WO2014136772A1 - Film en couches et matière de conditionnement - Google Patents

Film en couches et matière de conditionnement Download PDF

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Publication number
WO2014136772A1
WO2014136772A1 PCT/JP2014/055462 JP2014055462W WO2014136772A1 WO 2014136772 A1 WO2014136772 A1 WO 2014136772A1 JP 2014055462 W JP2014055462 W JP 2014055462W WO 2014136772 A1 WO2014136772 A1 WO 2014136772A1
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WO
WIPO (PCT)
Prior art keywords
heat
layer
resin
laminated film
film
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PCT/JP2014/055462
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English (en)
Japanese (ja)
Inventor
松原　弘明
安達　敏明
佐藤　芳隆
Original Assignee
Dic株式会社
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Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to JP2014561623A priority Critical patent/JP6316212B2/ja
Publication of WO2014136772A1 publication Critical patent/WO2014136772A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/20—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising esters
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/02—Open containers
    • B32B2439/06—Bags, sacks, sachets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/40—Closed containers
    • B32B2439/46—Bags

Definitions

  • the present invention relates to a laminated film that enables heat resistance and good packaging suitability without bonding a stretched base material having heat resistance.
  • packaging materials are required to have high heat seal strength, pinhole resistance, low temperature impact resistance, etc. from the viewpoint of content protection. Further, from the viewpoint of automatic packaging by a packaging machine, it is preferable that the difference between the layer in contact with the seal bar that is a heat source and the melting point of the seal layer on the inner surface side to be sealed by thermal fusion is larger.
  • the high-rigidity film with low waist is easy for the operator to handle because it is easy to set in a packaging machine. From these viewpoints, biaxially oriented polypropylene (OPP) and biaxially oriented are generally excellent in heat resistance and high rigidity.
  • Bonding stretched base film such as polyester (OPET), biaxially stretched polyamide (OPA), etc., unstretched polyethylene (PE), unstretched polypropylene (CPP), etc. with excellent sealing and sealing properties with an adhesive, Many laminate films have been used.
  • OPET polyester
  • OPA biaxially stretched polyamide
  • PE unstretched polyethylene
  • CPP unstretched polypropylene
  • the volume of packaging materials used has been reduced by reducing the thickness of packaging materials
  • the laminating process has been reduced by the coextrusion method
  • the organic solvent used in adhesives has been reduced
  • the adhesive itself has been reduced. Use and other factors are gaining importance among users and end consumers.
  • the present inventor has already used heat-resistant polypropylene having a high melting point as a surface resin layer, and laminated a resin layer mainly composed of an olefin resin having a melting point lower than that of the polypropylene as a heat seal layer.
  • a coextruded multilayer film that can be used alone without using a stretched base material, has excellent packaging machine suitability and excellent pinhole resistance, and a packaging material composed of the film have been proposed (for example, (See Patent Document 1).
  • the object of the present invention has been made in view of the above problems, and has excellent surface heat resistance while having suitable packaging machine suitability, and can be used alone without using a stretched substrate or the like. It is providing a laminated film, its manufacturing method, and a packaging material using the same.
  • the subject of this invention is providing the laminated
  • the present inventors have provided a heat-resistant coating layer made of a cellulose acetate-based coating agent on a resin substrate having a heat-sealable thermoplastic resin layer, thereby improving surface heat resistance. It has been found that it can be effectively improved and that a suitable heat sealing property can be realized, and the present invention has been completed.
  • the present invention is a laminated film having a heat-resistant coating layer on a resin substrate, the surface of the resin substrate having a heat-resistant coating layer is a surface layer on the other surface is a heat-sealable thermoplastic resin layer,
  • the heat-resistant coating layer is a layer made of a cellulose acetate coating agent, and provides a laminated film and a packaging material using the laminated film.
  • the heat-resistant thermoplastic laminated film of the present invention has a heat-resistant coating layer made of a cellulose acetate-based coating agent and can achieve extremely high heat resistance with a simple structure, it has a high heat seal temperature even in a thinned structure. Heat sealing is possible, and the temperature range that can be sealed is greatly expanded, which can greatly contribute to the improvement of production efficiency and the reduction of manufacturing costs. Moreover, it can obtain simply by apply
  • the design can be easily changed by selecting the layer structure of the multilayer film according to the target performance (transparency, rigidity, workability, etc.) and application (packaging material, poster, label, etc.). Excellent.
  • the present invention is a laminated film having a heat-resistant coating layer on a resin substrate, the surface of the resin substrate having a heat-resistant coating layer on the other surface is a heat-sealable thermoplastic resin layer, It is a laminated film in which the coat layer is a layer comprising a cellulose acetate-based coating agent.
  • the resin substrate used in the present invention is a resin substrate having one surface made of a heat-sealable thermoplastic resin layer (hereinafter referred to as a heat-sealable thermoplastic resin layer (A1)).
  • a heat-sealable thermoplastic resin layer A1
  • the surface made of the heat-sealable thermoplastic resin layer becomes one surface layer, and the other surface becomes the surface made of a heat-resistant coating layer.
  • the heat-sealable thermoplastic resin layer (A1) used in the present invention is a layer mainly composed of a heat-sealable thermoplastic resin (hereinafter referred to as heat-sealable thermoplastic resin (a1)).
  • heat-sealable thermoplastic resin heat-sealable thermoplastic resins used for packaging materials and the like can be used, and polyolefin-based resins, polyester-based resins, and polystyrene-based resins can be preferably used.
  • polyolefin resin can be preferably used.
  • polyolefin resin examples include homopolymers or copolymers of ⁇ -olefins having 2 to 6 carbon atoms.
  • the copolymerization type may be a block copolymer or a random copolymer.
  • polyolefin resin it is preferable to use what has the melting
  • polystyrene resin for example, any of those known as a polypropylene resin, a polyethylene resin, a cyclic olefin resin or the like can be used.
  • polypropylene resins include propylene homopolymers, propylene-ethylene copolymers, propylene-butene-1 copolymers, propylene-ethylene-butene-1 copolymers, ethylene-propylene block copolymers, metallocene catalysts. And polypropylene. These may be used alone or in combination of two or more.
  • crystallinity means having a peak of 0.5 J / g or more in the range of 95 to 250 ° C. in DSC (differential scanning calorimetry).
  • the polypropylene resin has a melt flow rate (hereinafter referred to as “230 ° C. MFR”; a value measured at 230 ° C. and 21.18 N in accordance with JIS K7210: 1999) of 0.5 to 30.
  • 230 ° C. MFR melt flow rate
  • Those having a melting point of 120 to 165 ° C. at 0.0 g / 10 min are preferred, more preferably those having an MFR of 230 to 120 ° C. of 2.0 to 15.0 g / 10 min and a melting point of 125 to 162 ° C. .
  • the MFR and the melting point are in this range, the film shrinkage is small even when secondary molding such as heat molding is performed after multilayering, so that the appearance can be maintained and the warping of the medium itself does not occur.
  • the film formability when a coextruded multilayer film is also improved.
  • the density is preferably 0.890 to 0.910 g / cm 3 and more preferably 0.895
  • the propylene-ethylene block copolymer is a resin obtained by block polymerization of propylene and ethylene.
  • propylene obtained by performing polymerization of ethylene or polymerization of ethylene and propylene in the presence of a propylene homopolymer. -Ethylene block copolymers and the like.
  • the surface of the layer (A1) can be easily modified into a satin finish.
  • a mixed resin of crystalline propylene resin and ethylene / propylene rubber hereinafter referred to as “EPR”
  • the surface of the layer (A1) can be easily modified into a satin finish.
  • the crystalline propylene-based resin used at this time a highly versatile propylene homopolymer is preferable.
  • those having a weight average molecular weight in the range of 400,000 to 1,000,000 are preferable in that irregularities can be formed on the film surface and the surface can be modified into a satin finish. A range is more preferable.
  • the content of EPR in the mixed resin is preferably in the range of 5 to 35% by mass from the viewpoint that the film surface can be uniformly modified into a satin finish.
  • the MFR (230 ° C.) of the mixed resin of the crystalline propylene polymer and EPR is preferably in the range of 0.5 to 15 g / 10 minutes from the viewpoint of easy extrusion.
  • the weight average molecular weight of the EPR was obtained by calculating a component extracted from the mixed resin by a cross fractionation method at 40 ° C. using orthodichlorobenzene as a solvent by GPC (gel permeation chromatography). It is.
  • the content of EPR in the mixed resin is obtained from the amount of EPR extracted by cross-fractionation at 40 ° C. using orthodichlorobenzene as a solvent.
  • the method for producing the mixed resin of the crystalline propylene-based resin and EPR is not particularly limited.
  • a propylene homopolymer and ethylene / propylene rubber are separately mixed using a Ziegler type catalyst.
  • a propylene homopolymer is produced in the first stage by a method of mixing both with a mixer or a two-stage polymerization method, and then the second stage. And a method of generating EPR in the presence of this polymer.
  • the Ziegler-type catalyst is a so-called Ziegler-Natta catalyst, and is obtained by supporting a transition metal compound such as a titanium-containing compound or a transition metal compound on a support such as a magnesium compound.
  • a transition metal compound such as a titanium-containing compound or a transition metal compound
  • a support such as a magnesium compound.
  • the combination with the promoter of an organometallic compound is mentioned.
  • polyethylene-based resin a density of 0.900 g / cm 3 or more 0.970 g / cm 3 less than the ethylene-based resin is preferably exemplified specifically a resin, for example, ultra low density polyethylene (VLDPE), Polyethylene resins such as linear low density polyethylene (LLDPE), linear medium density polyethylene (LMDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), and ethylene-vinyl acetate copolymer Polymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate (EMA) copolymer, ethylene-ethyl acrylate-maleic anhydride copolymer (E-EA-MAH), ethylene Ethylene copolymers such as crylic acid copolymer (EAA) and ethylene-methacrylic acid copolymer (EMAA); further
  • the density of the ethylene-based resin as described above is preferably less than 0.900 g / cm 3 or more 0.970 g / cm 3, is particularly in a range of less than 0.905 g / cm 3 or more 0.965 g / cm 3 It is more preferable. As long as it corresponds to this density, two or more types of polyethylene resins may be blended. If the density is less than 0.900 g / cm 3 , the rigidity may decrease and the suitability of the packaging machine may deteriorate. On the other hand, if it is 0.970 g / cm 3 or more, the pinhole resistance may be deteriorated.
  • the density is within this range, it has appropriate rigidity, excellent mechanical strength such as pinhole resistance, and film film formability and extrusion suitability are improved.
  • the melting point is preferably in the range of 95 to 130 ° C, more preferably 100 to 125 ° C. If the melting point is within this range, the film shrinkage is small even when heated at the time of coating or secondary molding of the heat-resistant coating layer, so that the appearance of the film can be maintained and the warping of the film itself can be suppressed. it can.
  • this multilayer film is used to form a packaging bag, that is, when the layers (A1) are heat sealed with the layers (A1) inside, the sealing property is excellent. These may be used alone or in combination of two or more.
  • the cyclic polyolefin resin examples include a norbornene polymer, a vinyl alicyclic hydrocarbon polymer, and a cyclic conjugated diene polymer.
  • norbornene-based polymers are preferable.
  • the norbornene-based polymer includes a ring-opening polymer of a norbornene-based monomer (hereinafter referred to as “COP”), a norbornene-based copolymer obtained by copolymerizing a norbornene-based monomer and an olefin such as ethylene (hereinafter, referred to as “COP”). , “COC”).
  • COP and COC hydrogenates are particularly preferred.
  • the weight average molecular weight of the cyclic olefin resin is preferably 5,000 to 500,000, more preferably 7,000 to 300,000.
  • the norbornene polymer and the norbornene monomer used as a raw material are alicyclic monomers having a norbornene ring.
  • Examples of such norbornene-based monomers include norbornene, tetracyclododecene, ethylidene norbornene, vinyl norbornene, ethylidene tetracyclododecene, dicyclopentadiene, dimethanotetrahydrofluorene, phenyl norbornene, methoxycarbonyl norbornene, methoxycarbonyl And tetracyclododecene.
  • These norbornene monomers may be used alone or in combination of two or more.
  • the norbornene-based copolymer is a copolymer of the norbornene-based monomer and an olefin copolymerizable with the norbornene-based monomer.
  • olefin include the number of carbon atoms such as ethylene, propylene, and 1-butene.
  • examples thereof include olefins having 2 to 20; cycloolefins such as cyclobutene, cyclopentene, and cyclohexene; and non-conjugated dienes such as 1,4-hexadiene. These olefins can be used alone or in combination of two or more.
  • examples of the ring-opening polymer (COP) of the norbornene monomer include “ZEONOR” manufactured by Nippon Zeon Co., Ltd., and norbornene.
  • examples of the system copolymer (COC) include “Appel” manufactured by Mitsui Chemicals, Inc., “TOPAS” manufactured by Polyplastics Co., Ltd., and the like.
  • the MFR (190 ° C., 21.18 N) of the polyethylene resin is preferably 2 to 20 g / 10 min. More preferably, it is ⁇ 10 g / 10 min.
  • the heat-sealable thermoplastic resin (a1) of the heat-sealable thermoplastic resin layer (A1) used in the present invention the above-mentioned various polyolefin resins, polyester resins and polystyrene resins should be used alone. However, a plurality of resins may be used in combination. It is preferable that 50% by mass or more in the heat-sealable thermoplastic resin used for the heat-sealable thermoplastic resin layer (A1) is a polyolefin-based resin, more preferably 70% by mass or more, and 80% by mass or more. Is more preferable, and it is especially preferable that it is 90 mass% or more.
  • the heat-sealable thermoplastic resin layer (A1) is composed of 1-butene and propylene as essential components as described in JP-A-2006-213065. -By making a heat seal layer containing a butene copolymer and a copolymer containing propylene and ethylene as essential components, an easily openable bag can be obtained.
  • the heat-sealable thermoplastic resin layer (A1) as the components other than the heat-sealable thermoplastic resin (a1), if necessary, other resin components, antifogging agents, antistatic agents, heat stabilizers
  • components such as a nucleating agent, an antioxidant, a lubricant, an antiblocking agent, a mold release agent, an ultraviolet absorber, and a colorant can be added within a range that does not impair the object of the present invention.
  • the surface friction coefficient is preferably 1.5 or less, more preferably 1.0 or less in order to impart processing suitability when forming a film or packaging suitability when used as a packaging material. It is preferable to add an antistatic agent as appropriate.
  • additives such as a lubricant and an antistatic agent are contained, 10 parts by mass or less is preferable with respect to 100 parts by mass of the resin component contained in the heat-sealable thermoplastic resin layer (A1). More preferable is 5 parts by mass.
  • the heat-sealable thermoplastic resin layer (A1) may be a single layer or a multilayer structure having two or more layers. From the viewpoint of more excellent rigidity, heat resistance and transparency, a film having a single layer or a multilayer structure mainly composed of a polypropylene resin is preferable.
  • the resin base material used in the present invention may be a resin base material composed only of the heat sealable thermoplastic resin layer (A1) as long as the heat sealable thermoplastic resin layer (A1) is included in the surface layer. Or the resin base material by which the heat-sealable thermoplastic resin layer (A1) and the other layer were laminated
  • the resin base material is composed only of the heat-sealable thermoplastic resin layer (A1), it is preferable because it can greatly contribute to the volume reduction of the packaging material by reducing the thickness of the obtained laminated film and the manufacturing cost.
  • stacked can be used preferably.
  • an anchor coat layer that improves the adhesion of the heat-resistant coat layer can be preferably exemplified.
  • the anchor coat layer is not particularly limited as long as it can improve the adhesion of the heat resistant coat layer, and an anchor coat layer made of various anchor coat agents and resin films can be used.
  • a layer containing an acid-modified olefin resin (hereinafter referred to as a layer (A2) containing an acid-modified olefin resin) is provided as an anchor coat layer on the surface of the resin base material on which the heat-resistant coating layer is provided.
  • the layer containing the acid-modified olefin resin is particularly excellent in the coating properties of the cellulose acetate-based coating agent and the adhesion to the heat-resistant coating layer made of the coating agent, and impact (rubbing, heating, etc.) during secondary processing It is possible to particularly suitably suppress peeling due to.
  • acid-modified olefin resin (a2)) used for the layer (A2) containing the acid-modified olefin resin is not particularly limited, ethylene, propylene Alkenes having 2 to 6 carbon atoms such as isobutylene, 2-butene, 1-butene, 1-pentene and 1-hexene are preferred, and mixtures thereof may be used. Of these, alkenes having 2 to 4 carbon atoms such as ethylene, propylene, isobutylene and 1-butene are more preferred, ethylene and propylene are more preferred, and ethylene is most preferred.
  • the acid-modified polyolefin resin (a2) needs to contain a (meth) acrylic acid ester component.
  • (Meth) acrylic acid ester components include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic acid Examples include octyl, decyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and the like.
  • the (meth) acrylic acid ester component may be copolymerized with the olefin component, and the form thereof is not limited. Examples of the copolymerization state include random copolymerization, block copolymerization, and graft copolymerization. (Graft modification) and the like. (Note that “(meth) acrylic acid” means “acrylic acid or methacrylic acid”).
  • ethylene- (meth) acrylic acid ester copolymers include Elvalloy ( Product name: Mitsui-DuPont Polychemical Co., Ltd.), Aklift (trade name: Sumitomo Chemical Co., Ltd.), etc. These may be used alone or in combination of two or more.
  • the acid-modified polyolefin resin (a2) may be acid-modified with an unsaturated carboxylic acid component.
  • unsaturated carboxylic acid components include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, and the like, as well as unsaturated dicarboxylic acid half esters and half amides. It is done. Of these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable, and acrylic acid and maleic anhydride are particularly preferable.
  • the unsaturated carboxylic acid component may be copolymerized with the olefin component, and the form thereof is not limited.
  • copolymerization state examples include random copolymerization, block copolymerization, and graft copolymerization (grafting). Modification).
  • ethylene-acrylic acid copolymer examples include Nucrel (trade name: Mitsui, manufactured by DuPont Polychemical Co., Ltd.) and the like can be mentioned.
  • ethylene- (meth) acrylic acid ester-maleic anhydride copolymer examples include bondine (trade name: manufactured by Tokyo Materials Co., Ltd.). These may be used alone or in combination of two or more.
  • the acid modification rate of the acid-modified olefin resin (a2) adhesion with a cellulose acetate-based coating agent to be described later, blocking suppression when winding and storing a multilayer film, and after applying the coating agent It is preferable to use 3 to 40%, more preferably 7 to 35%, and more preferably 10 to 30% from the viewpoint of excellent balance such as suppression of appearance defects such as film wrinkles in the drying step. Is most preferred.
  • the layer (A2) containing the acid-modified polyolefin resin may further use other resins in addition to the acid-modified olefin resin (a2).
  • the content of the acid-modified polyolefin resin (a2) in the layer (A2) containing the acid-modified polyolefin resin is preferably 3% by mass or more, more preferably 5% by mass or more, and 10% by mass. More preferably, it is the above.
  • any of those exemplified for the heat-sealable thermoplastic resin (a1) used for the layer (A1) can be suitably used.
  • the thermoplastic resins used in the layer (A1) and the layer (A2) may be the same or different.
  • the polyolefin resin used in the layer (A2) may be a single resin or a mixture of plural kinds.
  • a polyolefin resin other than the acid-modified polyolefin resin (a2) in the layer (A2) is preferable to use.
  • the polyolefin resin the polyolefin resin exemplified in the resin (a1) used for the layer (A1) can be suitably used.
  • the content of the polyolefin resin other than the resin (a2) in the resin component contained in the layer (A2) is preferably less than 90% by mass, and more preferably less than 80% by mass.
  • the resin component used for the layer (A2) may contain any other resin in addition to the polyolefin resin other than the acid-modified polyolefin resin (a2) and the acid-modified polyolefin resin (a2).
  • the content of the resin component other than the polyolefin-based resin is preferably less than 30% by mass in the resin component.
  • an antifogging agent for the layer (A2) containing the acid-modified polyolefin resin, an antifogging agent, an antistatic agent, a thermal stabilizer, a nucleating agent, an antioxidant, a lubricant, an antiblocking agent, a release agent, and an ultraviolet ray are optionally added.
  • Components such as an absorbent and a colorant can be added as long as the object of the present invention is not impaired.
  • the surface friction coefficient is preferably 1.5 or less, more preferably 1.0 or less in order to impart processing suitability when forming a film or packaging suitability when used as a packaging material. It is preferable to appropriately add a lubricant, an antiblocking agent, or an antistatic agent to the corresponding resin layer.
  • additives such as a lubricant and an antistatic agent are contained, 10 parts by mass or less is preferable with respect to 100 parts by mass of the resin component contained in the layer (A2) containing the acid-modified polyolefin resin. 1 to 5 parts by mass is more preferable.
  • the thickness of the resin base material used in the present invention can be appropriately set according to the use of the film.
  • the thickness is 20 to 70 ⁇ m.
  • it is preferably in the range of 70 to 1000 ⁇ m.
  • a resin base material a resin base material obtained by laminating the heat-sealable thermoplastic resin layer (A1) and a layer (A2) containing an acid-modified polyolefin resin, in particular, a resin comprising only the layer (A1) and the layer (A2)
  • the ratio of the thickness of the layer (A2) to the total thickness of the layers (A1) and (A2) is 5 to 50% because adhesion with the heat-resistant coating layer is particularly easily secured.
  • the thickness of the layer (A2) is preferably in the range of 2 to 40 ⁇ m.
  • the layer (A1) and the layer (A2) are laminated adjacently.
  • the extrusion lamination molding method is preferable.
  • steps such as coating and lamination can be omitted, and there are effects of reducing environmental burdens and manufacturing time and costs, which are extremely useful in practical use.
  • a layer (A1) and a layer (A2) in a molten state by various coextrusion methods such as a coextrusion multilayer die method and a feed block method, which are melt-extruded using two or more extruders.
  • a method of processing into a long wound film by a method such as inflation or T-die / chill roll method is particularly preferable, and a co-extrusion method using a T-die is most preferable.
  • the surface having the heat-resistant coating layer obtained in this configuration is a layered film characterized in that the surface layer on the other side is a layer composed of a heat-sealable thermoplastic resin layer, Also good.
  • the stretching may be uniaxial stretching that extends only in the longitudinal direction (MD direction) or the width direction (TD direction), or biaxial stretching that extends both.
  • the surface layer is a layer composed of a heat-sealable thermoplastic resin layer
  • the heat-resistant coating layer is applied by coating after stretching or the surface having the heat-resistant coating layer is the surface layer on the other side May be stretched after making a laminated film having a layer comprising a heat-sealable thermoplastic resin layer.
  • the stretching ratio at the time of stretching in the longitudinal direction (MD direction) of the multilayer sheet is preferably 2 to 10 times, and if it is less than 2 times, improvement in mechanical strength and moisture resistance due to stretching is insufficient. Since the tear strength of the obtained stretched film is lowered, it is not preferable.
  • the stretching ratio in stretching in the width direction (TD direction) is preferably 2 to 20 times, and if it is less than 2 times, the mechanical strength and moisture resistance are not sufficiently improved by stretching. Uneven thickness is generated, which is not preferable.
  • the stretching temperature is not limited because it affects the properties of each resin, but is 60 to 180 ° C., preferably 80 to 160 ° C. It is preferable to perform heat setting after completion of stretching. Heat setting can be performed by a known method, preferably at 80 to 170 ° C, more preferably at 100 to 160 ° C.
  • the surface of the layer (A2) containing the acid-modified polyolefin resin may be continuously subjected to surface treatment using corona discharge or plasma discharge under heating or in an inert gas atmosphere during the production of the multilayer film.
  • the resin substrate used for the laminated film of the present invention may appropriately use a layer other than the above layers (A1) and (A2) depending on the application to be used.
  • a layer other than the above layers (A1) and (A2) depending on the application to be used.
  • it when used as a lid member, it can be easily opened by adopting a multilayer structure as described in JP-A-2004-75181 and JP-A-2008-80543.
  • a cyclic polyolefin resin as described in JP-A-2010-234660 is used as one layer in a multilayer structure, it is possible to obtain a film having easy tearing properties. It is preferable to employ a multilayer structure.
  • Decorative layers such as characters, figures, symbols, etc. may be provided by printing or the like on the surface of the resin substrate used for the laminated film of the present invention, particularly the surface of the resin substrate on the side where the heat-resistant coating layer is provided.
  • the decoration layer may be provided on a part of the surface of the resin base material, or may be provided on the entire surface, or a plurality of decoration layers may be laminated.
  • the method for providing the decoration layer is preferable because the printing method is simple, and examples of the printing method include a silk printing method, a screen printing method, a gravure printing method, a flexographic printing method, and a thermal transfer printing method.
  • the ink used in the silk printing method and the screen printing method various inks used for printing on a film can be used, and a solvent system and a UV curing system are used.
  • solvent-based inks are preferably used because they only need to dry the solvent in a drying furnace, and therefore can be printed at low cost because no device such as a UV irradiation device is required.
  • the ink used for the thermal transfer system a resin type or a wax type is used. Of these, the resin type is preferably used because of its excellent weather resistance.
  • the heat-resistant coating layer (B)) used in the present invention is a heat-resistant coating layer comprising a cellulose acetate-based coating agent (hereinafter referred to as cellulose acetate-based coating agent (b)).
  • the heat-resistant coating layer (B) can impart extremely high heat resistance to the heat-sealable laminated film. Further, the heat resistance coating layer (B) used in the present invention can favorably improve the wear resistance and pinhole resistance.
  • the thickness of the heat-resistant coating layer (B) is preferably in the range of 0.2 ⁇ m to 50 ⁇ m in order to maintain heat resistance and transparency characteristics at a practical level and maintain good production efficiency. Taking into consideration the strength applied to the seal bar and the coating strength of the heat-resistant coating layer (B), a thickness in the range of 0.5 to 30 ⁇ m is more preferable.
  • the cellulose acetate-based coating agent (b) used for the heat-resistant coating layer (B) is a coating agent containing at least cellulose acetate, a crosslinking agent and an organic solvent, and the cellulose acetate-based coating agent (b) is used as the resin base material. After coating on, the heat-resistant coating layer can be formed by volatilizing the organic solvent contained in the cellulose acetate-based coating agent (b).
  • the cellulose acetate-based coating agent (b) is not particularly limited, and can be appropriately selected depending on the drying speed and heat resistance performance of the coating.
  • the cellulose acetate used in the cellulose acetate-based coating agent (b) that can easily impart such performance is a semi-synthetic polymer obtained by esterifying cellulose, which is a natural polymer.
  • Cellulose is a polymer having anhydroglucose as a repeating unit, and has three hydroxyl groups per repeating unit, and cellulose acetate resins having different properties depending on the degree of esterification (degree of substitution) are obtained.
  • the degree of substitution is represented by an index called acetylation degree. All three hydroxyl groups are acetylated, that is, triacetyl cellulose has an acetylation degree of 62.5%.
  • the acetylation degree of the cellulose acetate used in the present invention is preferably 40 to 70%, more preferably 43 to 62%.
  • the average degree of polymerization is preferably about 100 to 400.
  • the cellulose acetate content in the cellulose acetate-based coating agent (b) is preferably 5% by mass or more, more preferably 10% by mass or more in terms of the solid content excluding the organic solvent.
  • the cellulose acetate-based coating agent (b) may contain a crosslinking agent such as an isocyanate compound that can react with the unsubstituted hydroxyl group in order to further increase heat resistance, adhesion, and surface hardness.
  • a crosslinking agent such as an isocyanate compound that can react with the unsubstituted hydroxyl group in order to further increase heat resistance, adhesion, and surface hardness.
  • polyisocyanate (b-1) used for producing the cellulose acetate-based coating agent (b) used in the present invention various types can be used.
  • the aromatic diisocyanate is preferably used when considering the mechanical strength and the like, and when considering the durability and light resistance, the aliphatic or cycloaliphatic diisocyanate compound. Use is desirable.
  • aromatic diisocyanate because it is easy to obtain suitable adhesion to the printing layer, and when applying the cellulose acetate coating agent (b) on the printing layer, use MDI polyisocyanate. It is particularly preferable to do this.
  • a crosslinking agent such as an amino resin, an epoxy compound, an aziridine compound, a carbodiimide compound, or an oxazoline compound is used in combination.
  • amino resins and isocyanate compounds typified by melamine crosslinking agents are most preferred because of their fast reactivity.
  • Two or more kinds of crosslinking agents may be used in combination, or an appropriate amount of a curing accelerator may be used in combination.
  • the addition amount of the cross-linking agent is preferably 1 to 20 parts by mass, and more preferably 3 to 10 parts by mass with respect to 100 parts by mass of the solid content of the cellulose acetate-based coating agent (b). If it is this range, the blocking resistance, heat resistance, heat-and-moisture resistance, and solvent resistance of the formed coating layer (B) will be improved without impairing the suitability when printing on the coating layer (B). It becomes possible to make it.
  • the crosslinking agent is used in an amount of 5 parts by mass or more in terms of solid content with respect to 100 parts by mass of the cellulose acetate coating agent (b). It is preferable to do.
  • an organic solvent used when producing the cellulose acetate-based coating agent (b) it is possible to use an organic solvent having a boiling point of 150 ° C. or less in consideration of removing the residual solvent contained in the coating layer. preferable.
  • Examples of the organic solvent having a boiling point of 150 ° C. or lower include MEK (methyl ethyl ketone), benzene, toluene, ethyl acetate, acetone, methyl ethyl ketone, diethyl ether, tetrahydrofuran, methyl acetate, acetonitrile, chloroform, and methylene chloride. These can be used alone or in combination. Among them, it is particularly preferable to use acetone, methyl ethyl ketone, toluene, and ethyl acetate as a solvent having high solubility for the cellulose acetate-based coating agent (b).
  • MEK methyl ethyl ketone
  • benzene toluene
  • ethyl acetate acetone
  • methyl ethyl ketone diethyl ether
  • tetrahydrofuran methyl acetate
  • Alcohol solvents such as methanol, ethanol and isopropyl alcohol may be used for the purpose of improving processability after completion of the urethanization reaction. Also, after part or all of these organic solvents are distilled off, the aqueous (water-soluble, water-dispersible) polyurethane coating is changed to an aqueous solvent comprising a mixed solvent of water or a hydrophilic solvent compatible with water. It may be an agent.
  • the cellulose acetate coating agent (b) includes nitrocellulose, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-vinyl alcohol copolymer, urethane resin, fluorine resin, acrylic resin, epoxy together with cellulose acetate.
  • An organic polymer such as a resin or a polybutyral resin may be contained.
  • various lubricant components such as silicone oil, fluorine oil, higher fatty acid, paraffin, and fatty acid esters may be added as necessary.
  • the cellulose acetate-based coating agent (b) can contain an acrylic resin, a polyester resin, a synthetic rubber resin such as SBR, or the like as long as the transparency and heat resistance are not impaired. These resins are preferably 30% or less, particularly preferably 10% or less, in terms of solid content in the coating agent.
  • the cellulose acetate coating agent (b) may be supplemented with inorganic fine particles (colloidal silica) for improving blocking resistance or slip resistance, if necessary, and with an antistatic agent for improving wettability.
  • inorganic fine particles colloidal silica
  • An agent can also be blended.
  • the cellulose acetate-based coating agent (b) preferably has a minimum film forming temperature of 50 ° C. or lower, more preferably 30 ° C. or lower. If it is this range, it will become possible to coat without forming pinholes that are likely to occur during film formation.
  • the laminated film of the present invention has a structure in which a heat-resistant coating layer (B) comprising the cellulose acetate-based coating agent (b) is provided on a resin substrate having the heat-sealable thermoplastic resin layer (A1).
  • the laminated film is such that one surface of the laminated film is the surface of the heat-resistant coating layer (B) and the other surface is the surface of the heat-sealable thermoplastic resin layer (A1).
  • the laminated film of the present invention can realize extremely high heat resistance with the simple structure without impairing the suitability of packaging machinery, the surface layer does not adhere to the seal bar even during heat sealing at high temperatures, and the seal bar It is possible to suitably suppress the deterioration of the appearance due to the occurrence of dirt and wrinkles on the seal portion. For this reason, even in a thinned configuration, heat sealing can be suitably performed at a high heat sealing temperature, which can greatly contribute to the reduction of manufacturing cost and can be used alone without using a stretched substrate.
  • the thickness of the laminated film of the present invention may be appropriately adjusted according to the application to be used, but when used for various packaging materials, the heat sealability and handleability are preferably 15 to 150 ⁇ m. Therefore, it is preferable.
  • the laminated film of the present invention is prepared by adjusting the cellulose acetate-based coating agent (b) to an arbitrary resin concentration, then applying the cellulose acetate coating agent on the resin substrate, and then drying, and performing a curing treatment such as thermosetting as necessary. It can be manufactured.
  • the method for coating the cellulose acetate-based coating agent (b) on the resin substrate is not particularly limited. For example, coating such as an air knife coater, blade coater, roll coater, gravure coater, comma coater, gate roll coater, etc. A method using a machine is simple.
  • the method of volatilizing the medium contained in the coating agent after coating the cellulose acetate-based coating agent (b) on the film is not particularly limited, but for example, drying using a dryer.
  • the method is common.
  • the drying temperature may be a temperature that can volatilize the medium and does not adversely affect the substrate.
  • the surface on which the heat-resistant coating layer is applied in the production of the multilayer film may be continuously subjected to surface treatment using heating or an inert gas atmosphere using corona discharge or plasma discharge.
  • thermoplastic laminated film of the present invention can be obtained as a substantially unstretched multilayer film by the above-described production method, secondary molding such as deep drawing by vacuum molding, foil pressing, embossing, etc. is also possible. .
  • the laminated film of the present invention may be provided with a decorative layer such as letters, figures and symbols on the heat-resistant coating layer (B) by printing or the like.
  • a printing method is preferable because it is simple. Examples of the printing method include a silk printing method, a screen printing method, a gravure printing method, and a thermal transfer printing method.
  • a surface treatment on the resin base material layer in order to improve adhesion with printing ink.
  • examples of such surface treatment include corona treatment, plasma treatment, chromic acid treatment, flame treatment, hot air treatment, surface oxidation treatment such as ozone / ultraviolet treatment, and surface unevenness treatment such as sandblasting. Corona treatment is preferable.
  • the laminated film of the present invention has suitable heat sealability and high heat resistance, it can be suitably applied to various packaging materials.
  • the packaging material include packaging bags, containers, container lids and the like used for foods, medicines, industrial parts, miscellaneous goods, magazines and the like. In particular, it can be suitably used for medicines, industrial parts, foods and confectionery stored at room temperature, refrigerated and frozen, which are filled, packaged and sealed at high speed.
  • the packaging material is heat-sealed by stacking layers (A1) with the heat-sealable thermoplastic resin layer (A1) side of the laminated film of the present invention as a heat-seal layer, or a layer (A1) and a heat-resistant coating layer (B ) Is heat-sealed and is preferably a packaging bag formed with the layer (A1) as the inner side.
  • a packaging bag formed with the layer (A1) as the inner side.
  • thermoplastic resin layer (A1) it is also possible to form a lid of a packaging bag / container / container by heat-sealing with the heat-sealable thermoplastic resin layer (A1) and another film, sheet, or container that can be heat-sealed.
  • a film or sheet using a thermoplastic resin such as a polyethylene resin, a polypropylene resin, or a polyester resin can be used.
  • any tear such as V-notch, I-notch, perforation, micro-porosity, etc. is used in the seal portion in order to weaken initial tear strength and improve openability.
  • a starting portion may be formed.
  • the laminated film of the present invention after providing a pressure-sensitive adhesive layer on the heat-sealable thermoplastic resin layer (A1), heat-sealing the laminated film of the present invention and other resin films, A resealable packaging bag can also be provided.
  • the type of the adhesive is not particularly limited.
  • the pressure-sensitive adhesive layer may contain, for example, a terpene resin such as ⁇ -pinene, ⁇ -pinene polymer, diterpene polymer, ⁇ -pinene / phenol copolymer, Appropriate tackifiers such as aromatic resins, aromatic resins, aliphatic / aromatic copolymer systems, other rosin resins, coumarone indene resins, (alkyl) phenol resins and xylene resins Can be blended.
  • a terpene resin such as ⁇ -pinene, ⁇ -pinene polymer, diterpene polymer, ⁇ -pinene / phenol copolymer
  • Appropriate tackifiers such as aromatic resins, aromatic resins, aliphatic / aromatic copolymer systems, other rosin resins, coumarone indene resins, (alkyl) phenol resins and xylene resins Can be blended.
  • Example 1 As the resin for the resin layer (A1), a propylene-ethylene copolymer [MFR: 8 g / 10 min (230 ° C., 21.18 N), melting point: 138 ° C .; hereinafter referred to as “COPP”] was used. As the resin for the resin layer (A2), an ethylene- (meth) methyl acrylate copolymer (density: 0.940 g / cm 3 , MA content 18%; hereinafter referred to as “MA1”) was used.
  • MA1 ethylene- (meth) methyl acrylate copolymer
  • Each of these resins is supplied to an extruder for the resin layer (A1) (caliber 50 mm) and an extruder for the resin layer (A2) (caliber 50 mm) and melted at 200 to 250 ° C., and the melted resin is fed into the feed block.
  • Co-extruded multilayer film manufacturing apparatus feed block and T-die temperature: 250 ° C.
  • T die / chill roll method and co-melt extrusion are carried out, and the layer structure of the film is (A1) / (A2)
  • the surface of the support (A2) layer is subjected to corona discharge treatment so that the wetting tension is 40 mN / m, and then the cellulose acetate-based coating agent (b-1) obtained in Preparation Example 1 is dried. Was applied to give a heat-resistant olefin-based laminated film of Example 1.
  • Example 2 A heat-resistant olefin-based laminated film was prepared in the same manner as in Example 1 except that the cellulose acetate-based coating agent (b-1) in Example 1 was changed to the polyurethane coating agent (b-2) obtained in Preparation Example 2. .
  • Example 3 The acid-modified olefin resin of the resin layer (A2) of Example 1 was replaced with an ethylene-methyl acrylate copolymer (MA content 12%, density: 0.933 g / cm 3 ; hereinafter referred to as “MA2”).
  • MA2 ethylene-methyl acrylate copolymer
  • a heat-resistant olefin-based laminated film was produced in the same manner as in Example 1 except that the cellulose acetate-based coating agent (b-1) was applied so that the film thickness after drying was 0.5 ⁇ m.
  • Example 4 The acid-modified olefin resin of the resin layer (A2) of Example 1 is an ethylene-methyl acrylate-maleic anhydride copolymer [density: 1.00 g / cm 3 , copolymer content: 15%; hereinafter referred to as “MA3”.
  • MA3 ethylene-methyl acrylate-maleic anhydride copolymer
  • Example 5 50% of resin MA1 for resin layer (A2) of Example 2 and propylene-ethylene copolymer [density: 0.900 g / cm 3 , MFR: 7 to 9 g / 10 min (230 ° C., 21.18 N), Melting point: 150 ° C .; hereinafter referred to as “COPP”]
  • a heat-resistant olefin-based laminated film was produced in the same manner as in Example 2 except that the composition was replaced with 50%.
  • Example 6 A heat-resistant olefin-based laminated film was produced in the same manner as in Example 1 except that the resin MA1 for the resin layer (A2) of Example 2 was replaced with a blend of 20% and COPP of 80%.
  • COPP of the resin layer (A1) of Example 5 was made of high-density polyethylene [density: 0.93 g / cm 3 , MFR: 5 g / 10 min (190 ° C., 21.18 N), melting point 120 ° C .; hereinafter referred to as “MDPE”.
  • MDPE melting point 120 ° C .
  • a heat-resistant olefin-based laminated film was produced in the same manner as in Example 5 except that the description was replaced.
  • Example 8 COPP of the resin layer (A1) of Example 5 was changed to linear low density polyethylene [density: 0.905 g / cm 3 , MFR: 5.0 g / 10 min (190 ° C., 21.18 N), melting point 100 ° C .; , Described as “LLDPE”], and the thickness of each layer of the layer structure (A1) / (A2) of the film is 25 ⁇ m / 5 ⁇ m (total 30 ⁇ m), and the cellulose acetate-based coating agent (b-1) is dried.
  • a heat-resistant olefin-based laminated film was produced in the same manner as in Example 5 except that the film thickness was 5 ⁇ m.
  • Example 9 Example 1 except that the acrylic acid-modified resin of Example 1 was replaced with an ethylene- (meth) acrylic acid copolymer (density: 0.940 g / cm 3 , acid modification rate 12%; hereinafter referred to as “MA4”). In the same manner as in Example 2, a heat-resistant olefin-based laminated film was produced.
  • MA4 ethylene- (meth) acrylic acid copolymer
  • Example 10 The thickness of each layer of the layer structure (A1) / (A2) of Example 1 is 114 ⁇ m / 6 ⁇ m (total 120 ⁇ m), and the film thickness after drying the cellulose acetate coating agent (b-1) is 2 ⁇ m.
  • a heat-resistant olefin-based laminated film was produced in the same manner as in Example 1 except that the coating was performed as described above.
  • each layer of the layer structure (A1) / (A2) of Example 1 is 90 ⁇ m / 30 ⁇ m (total 120 ⁇ m), and the film thickness after drying the cellulose acetate coating agent (b-1) is 2 ⁇ m.
  • a heat-resistant olefin-based laminated film was produced in the same manner as in Example 1 except that the coating was performed as described above.
  • Example 12 An olefin-based single layer film composed of the resin layer (A1) was produced in the same manner as in Example 1 except that the resin layer (A2) of Example 1 was not extruded. One surface of this support is subjected to corona discharge treatment so that the wetting tension is 40 mN / m, and then the cellulose acetate coating agent (b-3) obtained in Preparation Example 3 is dried to have a thickness of 2 ⁇ m. The heat-resistant olefin-based laminated film of Example 12 was produced.
  • Example 1 An olefin-based laminated film was produced in the same manner as in Example 1 except that the cellulose acetate-based coating agent (b-1) was not applied.
  • Resin layers (B) were sealed while changing in increments of 10 ° C. from a temperature of 30 bags / minute, a vertical heat sealing temperature of 150 ° C., an air gauge pressure of 4 kg / cm 2, and a horizontal heat sealing temperature of 140 ° C. to 200 ° C.
  • a flat bag measuring 200 mm long and 150 mm wide was used.
  • Example 13 As the resin for the resin layer (A1), a propylene-ethylene copolymer [MFR: 8 g / 10 min (230 ° C., 21.18 N), melting point: 138 ° C .; hereinafter referred to as “COPP”] was used. As the resin for the resin layer (A2), an ethylene- (meth) methyl acrylate copolymer (density: 0.940 g / cm 3 , MA content 18%; hereinafter referred to as “MA1”) was used.
  • MA1 ethylene- (meth) methyl acrylate copolymer
  • Each of these resins is supplied to an extruder for the resin layer (A1) (caliber 50 mm) and an extruder for the resin layer (A2) (caliber 50 mm) and melted at 200 to 250 ° C., and the melted resin is fed into the feed block.
  • Co-extruded multilayer film manufacturing apparatus feed block and T-die temperature: 250 ° C.
  • T die / chill roll method and co-melt extrusion are carried out, and the layer structure of the film is (A1) / (A2)
  • the surface of the support (A2) layer is subjected to corona discharge treatment so that the wetting tension is 40 mN / m, and then the cellulose acetate-based coating agent (b-1) obtained in Preparation Example 1 is dried.
  • the coating layer was formed by coating and drying to a thickness of 1 ⁇ m.
  • nitrified cotton / urethane ink (c-1) (ULTIMA NT507 primary color indigo produced by DIC Graphics) was printed to a thickness of 1 ⁇ m after drying. A laminated film was produced.
  • Example 14 The same procedure as in Example 13 was followed, except that the nitrified cotton / urethane ink (c-1) in Example 13 was changed to nitrified cotton / polyamide ink (c-2) (Glosser 507 primary indigo produced by DIC Graphics). A heat-resistant olefin-based laminated film was prepared.
  • Example 15 The same procedure as in Example 13 was repeated except that the nitrified cotton / urethane ink (c-1) in Example 13 was changed to urethane ink (c-3) (Univia NT R507 primary color indigo K-1 manufactured by DIC Graphics). Thus, a heat-resistant olefin-based laminated film was prepared.
  • Example 16 A heat-resistant olefin-based laminated film was prepared in the same manner as in Example 13 except that the cellulose acetate-based coating agent (b-1) in Example 13 was changed to the polyurethane coating agent (b-2) obtained in Preparation Example 2. did.
  • Example 17 The same method as in Example 16 except that the nitrified cotton / urethane ink (c-1) in Example 16 is nitrified cotton / polyamide ink (c-2) (Glosser 507 primary indigo produced by DIC Graphics). A heat-resistant olefin-based laminated film was prepared.
  • Example 18 The same procedure as in Example 16 was conducted except that the nitrified cotton / urethane-based ink (c-1) in Example 16 was changed to urethane-based ink (c-3) (Univia NT R507 primary color indigo K-1 manufactured by DIC Graphics). Thus, a heat-resistant olefin-based laminated film was prepared.
  • Example 19 A heat-resistant olefin-based laminated film was prepared in the same manner as in Example 13 except that the cellulose acetate-based coating agent (b-1) in Example 13 was changed to the polyurethane coating agent (b-3) obtained in Preparation Example 3. did.
  • Example 20 The same procedure as in Example 19 was repeated except that the nitrified cotton / urethane ink (c-1) in Example 19 was changed to nitrified cotton / polyamide ink (c-2) (Glosser 507 primary indigo produced by DIC Graphics). A heat-resistant olefin-based laminated film was prepared.
  • Example 21 The same procedure as in Example 19 was repeated except that the nitrified cotton / urethane ink (c-1) in Example 19 was changed to urethane ink (c-3) (Univia NT R507 primary color indigo K-1 manufactured by DIC Graphics). Thus, a heat-resistant olefin-based laminated film was prepared.
  • Example 22 As the resin for the resin layer (A1), a propylene-ethylene copolymer [MFR: 8 g / 10 min (230 ° C., 21.18 N), melting point: 138 ° C .; hereinafter referred to as “COPP”] was used. As the resin for the resin layer (A2), an ethylene- (meth) methyl acrylate copolymer (density: 0.940 g / cm 3 , MA content 18%; hereinafter referred to as “MA1”) was used.
  • MA1 ethylene- (meth) methyl acrylate copolymer
  • Each of these resins is supplied to an extruder for the resin layer (A1) (caliber 50 mm) and an extruder for the resin layer (A2) (caliber 50 mm) and melted at 200 to 250 ° C., and the melted resin is fed into the feed block.
  • Co-extruded multilayer film manufacturing apparatus feed block and T-die temperature: 250 ° C.
  • T die / chill roll method and co-melt extrusion are carried out, and the layer structure of the film is (A1) / (A2)
  • Corona discharge treatment was applied to the surface of the (A2) layer of this support so that the wetting tension was 40 mN / m, and then a nitrified cotton / urethane ink (c-1) (ULTIMA NT507 primary color indigo made by DIC Graphics) was applied. It printed so that a film thickness might be set to 1 micrometer after drying.
  • the cellulose acetate-based coating agent (b-1) obtained in Preparation Example 1 was applied to the obtained printed surface so as to have a film thickness after drying of 1 ⁇ m, and dried to heat-resistant olefin-based laminate of Example 22. A film was prepared.
  • Example 23 The same procedure as in Example 22 was repeated except that the nitrified cotton / urethane ink (c-1) in Example 22 was changed to nitrified cotton / polyamide ink (c-2) (Glosser 507 primary indigo produced by DIC Graphics). A heat-resistant olefin-based laminated film was prepared.
  • Example 24 The same procedure as in Example 22 was conducted except that the nitrified cotton / urethane ink (c-1) in Example 22 was changed to urethane ink (c-3) (Univia NT R507 primary color indigo K-1 manufactured by DIC Graphics). Thus, a heat-resistant olefin-based laminated film was prepared.
  • Example 25 A heat-resistant olefin-based laminated film was prepared in the same manner as in Example 22 except that the cellulose acetate-based coating agent (b-1) in Example 22 was changed to the polyurethane coating agent (b-2) obtained in Preparation Example 2. did.
  • Example 26 The same procedure as in Example 25 was repeated except that the nitrified cotton / urethane ink (c-1) in Example 25 was changed to nitrified cotton / polyamide ink (c-2) (Glosser 507 primary color indigo by DIC Graphics). A heat-resistant olefin-based laminated film was prepared.
  • Example 27 The same procedure as in Example 25 was repeated except that the nitrified cotton / urethane ink (c-1) in Example 25 was changed to urethane ink (c-3) (Univia NT R507 primary color indigo K-1 manufactured by DIC Graphics). Thus, a heat-resistant olefin-based laminated film was prepared.
  • Example 28 A heat-resistant olefin-based laminated film was prepared in the same manner as in Example 22 except that the cellulose acetate-based coating agent (b-1) in Example 22 was changed to the polyurethane coating agent (b-3) obtained in Preparation Example 3. did.
  • Example 29 The same procedure as in Example 28 was repeated except that the nitrified cotton / urethane ink (c-1) in Example 28 was changed to nitrified cotton / polyamide ink (c-2) (Glosser 507 primary indigo produced by DIC Graphics). A heat-resistant olefin-based laminated film was prepared.
  • Example 30 The same procedure as in Example 28 was followed except that the nitrified cotton / urethane ink (c-1) in Example 28 was changed to urethane ink (c-3) (Univia NT R507 primary color indigo K-1 manufactured by DIC Graphics). Thus, a heat-resistant olefin-based laminated film was prepared.
  • the laminated films of the present invention of Examples 1 to 12 were excellent in surface heat resistance and had suitable packaging machine suitability.
  • the laminated film of Comparative Example 1 having no heat-resistant coating layer had low heat resistance and was inferior in packaging machine suitability at a high heat seal temperature.
  • the laminated film of the present invention was capable of printing with various inks on the heat-resistant coating layer, and had suitable printability.
  • a coat layer can be suitably laminated even when a resin film having a printed layer surface is used.
  • lamination of Examples 23 to 24, 26 to 27, and 28 to 29 is possible.
  • the film was particularly excellent in the adhesion of the coat layer.

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Abstract

La présente invention concerne un film en couches et une matière de conditionnement utilisant ledit film en couches. Ledit film en couches a une couche de revêtement tolérant à la chaleur au-dessus d'un substrat de résine. La couche de surface du substrat de résine à l'opposé de la couche de revêtement tolérant à la chaleur comprend une couche de résine thermoplastique de thermoscellage et la couche de revêtement tolérant à la chaleur comprend un agent de revêtement d'acétate de cellulose. L'utilisation d'une couche de revêtement tolérant à la chaleur comprenant un agent de revêtement d'acétate de cellulose permet à ce film en couches de présenter une tolérance extrêmement élevée à la chaleur avec une structure simple, permet un thermoscellage à une température élevée de thermoscellage même dans une conception à épaisseur réduite et augmente sensiblement la plage des températures sur lesquelles un thermoscellage est possible, permettant ainsi de contribuer de façon significative à une amélioration en rendement de production et à une réduction en coût de fabrication.
PCT/JP2014/055462 2013-03-06 2014-03-04 Film en couches et matière de conditionnement WO2014136772A1 (fr)

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WO2022069805A1 (fr) * 2020-10-02 2022-04-07 Woodly Oy Film multicouche co-extrudé à base de cellulose, son procédé de fabrication et produits ainsi fabriqués

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JP7346871B2 (ja) * 2019-03-28 2023-09-20 Dic株式会社 コーティング剤、これを塗工した積層体、包装材及び加工品

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