, the stability of casting and the degree of sticking to the roll were observed, and the film forming stability was evaluated according to the following criteria.
  • the obtained roll of film was stored in a temperature-controlled room at a temperature of 43 ° C and a relative humidity of 40% for 5 days, and then the surface condition and rewinding property were observed and evaluated according to the following criteria.
  • ⁇ A level where there is a little blocking between films but no problem in practical use.
  • Adhesion to the container when it was packaged in a bowl-shaped ceramic container with a diameter of 10 cm and a depth of 5 cm was evaluated according to the following criteria.
  • ⁇ Level that can be packaged moderately.
  • ⁇ A level where there is no problem in practical use although the shape of the container is slightly increased.
  • the force of the SUS304 cylinder is affixed to the opening on one side of the SUS304 cylinder, and the opening on the side where the film is not affixed in an ambient temperature of 0-5 ° C
  • the cylindrical end of 30 mm was immersed in water at a water temperature of 20 ° C, and after 1 hour from the start of immersion, the antifogging property was visually observed and evaluated according to the following criteria.
  • ⁇ There are water droplets with a diameter of about lmm in some places.
  • the film-rewinding test of the formed film was performed at a winding speed of 200 mZmin to 600 mZmin, and the suitability for changing the size of the film was evaluated according to the following criteria.
  • ⁇ Can be changed to a small size with no problem at a winding speed of 200mZmin or more and less than 600mZmin.
  • X 200 mZmin or more and less than 600 mZmin During the rewinding, delamination and film breakage occur.
  • the appearance of the film formed was evaluated according to the following criteria.
  • the film formed is excellent in transparency because no striped pattern or whitening of the film due to the difference in fluidity during extrusion of each layer is observed.
  • ⁇ A force for observing a striped pattern caused by a difference in fluidity at the time of extrusion of each layer in the formed film. Whitening of the film is not observed and is at a practical level.
  • the strength when the formed film was peeled off by TD at a test speed of 200 mmZ by the T-type peeling method in an environment of 23 ° C and 50% RH was evaluated according to the following criteria.
  • ⁇ More than 200gZl5mm width and less than 500gZl5mm.
  • ⁇ More than 50gZl5mm width and less than 200gZl5mm.
  • the formed film was placed in a carton box with a metal saw blade, and the film was pulled out and cut.
  • the ease of cutting was evaluated according to the following criteria.
  • ⁇ Level that can be used without a sense of incompatibility when cutting.
  • ⁇ A level where there is no problem in practical use although some resistance is felt during cutting.
  • X At the level where the wrap bites into the metal saw blade and feels excessive resistance when cutting.
  • the film thickness was measured at 12 ⁇ m according to JIS K7105, and the haze value at that time was evaluated according to the following criteria.
  • ⁇ Haze value is less than 1%.
  • Haze value is 1% or more and less than 2%.
  • X Haze value is 2% or more.
  • the ethylene acetate butyl copolymer “LV440” manufactured by Nippon Polyethylene Co., Ltd. as the polyolefin polymer (A) (vinyl acetate content: 15% by mass, MFR: 2.2 gZlO content) ) (Hereinafter abbreviated as “A-1”) and 100 parts by mass of diglycerin monooleate “DGO-1” manufactured by Riken Vitamin Co.
  • A-1 the polyolefin polymer
  • DGO-1 diglycerin monooleate manufactured by Riken Vitamin Co
  • D-1 Riquemar PL019J
  • a packaging film having a total thickness of 12 m was obtained in the same manner as in Example (1-1) except that ⁇ / 9 ⁇ / 1.
  • a layer 1.5 m / 9 mZl. 5 m) packaging film was obtained.
  • Example (1-1) instead of A-1 as the resin composition forming both surface layers and the antifogging agent, the resin composition (C 1 and D-1) forming the intermediate layer and Example (1-1), except that a pre-compound of the same composition was prepared to prepare pellets, and the pellets were put into an extruder for both surface layers to form a substantially single-layer film. ), A packaging film having a total thickness of 12 m was obtained.
  • Example (1-3) except that A-2 was introduced into the extruder for the intermediate layer to make a substantially single layer film, the total thickness was 12 / A zm packaging film was obtained. The results of evaluating the obtained film are shown in Table 1.
  • the films obtained in Examples (1-1) to (1-5) are molecules of packaging films. Decrease over time can be suppressed, and the formed film can be stored in the fresh state. Blocking does not occur even when the film is formed, and antifogging properties and container adhesion are also good. confirmed.
  • Comparative Example (1-1) to Comparative Example (1-4) since the thickness ratio of the intermediate layer to the entire film is low, the storage elastic modulus is defined by the present invention.
  • the content is lower than the range (Comparative Example (1-1)), or when it does not have an intermediate layer mainly composed of a lactic acid-based polymer-based resin composition (Comparative Example (1-3)), blocking, Anti-fogging property and film-forming stability were good.
  • the front and back layers mainly composed of an ethylene-based polymer were not used (Comparative Example (1-2)
  • the container adhesion was good, but the film-forming stability, blocking, and antifogging properties were good.
  • a linear low density polyethylene “NUCG5225” (density: 0.92 g / cm 3 , MFR: 2) manufactured by Nippon Car Co. as a polyolefin polymer (A) is used.
  • OgZlO) (abbreviated as “A-2”) 100 parts by weight of diglycerin monooleate “DGO-1” manufactured by Riken Vitamin Co. The mixture was put into the same direction twin screw extruder set at 200 ° C. and melt kneaded.
  • Admer SE 800 acid-modified polyolefin (hereinafter abbreviated as “F-1”) manufactured by Mitsui Chemicals, Inc. as an adhesive resin (F) was charged into an extruder for an adhesive layer.
  • the resin composition for forming both surface layers melt-kneaded as described above, the resin composition for forming the intermediate layer, and the resin composition for forming both adhesive layers are separately extruded.
  • Z adhesive layer Z surface layer 2 m / 1 ⁇ m / 6 ⁇ m / 1 ⁇ / 2 ⁇ m) was obtained.
  • Modic M545J acid-modified LLDPE
  • Example (2-1) the adhesive resin (F) was added to “bond first” (ethylene ethyl acrylate-glycidyl methacrylate terpolymer) manufactured by Sumitomo Chemical Co., Ltd. (hereinafter referred to as “F-3”).
  • Example (2-3) pre-compounded pellets were introduced into the extruder for the intermediate layer so as to have the same composition as both surface layers of Example (2-1).
  • Table 2 shows the results of evaluating the film obtained to obtain a packaging film with a total thickness of 12 ⁇ m in the same manner as in Reference Example (2-3) except that a single-layer film was used.
  • Example (2-1) and Example (2-2) is the molecular weight of the packaging film. It is possible to prevent the amount from decreasing over time, and even if the formed film is stored in a fresh state, blocking does not occur, and antifogging properties and container adhesion are also good. Was confirmed. In addition, it was confirmed that by providing a specific adhesive layer, a delamination was suppressed and a packaging film excellent in small-size changeability and a good packaging appearance was obtained.
  • ethylene Z epoxy Z alkyl acrylate copolymer which is an acrylic-modified polyethylene resin
  • the thickness ratio of the intermediate layer to the entire film is low, the storage elastic modulus is lower than the range specified in the present invention (Reference Example (2-3)), and the lactic acid polymer-based resin composition. In the case of not having an intermediate layer composed mainly of a product (Reference Example (2-4) had good blocking, anti-fogging properties and film-forming stability, but the container adhesion was insufficient. there were.
  • a linear low density polyethylene “NUCG5225” (density: 0.92 g / cm 3 , MFR: 2) manufactured by Nippon Carre as a polyolefin polymer (A) OgZlO) (abbreviated as “A-2”) and 100 parts by weight of diglycerin monooleate “DGO-1” manufactured by Riken Vitamin as an antifogging agent, and the extrusion set temperature
  • A-2 polyolefin polymer
  • DGO-1 diglycerin monooleate manufactured by Riken Vitamin as an antifogging agent
  • Txtec H styrene-ethylene-ethylene-butadiene block copolymer
  • the resin composition for forming both surface layers melt-kneaded as described above, the resin composition for forming the intermediate layer, and the resin composition for forming both adhesive layers are separately extruded.
  • Z adhesive layer Z surface layer 2 m / 1 ⁇ m / 6 ⁇ m / 1 ⁇ / 2 ⁇ m) was obtained.
  • Example (3-1) the adhesive resin (F) was changed to “Hibler 5125” (styrene butyl isoprene block copolymer) (hereinafter abbreviated as “F-5”) manufactured by Kurarene.
  • a packaging film of m was obtained.
  • “Primalloy A” a mixture of a thermoplastic polyester block copolymer and a styrene ethylene butadiene block copolymer
  • Example (3-4) the total thickness (surface layer Z adhesive layer was the same as Example (3-4) except that adhesive resin (F) was changed to “F-5J”.
  • Z intermediate layer Z adhesive layer Z surface layer 2 ⁇ m / 1 ⁇ m / 6 ⁇ m / 1 ⁇ / 2 ⁇ m) was obtained.
  • Example (3-1) the addition amount of glycerin fatty acid ester (D-1) contained in the resin composition forming the intermediate layer is set to the sum of C 2 and C 3 (100 parts by mass).
  • the film was stretched uniaxially to MD by roll stretching at a stretching temperature of 60 ° C, a heat treatment temperature of 90 ° C, and a stretching ratio of 3 times to obtain a packaging film having a thickness of 12 ⁇ m.
  • Example (3-3) pellets pre-compounded so as to have the same composition as both surface layers of Example (3-1) were put into the extruder for the intermediate layer.
  • Table 3 shows the results of evaluating the film obtained to obtain a packaging film with a total thickness of 12 ⁇ m in the same manner as in Reference Example (3-3) except that a single-layer film was used.
  • Reference Example (3-1) to Reference Example (3-4) as an adhesive layer between the front and back layers and the intermediate layer, ethylene Z epoxy Z alkyl atrelay, which is an acrylic-modified polyethylene resin, is used. If the copolymer is used, the suitability and transparency are not sufficient (Reference Example (3-1)), or because there is no adhesive layer, the suitability is not sufficient ( Reference example (3-2) (3-3)) was confirmed. Further, since the thickness ratio of the intermediate layer to the entire film is low, the storage elastic modulus is lower than the range specified in the present invention (Reference Example (3-3)), or the lactic acid-based polymer-based resin composition is used. In the case of having no intermediate layer as the main component (Reference Example (3-4)), blocking, anti-fogging and film-forming stability were good, but container adhesion was insufficient. .
  • Example (3-4) to (3-7) the blending amount of glycerin fatty acid ester (D) with respect to 100 parts by mass of lactic acid polymer (C) is 10 parts by mass or less, and the film appearance It was an excellent aspect in terms of workability.
  • Example (3-7) was excellent in stretch processability and excellent in cutability.
  • a linear low density polyethylene “NUCG5225” (density: 0.92 g / cm 3 , MFR: 2) manufactured by Nippon Carre as a polyolefin polymer (A) OgZlO) (abbreviated as “A-2”) and 100 parts by weight of diglycerin monooleate “DGO-1” manufactured by Riken Vitamin as an antifogging agent, and the extrusion set temperature
  • A-2 polyolefin polymer
  • DGO-1 diglycerin monooleate manufactured by Riken Vitamin as an antifogging agent
  • D-1 acetylenic monodallylide
  • the resin composition for forming both surface layers melt-kneaded as described above, the resin composition for forming the intermediate layer, and the resin composition for forming both adhesive layers are separately extruded.
  • Z adhesive layer Z surface layer 2 m / 1 ⁇ m / 6 ⁇ m / 1 ⁇ / 2 ⁇ m) was obtained.
  • Ebaslen 630 vinyl acetate content: 60% by mass
  • LV440 vinyl acetate content: 15% by mass, MFR: 2.2 g ZlO, manufactured by Nippon Polyethylene Co., Ltd.
  • Example (4-4) the total thickness (surface layer Z adhesive layer Z intermediate layer) was the same as Example (4 4) except that adhesive resin (F) was changed to “F-8” above.
  • Z adhesive layer Z surface layer 2 ⁇ m / 1 ⁇ m / 6 ⁇ m / 1 ⁇ m / 2 ⁇ m) was obtained.
  • Example (4-5) the total thickness (surface layer Z adhesive layer Z intermediate) was the same as in Example (4 5) except that the polyolefin polymer (A) was changed to “A-1”.
  • Layer Z adhesive layer Z surface layer 2 m / 1 ⁇ m / 6 ⁇ m / 1 ⁇ m / 2 ⁇ m) was obtained. The results of evaluating the obtained film are shown in Table 4.
  • Example (4-1) the adhesive resin (F) was replaced with “bond first” (ethylene ethyl acrylate daricidyl methacrylate terpolymer) (“F-3”) manufactured by Sumitomo Chemical Co., Ltd.
  • Example (4-1) pellets pre-compounded in advance so as to have the same composition as the intermediate layer in Example (4-1) were introduced into the adhesive layer extruder, and the three-layer film was substantially substantiated.
  • the films obtained in Examples (41) to (48) can suppress the molecular weight of the packaging film from decreasing over time, and the film formed film is covered. It was confirmed that blocking did not occur even when stored at 1, and that the antifogging property and container adhesion were also good. In addition, it was confirmed that by providing a specific adhesive layer, delamination was suppressed, and a packaging film excellent in refillability was obtained, and a packaging film excellent in transparency was obtained.
  • Example (4-4) When the intermediate layer was not included (Reference Example (4-4)), the blocking, antifogging property and film-forming stability were good, but the container adhesion was insufficient.
  • the blending amount of dalycerin fatty acid ester (D) with respect to 100 parts by mass of lactic acid polymer (C) is 10 parts by mass or less, and the film appearance is excellent. Therefore, it was an excellent aspect in terms of workability.
  • Example (48) was excellent in stretch processability and excellent in cutability.
  • a linear low density polyethylene “NUCG5225” (density: 0.92 g / cm 3 , MFR: 2) manufactured by Nippon Carre as a polyolefin polymer (A) OgZlO) (abbreviated as “A-2”) and 100 parts by weight of diglycerin monooleate “DGO-1” manufactured by Riken Vitamin as an antifogging agent, and the extrusion set temperature
  • A-2 polyolefin polymer
  • DGO-1 diglycerin monooleate manufactured by Riken Vitamin as an antifogging agent
  • D glycerin fatty acid ester
  • the adhesive layer extruder is fed with a lactic acid polymer (C), an n-butyl acrylate (PnBA) block (gl), and a methyl methacrylate polymer (F).
  • the resin composition for forming both surface layers melt-kneaded as described above, the resin composition for forming the intermediate layer, and the resin composition for forming both adhesive layers are separately extruded.
  • Z adhesive layer Z surface layer 2 m / 1 ⁇ m / 6 ⁇ m / 1 ⁇ / 2 ⁇ m) was obtained.
  • Example (5-1) the adhesive resin (F), lactic acid polymer (C), acrylic acid n-butyl polymer (PnBA) block (gl), and methyl methacrylate polymer were used.
  • Example (5-3) pellets pre-compounded to the same composition as both surface layers of Example (5-1) were added to the extruder for the intermediate layer.
  • Table 5 shows the results of evaluating the film obtained to obtain a packaging film with a total thickness of 12 ⁇ m in the same manner as in Reference Example (5-3) except that a single-layer film was used.
  • Example 5 From Table 5, the film obtained in Example (5-1) and Example (5-2) is the molecular weight of the packaging film. It is possible to prevent the amount from decreasing over time, and even if the formed film is stored in a fresh state, blocking does not occur, and antifogging properties and container adhesion are also good. Was confirmed. In addition, it was confirmed that by providing a specific adhesive layer, delamination was suppressed and the packaging film was excellent in changeability, and the appearance of the film was also improved.
  • the adhesive layer between the front and back layers and the intermediate layer is an acrylic-modified polyethylene-based resin, such as ethylene Z epoxy Z alkyl atari.
  • an acrylic-modified polyethylene-based resin such as ethylene Z epoxy Z alkyl atari.

Landscapes

  • Laminated Bodies (AREA)
  • Wrappers (AREA)

Abstract

L'invention concerne un film d'emballage fabriqué en utilisant un acide polylactique comme un des matériaux bruts principaux, qui peut fonctionner de façon particulièrement favorable en tant que petit rouleau de film d'emballage, qui ne souffre pas de blocages même lorsqu'il est stocké à l'état enroulé et qui ne se délamine pas même lorsqu'il est réenroulé en un petit rouleau. Un film d'emballage constitué d'un film stratifié qui comprend cinq couches essentielles, à savoir une couche de surface, une couche de liaison, une couche intermédiaire, une autre couche de liaison et une autre couche de surface, dans cet ordre, les deux couches de surface comprenant un polymère de polyoléfine (A) comme composant principal, la couche intermédiaire comprenant une composition de résine d'acide polylactique (B) comme composant principal et les deux couches de liaison comprenant une résine de polyoléfine modifiée (F) comme composant principal.
PCT/JP2007/063212 2006-07-03 2007-07-02 film d'emballage Ceased WO2008004510A1 (fr)

Applications Claiming Priority (14)

Application Number Priority Date Filing Date Title
JP2006-183319 2006-07-03
JP2006183319 2006-07-03
JP2006195889 2006-07-18
JP2006-195889 2006-07-18
JP2006195888 2006-07-18
JP2006195887 2006-07-18
JP2006-195888 2006-07-18
JP2006-195887 2006-07-18
JP2007049109 2007-02-28
JP2007-049109 2007-02-28
JP2007-049108 2007-02-28
JP2007049108 2007-02-28
JP2007-064047 2007-03-13
JP2007064047 2007-03-13

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WO2008004510A1 true WO2008004510A1 (fr) 2008-01-10

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JP2010125671A (ja) * 2008-11-27 2010-06-10 Mitsubishi Plastics Inc 包装用フィルム
JP2010125672A (ja) * 2008-11-27 2010-06-10 Mitsubishi Plastics Inc 包装用フィルム
WO2010084862A1 (fr) 2009-01-20 2010-07-29 三菱樹脂株式会社 Film multicouche
JP2011000770A (ja) * 2009-06-17 2011-01-06 Mitsubishi Plastics Inc 包装用フィルム
EP2246402A4 (fr) * 2008-02-20 2011-02-16 Unitika Ltd Composition de résine, stratifié l'utilisant et corps moulé utilisant le stratifié
JP2016007793A (ja) * 2014-06-25 2016-01-18 藤森工業株式会社 積層体
EP2939948A4 (fr) * 2012-12-28 2016-08-10 Mitsubishi Plastics Inc Film d'emballage

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JP2002019053A (ja) * 2000-07-07 2002-01-22 Mitsubishi Plastics Ind Ltd 収縮シート状物
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EP2246402A4 (fr) * 2008-02-20 2011-02-16 Unitika Ltd Composition de résine, stratifié l'utilisant et corps moulé utilisant le stratifié
US8114522B2 (en) 2008-02-20 2012-02-14 Unitika Ltd. Resin composition, laminate using the same, and molded body using the laminate
JP2010125671A (ja) * 2008-11-27 2010-06-10 Mitsubishi Plastics Inc 包装用フィルム
JP2010125672A (ja) * 2008-11-27 2010-06-10 Mitsubishi Plastics Inc 包装用フィルム
WO2010084862A1 (fr) 2009-01-20 2010-07-29 三菱樹脂株式会社 Film multicouche
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JP2011000770A (ja) * 2009-06-17 2011-01-06 Mitsubishi Plastics Inc 包装用フィルム
EP2939948A4 (fr) * 2012-12-28 2016-08-10 Mitsubishi Plastics Inc Film d'emballage
JP2016007793A (ja) * 2014-06-25 2016-01-18 藤森工業株式会社 積層体

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