WO2008001917A1 - Film, film thermorétractable, article moulé utilisant le film thermorétractable, étiquette thermorétractable, et récipient utilisant l'article moulé ou fixé avec l'étiquette - Google Patents

Film, film thermorétractable, article moulé utilisant le film thermorétractable, étiquette thermorétractable, et récipient utilisant l'article moulé ou fixé avec l'étiquette Download PDF

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Publication number
WO2008001917A1
WO2008001917A1 PCT/JP2007/063181 JP2007063181W WO2008001917A1 WO 2008001917 A1 WO2008001917 A1 WO 2008001917A1 JP 2007063181 W JP2007063181 W JP 2007063181W WO 2008001917 A1 WO2008001917 A1 WO 2008001917A1
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WIPO (PCT)
Prior art keywords
film
resin
heat
mass
shrinkable
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PCT/JP2007/063181
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English (en)
Japanese (ja)
Inventor
Takashi Hiruma
Takeyoshi Yamada
Original Assignee
Mitsubishi Plastics, Inc.
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Application filed by Mitsubishi Plastics, Inc. filed Critical Mitsubishi Plastics, Inc.
Priority to JP2008522667A priority Critical patent/JP5302679B2/ja
Publication of WO2008001917A1 publication Critical patent/WO2008001917A1/fr

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Classifications

    • 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
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones

Definitions

  • the present invention uses a film having a low environmental burden and excellent transparency, a heat-shrinkable film, and a molded product using the heat-shrinkable film, a heat-shrinkable label, and the molded product, or It relates to a container equipped with this label.
  • polyolefin resin is preferable because it has a relatively small problem with combustion-generated gases and so-called endocrine disrupting chemical substances that are endocrine disrupting chemicals. It is a material.
  • this heat-shrinkable film made of polyolefin-based resin does not have sufficient shrinkage at the time of heat shrinkage, which is not sufficient for film rigidity and low-temperature shrinkage, and further, spontaneous shrinkage (slightly higher than normal temperature, for example, in summer) There has been a problem that the film tends to shrink slightly before its original use (see, for example, Patent Document 1).
  • polylactic acid-based rosin is also attracting attention as a material with a low environmental impact.
  • Polylactic acid-based resin is a plant-derived resin that uses lactic acid obtained by fermentation of starch as a raw material, and can save fossil resources and suppress emission of carbon dioxide.
  • Polylactic acid based resin is also a material with excellent physical properties such as rigidity and transparency.
  • polylactic acid-based resin has the disadvantage of being brittle.
  • heat-shrinkable films made of polylactic acid-based resin show a sharp change in shrinkage rate with respect to the shrinkage temperature, so there is a problem in terms of shrink finish, such as uniform shrinkage and difficult shrinkage unevenness. (For example, see Patent Documents 2, 3, and 4).
  • a sheet-like material having a polyolefin resin composition comprising a polyolefin resin as a base component, a polylactic acid-based synthetic resin component, and a butyl acetate / ethylene copolymer is described.
  • the present invention is mainly intended to prevent adhesion to the roll surface and maintain biodegradability when processing into a sheet-like material by means of a tool. In this case, there was a problem that transparency and stretchability were still lacking.
  • Patent Document 1 Japanese Patent Laid-Open No. 2003-253008
  • Patent Document 2 Japanese Patent Laid-Open No. 2006-063302
  • Patent Document 3 Japanese Patent Laid-Open No. 2003-205548
  • Patent Document 4 Japanese Patent Laid-Open No. 2001-354786
  • Patent Document 5 JP 2005-68232 A
  • Patent Document 6 JP-A-5-179110
  • Patent Document 7 JP-A-9 316310
  • Patent Document 8 Japanese Patent Laid-Open No. 2003-301077
  • the present invention has been made in view of the above-mentioned problems of the prior art, and an object of the present invention is to provide a film excellent in transparency with less environmental load. [0008] Another object of the present invention is to provide a heat-shrinkable film suitable for applications such as shrink-wrapping, shrink-bound packaging, and shrink-labeling with a low environmental load and excellent shrinkage characteristics and transparency. is there.
  • the present invention provides a molded article, a heat-shrinkable label, and the molded article or heat-shrinkable label using the heat-shrinkable film suitable for applications such as shrink-wrapping, shrink-bound packaging, and shrinkable labels.
  • the heat-shrinkable film suitable for applications such as shrink-wrapping, shrink-bound packaging, and shrinkable labels.
  • the first aspect of the present invention has at least one layer containing a polyolefin-based resin (A) as a main component and containing a polylactic acid-based resin (B) and an acrylic resin (C). It is the film characterized by this.
  • this term is a concept including any of a stretched film, an unstretched film, and a heat-shrinkable film.
  • the polyolefin resin (A) is selected from the group consisting of polyethylene resin, polypropylene resin, ethylene-vinyl acetate copolymer, or a mixed resin thereof. It is preferable that it is some of the oil! /.
  • the content of the polylactic acid-based resin (B) is 10
  • It is preferably 1 part by mass or more and 50 parts by mass or less with respect to 0 part by mass.
  • the content of the acrylic resin (C) is preferably 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the polyolefin resin.
  • the film of the first aspect of the present invention preferably has front and back layers mainly composed of polylactic acid-based resin (B) on both sides.
  • the second invention is a heat-shrinkable film in which the film of the first invention has heat-shrinkability (hereinafter sometimes referred to as "heat-shrinkable film of the invention").
  • the shrinkage rate in at least one direction when immersed in warm water at 80 ° C for 10 seconds is 20% or more.
  • the third aspect of the present invention is a molded article using the heat-shrinkable film of the second aspect of the present invention as a substrate, a heat A shrinkable label, and a container equipped with the molded article and the heat shrinkable label.
  • the first aspect of the present invention it is possible to provide a film with less environmental burden and excellent transparency.
  • the second aspect of the present invention it is possible to provide a heat-shrinkable film having a low environmental load and excellent shrinkage characteristics and transparency.
  • the third aspect of the present invention it can be fixed in a desired position regardless of the shape of the attachment, and has a beautiful appearance free from abnormalities such as wrinkles, occurrence of avatar, insufficient shrinkage, etc.
  • a heat-shrinkable label, a molded product, and a container equipped with a heat-shrinkable label can be provided.
  • the film of the present invention a heat-shrinkable film, a molded article and a heat-shrinkable label using the heat-shrinkable film, and a container equipped with the molded article or the heat-shrinkable label (hereinafter referred to as these Are also referred to as “the molded article of the present invention”, “the label of the present invention”, and “the container of the present invention”).
  • main component is intended to allow other components to be included within a range that does not impede the action and effect of the fat constituting each layer. Further, this term does not limit the specific content, but it is 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass of the total components of each layer. It is a component occupying a range of not less than 100% and not more than 100% by mass.
  • the “main contraction direction” means a direction in which the heat contraction rate is large between the longitudinal direction (longitudinal direction) of the film and the lateral direction (width direction) of the film. In this case, it means a direction corresponding to the outer circumferential direction, and “orthogonal direction” means a direction orthogonal to the main contraction direction.
  • the film of the present invention has at least one layer containing a polyolefin resin (A) as a main component and a polylactic acid resin (B) and an acrylic resin (C).
  • A polyolefin resin
  • B polylactic acid resin
  • C acrylic resin
  • the polyolefin-based resin used as the resin (A) is not particularly limited, but from the viewpoints of heat shrinkage properties, mechanical properties, and moldability, polyethylene-based resin, polypropylene-based resin, ethylene -Use vinyl acetate copolymer or a mixture of these It is preferable. Examples of preferable polyethylene-based resin, polypropylene-based resin, and ethylene-vinyl acetate copolymer used in the present invention are shown below.
  • the density is 0. 94gZcm 3 or 0. 97 gZcm 3 following a high density polyethylene ⁇ (HDPE), density 0. 92gZcm 3 or 0. 94 gZcm 3 Less than medium density polyethylene resin (MDPE), low density polyethylene resin (LDPE) with a density less than 0.92 gZcm 3 and linear low density polyethylene resin (LLDPE).
  • MDPE medium density polyethylene resin
  • LDPE low density polyethylene resin
  • LLDPE linear low density polyethylene resin
  • linear low density polyethylene resin (LLDPE) is particularly preferably used from the viewpoints of stretchability, impact resistance of the film, transparency, and the like.
  • Examples of the linear low-density polyethylene resin include a copolymer of ethylene and a-olefin having 3 to 20 carbon atoms, preferably 4 to 12 carbon atoms.
  • Examples of a-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 3-methyl-1-butene, 4- Examples include methyl-1-pentene. Of these, 1-butene, 1-hexene, and 1-octene are preferably used.
  • copolymerization may be used alone or in combination of two or more.
  • the density of polyethylene ⁇ is 0. 80gZcm 3 or more, preferably 0. 85gZcm 3 or more, preferably 0. 90gZcm 3 above is al, and, 0. 945gZcm 3 or less, preferably 0.9
  • the range is 35 gZcm 3 or less, more preferably 0.925 gZcm 3 or less. If the density is 0.80 g Zcm 3 or more, the waist (rigidity at room temperature) and heat resistance of the entire film will not be remarkably lowered, which is preferable in practical use.
  • the density is 0.945 gZcm 3 or less, the ductility at low temperatures is maintained, and when it is configured as a heat-shrinkable film, it is within the practical temperature range (70 ° C or more and about 90 ° C or less). It is preferable in that it can obtain a sufficient heat shrinkage rate.
  • the melt flow rate (MFR) of polyethylene-based resin is not particularly limited. Usually, MFR (JIS K7210, temperature: 190 ° C, load: 21.18N) force is preferable. 0.5 gZlO min or more, more preferably 1. OgZlO min or more, and preferably 15 gZl0 min or less, more preferably 10 gZl0 min or less. In order to obtain a film having a uniform thickness, it is preferable that the MFR of the polyethylene resin is close to the viscosity at the time of melting of the polylactic acid resin.
  • examples of the polypropylene-based resin include homopropylene resin, random polypropylene resin, block polypropylene resin, and ethylene-propylene rubber. Among them, viewpoints such as stretchability, transparency, and rigidity. Random polypropylene resin is particularly preferably used.
  • the a-olefin to be copolymerized with propylene preferably includes those having 2 to 20 carbon atoms, more preferably 4 to 12 carbon atoms.
  • ethylene 1 Examples include -butene, 1-pentene, 1-hexene, 1-heptene, 1-otaten, 1-nonene, and 1-decene.
  • stretchability, NetsuOsamu contraction characteristics, impact resistance and transparency of the film, from the viewpoint of rigidity a - Orefuin content of E Ji Ren units 2 mass 0/0 to 10 wt% or less
  • the random polypropylene is particularly preferably used.
  • ⁇ -olefins to be copolymerized may be used alone or in combination of two or more.
  • the melt flow rate (MFR) of polypropylene-based resin is not particularly limited, but usually MFR (JIS K7210, temperature: 230 ° C, load: 21.18N) is preferable. Is 0.5 gZlO min or more and 15 gZlO min or less, more preferably 1. OgZlO min or more and lOgZl 0 min or less.
  • MFR JIS K7210, temperature: 230 ° C, load: 21.18N
  • OgZlO min or more and lOgZl 0 min or less For the MFR of polypropylene, it is preferable to select one that is close to the melt viscosity of the polylactic acid-based resin in order to obtain a film of uniform thickness.
  • ethylene acetate bi - Le It is desirable to use a copolymer. If the ethylene unit content is 50 mol% or more, the rigidity of the entire film can be maintained well, which is preferable. On the other hand, if the ethylene unit content is 95 mol% or less, the waist (rigidity at room temperature) and heat resistance of the entire film are not significantly lowered, which is preferable in practice.
  • the melt flow rate (MFR) of the ethylene-butyl acetate copolymer is not particularly limited, but is usually MFR (JIS K7210, temperature: 190 ° C, load: 21.18N) force 0 It is preferable that it is not less than 5 gZlO and not more than 15 gZlO. 1. More preferably, it is not less than OgZlO and not more than lOgZlO.
  • the MFR of the ethylene-vinyl acetate copolymer is close to the viscosity at the time of melting of the polylactic acid resin to select a film with a uniform thickness. It is preferable.
  • the method for producing the resin (A) is not particularly limited.
  • a known polymerization method using a known polyolefin polymerization catalyst such as a multisite represented by a Ziegler-Natta catalyst.
  • Examples include a slurry polymerization method, a solution polymerization method, a bulk polymerization method, a gas phase polymerization method, etc., and a bulk polymerization method using a radical initiator, etc. It is done.
  • the polyolefin resin is a polyethylene resin, for example, trade names "Novatec HD, LD, LLJ” Kernel "" Tuffmer A, P “(manufactured by Nippon Polyethylene),” Cliolex "( Asahi Kasei Chemicals), “Esplen SPO", “Etaselen VL” (Sumitomo Chemical), rEngagej (Dow Chemical) can be used.
  • examples of the polypropylene-based resin include “Novatech PP”, “WINTEC” (manufactured by Nippon Polypro), “Bersifai”, “Notio”, “Tafmer XR” (manufactured by Mitsui Chemicals), “Zeras”, “ Thermorun (Mitsubishi Chemical Co., Ltd.), Sumitomo Noblen, Tough Selenium (Sumitomo Chemical Co., Ltd.), ID EMITSU TPO (Idemitsu Kosan Co., Ltd.), Adflex, Adsyl (San Aromar Co., Ltd.) You can use products that are on the market.
  • ethylene vinyl acetate copolymer for example, commercially available products such as “Evaflex” (manufactured by Mitsui's DuPont Polychemical Co., Ltd.) and “Novatech EVA” (manufactured by Nippon Polyethylene Co., Ltd.) can be used.
  • the polyolefin-based resin (A) may further contain a hydrocarbon resin, and may contain!
  • hydrocarbon resin When hydrocarbon resin is included in polyolefin resin, it suppresses the crystallization of polyolefin resin (for example, polyethylene resin or polypropylene resin) and improves the transparency of the film. If the film can be maintained as a heat-shrinkable film, the heat shrinkability can be improved.
  • the hydrocarbon resin refers to petroleum resin, terpene resin, rosin resin, and the like.
  • petroleum fats and oils include cyclopentagen or alicyclic petroleum fats from dimers thereof and aromatic petroleum fats such as C component.
  • aromatic petroleum fats such as C component.
  • terpene rosin also as terpene rosin
  • rosin-based rosin examples include rosin-based rosin such as gum rosin and wood rosin, and esterified rosin-based rosin modified with glycerin, pentaerythritol and the like.
  • Hydrocarbon oils Is known to exhibit relatively good compatibility when mixed with polyolefin resin, but it is preferable to use a hydrogenated derivative in terms of color tone, thermal stability, and compatibility. Petroleum resin is particularly preferred as partially hydrogenated petroleum resin.
  • Some of the above-mentioned hydrocarbon resins have various softening temperatures depending on the molecular weight.
  • those having a softening temperature of 100 ° C or higher, preferably 110 ° C or higher, and 150 ° C or lower, preferably 140 ° C or lower are suitably used.
  • the softening temperature is 100 ° C. or higher, it is practical and preferable that when mixed, the sheet surface bleeds, causing blocking, and the mechanical strength of the entire sheet is reduced and the sheet is not easily broken.
  • the softening temperature is 150 ° C or lower, good compatibility with polyolefin resin is maintained, and the film surface may bleed over time, leading to blocking and reduced transparency. Is preferred.
  • the content of the above-mentioned hydrocarbon resin is preferably 5% by mass or more, more preferably 8% by mass or more, and still more preferably 10% based on the total amount of polyolefin resin (A) (100% by mass). It is not less than 50% by weight, and is preferably not more than 50% by weight, more preferably not more than 40% by weight, and further preferably not more than 30% by weight.
  • the content of the hydrocarbon resin is 5% by mass or more, when it is configured as a film transparency or heat-shrinkable film, the effect of improving the shrinkage property is remarkable, and 50% by mass. If it is less than the above, it is preferable that problems such as bleeding on the surface over time, the films tend to block each other, and the impact resistance is reduced are less likely to occur.
  • hydrocarbon resin examples include the trade names “Hiretz” (manufactured by Mitsui Chemicals), “Petrosin” (manufactured by Mitsui Chemicals), “Arcon” (manufactured by Arakawa Chemical Industries), Commercially available products such as “Clearon” (manufactured by Yashara Chemical Co., Ltd.), “Imabe” (manufactured by Idemitsu Petrochemical Co., Ltd.), “Escollet” (manufactured by Tonex Co., Ltd.) can be used.
  • the polylactic acid resin in the present invention is a homopolymer of D-lactic acid or L-lactic acid or a copolymer thereof, and a mixture thereof is also included. More specifically, poly (D-lactic acid) whose structural unit is D-lactic acid, poly (L-lactic acid) whose structural unit is L-lactic acid, and copolymerization of L-lactic acid and D-lactic acid.
  • the body is poly (DL-lactic acid), or a mixture thereof.
  • the polylactic acid-based resin used in the present invention is a mixture of D-lactic acid and L-lactic acid
  • Polylactic acid having D-lactic acid alone or L-lactic acid alone has very high crystallinity and tends to have a high melting point and excellent heat resistance and mechanical properties.
  • polylactic acid-based resin can be used by mixing copolymers of D-lactic acid and L-lactic acid having different copolymerization ratios.
  • the average value of the copolymerization ratios of D-lactic acid and L-lactic acid of a plurality of lactic acid polymers may be adjusted so as to fall within the above range.
  • the polylactic acid-based resin used in the present invention may be a copolymer of lactic acid and ⁇ -hydroxycarboxylic acid, aliphatic diol, or aliphatic dicarboxylic acid.
  • ⁇ -hydroxycarboxylic acid copolymerized with lactic acid-based rosin includes optical isomers of lactic acid (D-lactic acid for L-lactic acid and L-lactic acid for D-lactic acid).
  • Glycolic acid 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxy- ⁇ -butyric acid, 2-hydroxy-3,3-dimethylbutyric acid, 2-hydroxy-3-methylbutyric acid, 2- Examples include bifunctional aliphatic hydroxy-carboxylic acids such as methylbutyric acid and 2-hydroxycaprolatatonic acid, and latatones such as prolataton, butyllataton, and normouth rataton.
  • “fats” copolymerized with lactic acid-based rosin examples of the “group diol” include ethylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol and the like.
  • Examples of the “aliphatic dicarboxylic acid” to be copolymerized include succinic acid, adipic acid, suberic acid, sebacic acid, and dodecanedioic acid.
  • the polylactic acid-based resin can be produced by a known polymerization method such as a condensation polymerization method or a ring-opening polymerization method.
  • a condensation polymerization method polylactic acid-based resin having an arbitrary composition can be obtained by directly dehydrating condensation polymerization of D-lactic acid, L-lactic acid, or a mixture thereof.
  • lactide which is a cyclic dimer of lactic acid, has an arbitrary composition by ring-opening polymerization in the presence of a predetermined catalyst, using a polymerization regulator as necessary.
  • a polylactic acid-based rosin can be obtained.
  • the lactide includes DL-lactide, which is a racemic mixture of L-lactic acid and D-lactic acid, and these are mixed as needed to polymerize to form a polylactic acid system having an arbitrary composition and crystallinity. A rosin can be obtained. Further, for the purpose of increasing the molecular weight, a small amount of chain extender, for example, diisocyanate compound, gepoxy compound, acid anhydride, acid chloride and the like may be used.
  • chain extender for example, diisocyanate compound, gepoxy compound, acid anhydride, acid chloride and the like may be used.
  • the weight (mass) average molecular weight of the polylactic acid-based resin is preferably 20,000 or more, more preferably 40,000 or more, still more preferably 60,000 or more, and preferably 400. , 000 or less, more preferred ⁇ is less than 350,000, more preferably ⁇ is less than 300, 000.
  • the weight (mass) average molecular weight is 20,000 or more, an appropriate cohesive strength of the resin can be obtained, and the film can be prevented from being insufficiently stretched or brittle.
  • the weight (mass) average molecular weight is 400,000 or less, the melt viscosity can be lowered, which is preferable from the viewpoint of production and productivity improvement.
  • the content of the polylactic acid-based resin (B) is such that the polylactic acid-based resin (B) is preferably 1 part by mass with respect to 100 parts by mass of the polyolefin-based resin (A). Above, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, and preferably 50 parts by mass or less, more preferably 40 parts by mass or less.
  • the content of the polylactic acid-based resin (B) By setting the content of the polylactic acid-based resin (B) to 50 parts by mass or less, a film having excellent impact resistance and transparency can be obtained.
  • the polylactic acid-based resin (B) By including 1 part by mass or more of the polylactic acid-based resin (B), it can be made into a film with less environmental load, and when it is configured as a heat-shrinkable film, it has excellent heat-shrinkage characteristics, In addition, it is possible to obtain a film in which the natural shrinkage is suppressed.
  • the acrylic resin used in the present invention is a methyl methacrylate homopolymer or a copolymer of methyl methacrylate and another vinyl monomer.
  • the butyl monomer include ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, methacrylic acid phenyl, benzyl methacrylate, methacrylic acid-2-ethyl hexyl, and methacrylic acid-2-hydroxy.
  • Methacrylic acid esters such as ethyl acetate; methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, acrylic acid phenyl, benzyl acrylate, -2-ethylhexyl acrylate, alk Acrylic acid esters such as 2-hydroxyethyl laurate; Unsaturated acids such as methacrylic acid and acrylic acid; Styrene, ⁇ -methylstyrene, acrylonitrile, meta-tri-tolyl, maleic anhydride, phenol-maleimide, cyclo Hexylmaleimide and the like.
  • the copolymer may further contain an elastomer component such as polybutadiene or butadiene / butyl acrylate copolymer, polybutyl acrylate copolymer, a dartal anhydride unit, and a dartalimide unit.
  • an elastomer component such as polybutadiene or butadiene / butyl acrylate copolymer, polybutyl acrylate copolymer, a dartal anhydride unit, and a dartalimide unit.
  • polymethyl methacrylate resin ( ⁇ ) which is a homopolymer of methyl methacrylate, or methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, Copolymers with at least one other bulle monomer selected from ethyl acrylate, butyl acrylate, acrylic acid and methacrylic acid are preferably used.
  • the methyl methacrylate unit is preferably 30% by mass or more, more preferably 40% by mass, and still more preferably 50% by mass or more.
  • the acrylic resin may further contain other monomer units as a copolymerization component as long as the object of the present invention is not impaired.
  • the acrylic resin (C) may contain acrylic elastic particles.
  • the acrylic elastic particle is a particle having an acrylic polymer force and rubber elasticity.
  • the acrylic elastic particles may be a single layer or a multilayer structure acrylic polymer including a rubber elastic layer.
  • a multilayer structure acrylic polymer including a rubber elastic layer is preferably used in that it becomes an acrylic resin film excellent in transparency.
  • the multi-layer structure acrylic polymer is an acrylic polymer having a multi-layer structure of at least two layers, preferably three layers.
  • the inner layer is composed of an alkyl acrylate having an alkyl group having a carbon number of up to 8 and a polyfunctional monoester.
  • Examples thereof include a rubber elastic body made of a copolymer with a monomer, and a two-layer structure acrylic polymer whose outer layer is a hard polymer whose main component is methyl methacrylate.
  • the innermost layer is a hard polymer mainly composed of methyl methacrylate
  • the intermediate layer is a rubber made of a copolymer of an alkyl acrylate ester having 4 to 8 carbon atoms and a polyfunctional monomer.
  • a three-layer acrylic polymer that is an elastic body and whose outermost layer is a hard polymer mainly composed of methyl methacrylate is preferred.
  • a strong multilayer structure acrylic polymer can be produced by a method described in, for example, Japanese Patent Publication No. 55-27576.
  • the acrylic elastic particles are preferably 100 parts by mass or less, more preferably 60 parts by mass or less, based on 100 parts by mass of the acrylic resin (C) serving as a matrix. Setting the acrylic elastic particles to 100 parts by mass or less is preferable because the rigidity and transparency of the film can be maintained.
  • the Vicat soft saddle point of the acrylic resin (C) measured by JIS K7206 is preferably 100 ° C or lower, more preferably 80 ° C or lower, and further preferably 60 ° C or lower.
  • the Vicat softening point being 100 ° C or less, when the mixed resin composed of the resin (A), (B), (C) is stretched, the interface with the polyolefin resin (A) is increased. It is possible to suppress the generation of voids and maintain the transparency of the film, which is preferable.
  • the weight (mass) average molecular weight of the acrylic resin (C) used in the present invention is not less than 20,000, preferably not less than 40,000, more preferably not less than 60,000, It is 400,000 or less, preferably 350,000 or less, more preferably 300,000 or less. If the weight (mass) average molecular weight is 20,000 or more, it is possible to prevent the film from being insufficiently stretched or embrittled. On the other hand, if the weight (mass) average molecular weight is 400,000 or less, the melt viscosity can be lowered, and the viewpoint power for improving production and productivity is also preferable.
  • acrylic resin (C) Commercially available products of the above-mentioned acrylic resin (C) include, for example, "SUMIPEX” (manufactured by Sumitomo Chemical Co., Ltd.), “Ataripet” (manufactured by Mitsubishi Rayon Co., Ltd.), “Parapet” (manufactured by KURARENE), "(Manufactured by Fathuina Japan),” Delpet “(manufactured by Asahi Kasei Corporation) and the like.
  • the content of the acrylic resin (C) is 1 part by mass or more and 50 parts by mass of the acrylic resin (C) with respect to 100 parts by mass of the polyolefin resin (a). More preferably, it is 5 parts by mass or more and 40 parts by mass or less, and further preferably 10 parts by mass or more and 40 parts by mass or less.
  • the content of acrylic resin (C) is 50 parts by mass or less, a film having excellent impact resistance, and a heat-shrinkable film having excellent heat-shrinkability when configured as a heat-shrinkable film. It can be.
  • by including 1 part by mass or more of the acrylic resin (C) it is possible to obtain a film with improved transparency and reduced natural shrinkage.
  • the dispersibility of the polyolefin resin (resin), the polylactic acid resin (resin), and the acrylic resin (C) is improved, and the transparency and mechanical properties are further improved.
  • a compatibilizer can be added to form a thick film.
  • the compatibilizing agent is not particularly limited as long as it improves the dispersibility of the polyolefin-based resin (resin), the polylactic acid-based resin (resin), and the acrylic resin (C).
  • Preferred compatibilizers include ethylene and butyl acetate, acrylic acid, (meth) acrylic acid, ethyl (meth) acrylate, methyl (meth) acrylic acid, maleic anhydride, and (meth) acrylic acid.
  • Glycidilca also has a group power of at least one selected copolymer, such as maleic anhydride-modified SEBS, maleic anhydride-modified SEPS, epoxy-modified SEBS, and epoxy-modified SEPS.
  • examples thereof include modified olefin-based resins modified with unsaturated carboxylic acids or their anhydrides.
  • the compatibilizer may be used alone or in combination of two or more. [0058] Commercially available products of the above-mentioned compatibilizer include, for example, “Bond First”, “Bondyne”, “Aclift” (manufactured by Sumitomo Chemical Co., Ltd.), and “Elvalloy” (Mitsui's DuPont Polychemical Co., Ltd.).
  • the mixing amount of the compatibilizer is preferably 100 parts by mass of the mixed resin composed of polyolefin-based resin (A), polylactic acid-based resin (B), and talyl-based resin (C). 1 part by mass or more, more preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and preferably 30 parts by mass or less, more preferably 25 parts by mass or less, still more preferably 20 parts by mass or less. .
  • the mixing amount of the compatibility additive is 1 part by mass or more with respect to 100 parts by mass of the mixed resin, excellent transparency and impact resistance can be imparted to the film.
  • the content of the compatibilizer is 30 parts by mass or less, the rigidity of the film can be maintained.
  • the film of the present invention comprises, as a main component, the polyolefin-based resin (A), and a polylactic acid-based resin.
  • a layer containing acrylic resin (C) can be used as an intermediate layer, and front and back layers mainly comprising polylactic acid resin (B) can be provided on both sides thereof.
  • a film with better transparency can be obtained by providing a front and back layer mainly composed of polylactic acid-based resin (B).
  • rubber components other than the polylactic acid-based resin can be added to the front and back layers for the purpose of improving the impact resistance of the film.
  • the rubber component is not particularly limited, but aliphatic polyesters other than polylactic acid-based resin, aromatic-aliphatic polyesters, copolymers of diol, dicarboxylic acid, and lactic acid-based resin, and core-shell structure rubber Can be suitably used.
  • the film of the present invention comprises an intermediate layer composed of a mixed resin of a polyolefin resin (A), a polylactic acid resin (B), and an acrylic resin (C) and a polylactic acid resin (B).
  • An adhesive layer may be further provided between the front and back layers as the main component for the purpose of improving adhesiveness.
  • the resin constituting the adhesive layer is not particularly limited as long as it can exhibit adhesiveness, but the resin exemplified in the compatibilizing agent can be suitably used.
  • the thickness ratio of each layer can be appropriately determined in consideration of transparency and the like.
  • a table for the thickness of the entire film The thickness ratio of the back layer (total thickness ratio of the front and back layers) is preferably 10% or more, more preferably 15% or more, still more preferably 20% or more, and preferably 70% or less, more preferably 60% Below, more preferably 50% or less.
  • the adhesive layer preferably has a function of 0.5 ⁇ m or more, more preferably 0.75 ⁇ m or more, still more preferably 1 ⁇ m or more, and preferably 6 ⁇ m or less, more preferably 5 ⁇ m or more. ⁇ m or less.
  • the film of the present invention is within the range that does not significantly impair the effects of the present invention, moldability, productivity and Improved physical properties of heat-shrinkable film 'For the purpose of adjusting, recycled resin that generates trimming loss such as film ears, inorganic particles such as silica, talc, kaolin, calcium carbonate, titanium oxide, carbon black, etc.
  • Additives such as pigments, flame retardants, weather resistance stabilizers, heat resistance stabilizers, antistatic agents, melt viscosity improvers, crosslinking agents, lubricants, nucleating agents, plasticizers and antiaging agents can be added as appropriate.
  • the transparency of the film of the present invention is preferably 20% or less when the film having a thickness of 200 m is measured in accordance with JIS K7105. It is more preferably 15% or less, and even more preferably 10% or less. If the haze value is 20% or less, it can be used in applications that require transparency.
  • the film of the present invention includes an unstretched film, a stretched film, and a heat-shrinkable film. These films can be produced by a known method.
  • the form of the film may be either a flat shape or a tube shape, but the flat shape is preferred from the viewpoint of productivity.
  • a method of cutting a film produced by a tubular method into a flat shape can also be applied. By making it flat, several products can be taken in the width direction of the original film.
  • a method for producing a flat film for example, for an unstretched film, the resin is melted using a plurality of extruders, coextruded from a T die, cooled and solidified with a chilled roll, and then printed.
  • a method of obtaining a roll-shaped unstretched film by performing corona discharge treatment on the surface and then winding it with a winder is Using a plurality of extruders, the resin is melted, co-extruded from a T-die, cooled and solidified with chilled rolls, stretched in the machine direction, Z or transverse direction, annealed to promote crystallization of the resin, and printed.
  • a roll-shaped stretched film is obtained by winding with a winder. The method for producing the heat-shrinkable film will be described later.
  • the film of the present invention is a non-stretched film for use as a heat-shrinkable film, which will be described later, for food packaging, agriculture, horticulture, architectural civil engineering and the like, and stretched film. It can be used for applications such as PET bottle labels, shrink tubes, food packaging, and agriculture.
  • the heat-shrinkable film of the present invention is one in which the above-described film of the present invention has heat-shrinkability.
  • the heat shrinkability can be imparted, for example, by stretching in a predetermined temperature range and then cooling while regulating crystallization.
  • the heat-shrinkable film of the present invention is composed of a mixed resin of the polyolefin resin (A), polylactic acid resin (B), and acrylic resin (C), like the film of the present invention.
  • the layer can be an intermediate layer, and front and back layers mainly composed of polylactic acid-based resin (B) can be provided on both sides thereof.
  • front and back layers mainly composed of the polylactic acid-based rosin (B) it is possible to obtain a heat-shrinkable film having better transparency, heat-shrinkage characteristics and reduced natural shrinkage. In that case, the thickness ratio of each layer can be in the same range as the film.
  • the heat-shrinkable laminate is particularly suitable for applications such as shrink-wrapping, shrink-bound packaging and shrink-labeling, which are particularly excellent in heat-shrinkability and transparency and have reduced spontaneous shrinkage. You can get a finale well.
  • the front and back layers are provided, the front and back layers are provided for the purpose of improving the impact resistance of the film within the range without impairing the shrinkage characteristics and the rigidity (back strength) of the film as in the case of the film. It is also possible to add other rubber components other than polylactic acid-based rosin.
  • an intermediate layer composed of a mixed resin of polyolefin-based resin (A), polylactic acid-based resin (B), and acrylic-based resin (C) and front and back layers mainly composed of polylactic acid-based resin (B)
  • an adhesive layer can be provided with the same material and thickness as the above film.
  • the heat-shrinkable film of the present invention is formed within a range that does not significantly impair the effects of the present invention, in addition to the components described above, with respect to any one layer or two or more layers.
  • recycled particles such as trimming loss such as film ears are generated, and inorganic particles such as silica, talc, force oline, calcium carbonate, etc.
  • Additives such as pigments such as titanium oxide and carbon black, flame retardants, weather resistance stabilizers, heat stabilizers, antistatic agents, melt viscosity improvers, cross-linking agents, lubricants, nucleating agents, plasticizers and anti-aging agents It can be added as appropriate.
  • the heat-shrinkable film of the present invention preferably has a heat shrinkage rate of at least 20% in at least one direction when immersed in warm water at 80 ° C. for 10 seconds.
  • shrinkage rate required for heat-shrinkable films applied to PET bottle shrink label applications varies depending on the shape, but is generally about 20% to 70%.
  • the shrinkage processing machine that is most commonly used industrially for label mounting of PET bottles is generally called a steam shrinker that uses steam as a heating medium for shrinking.
  • a heat-shrinkable film must be sufficiently heat-shrinked at a temperature as low as possible from the viewpoint of the influence of heat on the object to be coated.
  • a film having a heat shrinkage rate of 20% or more under the above conditions is preferable because it can sufficiently adhere to the object to be coated within the shrinkage processing time.
  • the thermal shrinkage rate when immersed in warm water at 80 ° C for 10 seconds is preferably at least 20%, more preferably at least 30%, and more preferably at least in one direction and usually in the main shrinkage direction.
  • the upper limit is preferably not more than 85%, more preferably not more than 80%, and still more preferably not more than 75%.
  • the "main shrinkage direction” means a direction having a large heat shrinkage ratio in the longitudinal direction (longitudinal direction) and the transverse direction (width direction).
  • the “orthogonal direction” means a direction orthogonal to the main contraction direction. Also this specification In the examples of the document, the take-up (flow) direction of the laminated film and the direction perpendicular thereto are the same as the “orthogonal direction” and the “main shrinkage direction”, respectively.
  • the composition of the rosin is adjusted as described above.
  • the thermal shrinkage rate is further increased, the composition ratio of the polylactic acid-based resin (B) constituting the film is increased, the stretching ratio is increased, the stretching temperature is decreased, the polyolefin-based resin Means such as providing front and back layers mainly composed of (A) may be used.
  • the heat shrinkable film of the present invention has as small a natural shrinkage rate as possible, and the natural shrinkage rate when stored for 7 days in an environment of 40 ° C and 50% RH is less than 10%. More preferably, it is 8% or less, more preferably 6% or less, and most preferably less than 3%. If the natural shrinkage rate under the above conditions is less than 10%, even if the produced film is stored for a long period of time, it can be stably attached to a container or the like, and practical problems are unlikely to occur.
  • the transparency of the heat-shrinkable film of the present invention is such that the thickness is used in applications where transparency is required, for example, applications where the printed surface printed on the back surface of the heat-shrinkable film is visually recognized.
  • the haze value is preferably 10% or less, more preferably 7% or less, and even more preferably 5% or less. If the haze value is 10% or less, the transparency of the film can be obtained and a display effect can be achieved.
  • the impact resistance of the heat-shrinkable film of the present invention is evaluated by the tensile elongation at break, and the environment at 0 ° C
  • the elongation force in the take-off (flow) direction (MD) of the heat-shrinkable film is preferably 100% or more, more preferably 150% or more, and even more preferably 200% or more. If the tensile elongation at break in an environment of 0 ° C is 100% or more, it is preferable that problems such as breakage of the heat-shrinkable film during the process of printing and bag making are less likely to occur. Further, even when the tension to be applied to the heat-shrinkable film increases as the speed of the process such as printing and bag-making increases, it is preferable that the tensile breaking elongation is 100% or more, which makes it difficult to break.
  • the rosin composition is configured as described in the present invention. More specific adjustment methods include, for example, reducing the ratio of polylactic acid-based resin (B) and acrylic-based resin (C) constituting the heat-shrinkable film.
  • the heat-shrinkable film of the present invention has a tensile modulus measured in accordance with JIS K7127 in a direction orthogonal to the main shrinkage direction of the film of 1200 MPa or more, preferably 1300 MPa, more preferably 1400MPa or more.
  • the upper limit value of the tensile modulus of heat shrinkable film that is usually used is about 3000 MPa, preferably about 2900 MPa, and more preferably about 2800 MPa.
  • the waist as a whole film (rigidity at room temperature) is high.
  • bags are made in containers such as PET bottles.
  • the tensile modulus can be measured under the condition of 23 ° C according to JIS K7127.
  • the heat-shrinkable film of the present invention can be produced by a known method.
  • the heat-shrinkable film may be flat or tube-shaped, but it can be printed on the inner surface and productivity (a few products can be taken in the width direction of the original film). A planar shape is preferred.
  • the resin is melted using a plurality of extruders, co-extruded from a T-die, cooled and solidified with a chilled roll, roll-stretched in the vertical direction, Tenter stretching in the direction, annealing, and crystallization of rosin Cool under the conditions that can be regulated, wind up with a winder (with corona discharge treatment on the surface if printing is performed), and take a predetermined length (usually 1000 m or more, preferably A method for producing a heat-shrinkable film roll having a length of 2000 mm or more, more preferably 3000 m or more, and the same shall apply hereinafter.
  • a method of cutting a film produced by a tubular method into a flat shape can be applied.
  • the stretch ratio is preferably 2 times or more, more preferably 3 times or more, and preferably 10 times or less, more preferably in the machine direction in applications where shrinkage is performed in two directions, such as for overlap. Is 6 times or less, and the transverse direction is preferably 2 times or more, more preferably 3 times or more, and preferably 10 times or less, more preferably 6 times or less.
  • the direction corresponding to the main shrinkage direction is preferably 2 to 10 times, more preferably 4 to 8 times, and the direction perpendicular thereto is preferably 1 to 2 times (referred to when the film is not stretched), more preferably 1.
  • a ratio is selected.
  • a biaxially stretched film stretched at a stretch ratio within the above range does not have an excessively large thermal shrinkage rate in a direction perpendicular to the main shrinkage direction.
  • the height of the container when mounted on the container. V is preferred because the film can be shrunk in the direction V.
  • the stretching temperature is a force that needs to be changed depending on the glass transition temperature of the resin used and the properties required for the heat-shrinkable film.
  • the stretching temperature is 50 ° C or higher, preferably 60 ° C or higher. It is controlled within a range of C or lower, preferably 110 ° C or lower.
  • the stretched film is subjected to heat treatment or relaxation treatment at a temperature of about 50 ° C or more and about 100 ° C or less for the purpose of reducing the natural shrinkage rate or improving the heat shrinkage property, if necessary.
  • the molecular orientation is not relaxed! It cools quickly in time and becomes a heat-shrinkable film.
  • the heat-shrinkable film of the present invention may be subjected to surface treatment and surface treatment such as corona treatment, printing, coating, and vapor deposition, as well as bag making and perforation using various solvents and heat sealing, as necessary. Can be applied.
  • surface treatment and surface treatment such as corona treatment, printing, coating, and vapor deposition, as well as bag making and perforation using various solvents and heat sealing, as necessary. Can be applied.
  • the heat-shrinkable film of the present invention is processed into a cylindrical shape with a flat force by a package, and is provided for packaging. If you need to print on a cylindrical container such as a plastic bottle, Print the required image on one side of a wide flat film wound on a roll, and cut it to the required width and fold it so that the printed side is inside. It may be formed in a cylindrical shape by attaching an envelope.
  • a center sealing method an organic solvent bonding method, a heat sealing method, an adhesive method, and an impulse sealer method can be considered. Of these, an adhesion method using an organic solvent is preferably used from the viewpoint of productivity and appearance.
  • the heat-shrinkable film of the present invention is excellent in low-temperature shrinkage, shrinkage finish, transparency, natural shrinkage, etc. of the film, so that its use is not particularly limited.
  • a vapor deposition layer and other functional layers it can be used as various molded products such as bottles (blow bottles), trays, lunch boxes, prepared food containers, and dairy products containers.
  • the heat-shrinkable film of the present invention when used as a heat-shrinkable label for food containers (for example, PET bottles, glass bottles, preferably PET bottles for soft drinks or foods), the shape is complicated (for example, the center is Even if it is a constricted cylinder, a square column with a corner, a pentagonal column, a hexagonal column, etc., it can adhere to the shape, and a container with a beautiful label without any fluttering can be obtained.
  • the molded article and container of the present invention can be produced by using a normal molding method.
  • the heat-shrinkable film of the present invention has excellent shrinkage characteristics and shrinkage finishing properties, in addition to the heat-shrinkable label material of a plastic molded product that deforms when heated to a high temperature,
  • a material whose water absorption is very different from the heat-shrinkable film of the present invention for example, a polyolefin resin such as metal, porcelain, glass, paper, polyethylene, polypropylene, polybutene, polymethacrylate ester resin, polycarbonate resin
  • it can be suitably used as a heat-shrinkable label material for a package (container) using at least one selected from polyester-based resin such as polyethylene terephthalate and polybutylene terephthalate, and polyamide-based resin as a constituent material.
  • HIPS rubber-modified impact polystyrene
  • HIPS rubber-modified impact polystyrene
  • Styrene Butyl Atalylate Copolymer Styrene One Attorney Port Toly
  • the film take-up (flow) direction is described as MD
  • TD perpendicular direction
  • A-2 Ube Industries LLDPE UMERI T0540F (MFR4.0, Tml03 ° C)
  • A- 3 Hydrogenated petroleum resin made by Arakawa Chemical Co., Ltd. Alcon P140 (Soft point 90 ° C)
  • EVA Novatec EVA LV430 (MFR1.0, Tm: 89 ° C, manufactured by Japan Polyethylene Corporation)
  • B- l Polylactic acid manufactured by NatureWorks LLC (NatureWorks 4060D)
  • E-1 Modified PO Admer SE800 manufactured by Mitsui Chemicals
  • E-2 Mitsui DuPont Polychemical EMA Elvalloy AC1242
  • the film was cut to a size of MD 1 OOmm and TD 100mm from the obtained heat-shrinkable film roll, immersed in a hot water bath at 80 ° C for 10 seconds, and the shrinkage was measured.
  • the ratio of shrinkage to the original size before shrinkage is expressed in% for MD and TD.
  • the film was cut to a size of MD 100mm and TD 1000mm from the obtained heat-shrinkable film roll, left in a thermostatic chamber at 40 ° C and 50% RH for 7 days, and shrunk in the main shrink direction (TD).
  • the amount of shrinkage relative to the previous original size was measured, the ratio was calculated as a% value, and evaluated according to the following criteria.
  • the haze value of a film having a thickness of 40 / z m was measured in accordance with JIS K7105. Measurement results were evaluated according to the following criteria.
  • Haze value is 5% or more and less than 10%
  • tensile fracture elongation was measured in the direction (MD) perpendicular to the main shrinkage direction of the film under the conditions of type 1 test piece, temperature 0 ° C, test speed lOOmmZ. The measurement results were evaluated according to the following criteria.
  • Tensile breaking elongation is 200% or more
  • Tensile elongation at break is 100% or more and less than 200%
  • a film printed with a grid of 10 mm intervals was cut into a size of MD100 mm XTD298 mm, and both ends of the TD were overlapped 10 mm and heat-sealed with a heat sealer to produce a cylindrical film.
  • This cylindrical film is attached to a cylindrical PET bottle with a capacity of 1.5 L, and it is allowed to pass in about 8 seconds without rotating through a steam tunnel with a length of 3.2 m (3 zones). It was.
  • the tunnel ambient temperature in each zone was set in the range of 75 to 95 ° C by adjusting the amount of steam with a steam valve. After film coating, the following criteria were evaluated.
  • Polyolefin resin, polylactic acid resin, acrylic resin, and other resins and additives shown in Table 1 are put into a twin-screw extruder manufactured by Toshiba Machine Co., Ltd. and melted at a set temperature of 200 ° C. After mixing, the sheet was extruded from a single layer or laminated T-die, taken up with a cast roll at 50 ° C., and cooled and solidified to obtain an unstretched sheet having a width of 300 mm and a thickness of 150 m.
  • the laminated film of Example 3 is a back layer (40 ⁇ m) Z core layer (70 ⁇ m) Z surface layer (40 ⁇ m), and the laminated film of Example 4 is a back layer (40 ⁇ m) Z Adhesive layer (10 m) Z core layer (50 ⁇ m) Z adhesive layer (10 m) Z surface layer (40 / zm).
  • Polyolefin resin, polylactic acid resin, acrylic resin, and other resins and additives shown in Table 3 are put into a twin-screw extruder manufactured by Toshiba Machine Co., Ltd. and melt mixed at a set temperature of 200 ° C. Thereafter, the sheet was extruded from a single layer or a laminated T die, taken up with a cast roll at 50 ° C., and cooled and solidified to obtain an unstretched sheet having a width of 300 mm and a thickness of 200 ⁇ m.
  • This unstretched sheet was stretched 5.0 times in the horizontal uniaxial direction at a preheating temperature of 80 ° C and a stretching temperature of 73 ° C using a film tenter manufactured by Kyoto Machine Co., Ltd., and then heat treated at 80 ° C.
  • a heat-shrinkable film was obtained.
  • this film was wound up by 1000 m.
  • the thickness of the obtained heat-shrinkable film was 40 m.
  • Each layer thickness of the unstretched sheet of Example 8 is a back layer (50 ⁇ m), a Z core layer (100 ⁇ m), a Z surface layer (50 ⁇ m), and the unstretched sheets of Examples 9 and 10
  • Each layer thickness is a back layer (50 / zm) Z adhesive layer (10 m) Z core layer (80 ⁇ m) Z adhesive layer (10 m) Z surface layer (50 ⁇ m).
  • the heat shrinkable films (Examples 5 to 10) defined in the present invention were excellent in the evaluation results of the respective performances.
  • the heat-shrinkable films having the structures shown in Examples 9 and 10 showed high overall performance evaluation results.
  • the film of Comparative Example 3 having only the power of the resin (A) was inferior in evaluation in terms of the natural shrinkage rate and shrinkage finish.
  • Comparative Example 4 consisting of rosins (A) and (B) and not having rosin (C) had a haze value exceeding 10% and was inferior in transparency.
  • the film and heat-shrinkable film of the present invention can be used for forming molded articles such as bottles and trays, or as heat-shrinkable labels for packaging bodies such as bottles.

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Abstract

La présente invention concerne un film comportant au moins une couche constituée d'une résine polyoléfinique (A) et contenant également une résine d'acide polylactique (B) et une résine acrylique (C). Le film présente une excellente transparence et est peu nuisible à l'environnement.
PCT/JP2007/063181 2006-06-30 2007-06-29 Film, film thermorétractable, article moulé utilisant le film thermorétractable, étiquette thermorétractable, et récipient utilisant l'article moulé ou fixé avec l'étiquette WO2008001917A1 (fr)

Priority Applications (1)

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JP2008522667A JP5302679B2 (ja) 2006-06-30 2007-06-29 フィルム、熱収縮性フィルム、ならびにこの熱収縮性フィルムを用いた成形品、熱収縮性ラベル、およびこの成形品を用いた、またはこのラベルを装着した容器

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Cited By (4)

* Cited by examiner, † Cited by third party
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JP2010275534A (ja) * 2009-04-30 2010-12-09 Mitsubishi Rayon Co Ltd 相容化剤、熱可塑性樹脂組成物及び成形体
JP2011148258A (ja) * 2010-01-25 2011-08-04 Mitsubishi Plastics Inc 熱収縮性積層フィルム、並びに該フィルムを用いた成形品、熱収縮性ラベル、および該成形品を用いた、又は該ラベルを装着した容器
JP2011209485A (ja) * 2010-03-30 2011-10-20 Fuji Seal International Inc プラスチックラベル
JP2012057047A (ja) * 2010-09-09 2012-03-22 Unitika Ltd 樹脂組成物

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