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WO2013002176A1 - Pellicule multicouche à base d'oléfine résistante à la chaleur, son procédé de production et matériau d'emballage comprenant celle-ci - Google Patents

Pellicule multicouche à base d'oléfine résistante à la chaleur, son procédé de production et matériau d'emballage comprenant celle-ci Download PDF

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Publication number
WO2013002176A1
WO2013002176A1 PCT/JP2012/066144 JP2012066144W WO2013002176A1 WO 2013002176 A1 WO2013002176 A1 WO 2013002176A1 JP 2012066144 W JP2012066144 W JP 2012066144W WO 2013002176 A1 WO2013002176 A1 WO 2013002176A1
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WO
WIPO (PCT)
Prior art keywords
layer
heat
multilayer film
resistant
resin
Prior art date
Application number
PCT/JP2012/066144
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English (en)
Japanese (ja)
Inventor
松原　弘明
北田　満
Original Assignee
Dic株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to JP2012543826A priority Critical patent/JP5158458B2/ja
Priority to CN201280032338.4A priority patent/CN103635317B/zh
Publication of WO2013002176A1 publication Critical patent/WO2013002176A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • 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
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • 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 heat-resistant olefin-based multilayer film that enables heat resistance and good packaging suitability without bonding a heat-resistant stretched substrate, and more specifically, a heat-resistant coating agent and an olefin-based multilayer film.
  • a heat-resistant olefin-based multilayer film that is excellent in coating properties and adhesion with a film, has no problems such as peeling or falling off of a coating agent, and can be used as a packaging material as it is, a method for producing the same, and a method for producing the same It relates to the packaging material used.
  • 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 upper limit of the sealing temperature is 160 ° C., and at a temperature higher than this, adhesion of the surface layer to the sealing bar is unavoidable. There was a problem of deterioration of the appearance due to generation of dirt, wrinkles in the seal portion, etc., and it was sometimes impossible to make a bag under the same conditions as a multilayer film in which stretched substrates were bonded together.
  • Patent Documents 2 to 4 a technique that aims to enhance the function of the film by applying a functional paint to the surface of the plastic film and drying it is widely known (see, for example, Patent Documents 2 to 4).
  • the object of the present invention has been made in view of the above problems, and by applying a heat-resistant coating agent to an unstretched olefin-based film, it has excellent surface heat resistance and utilizes a stretched substrate and the like.
  • a heat-resistant olefin-based multilayer film excellent in suitability for packaging machinery and excellent in adhesion strength between a coat layer and an olefin-based film, a manufacturing method thereof, and a packaging material using the same are provided. That is.
  • the present inventors applied a heat-resistant coating agent to a specific multilayer film made of an olefin resin and dried it, so that the above-described problem can be solved without any special efforts. It has been found that the adhesion between the coating agent and the film is good, the surface heat resistance of the olefin-based multilayer film can be effectively improved, and the above problems can be solved, and the present invention has been completed.
  • the layer (A1) containing the polyolefin resin (a1) as a main component, the layer (A2) containing the acid-modified olefin resin (a2), and the heat-resistant coating layer (B) are: A1) / (A2) / (B), and the ratio of the layer (A2) to the total thickness of the layer (A1) and the layer (A2) is 5 to 40%.
  • a layer (B) is a layer made of a polyurethane coating agent (b), and a heat-resistant olefin-based multilayer film and a packaging material using the same are provided.
  • the layer (A1) containing the polyolefin resin (a1) as a main component, the layer (A2) containing the acid-modified olefin resin (a2), and the heat resistant coating layer (B) are (A1 ) / (A2) / (B) is a method for producing a multilayer film, in which the layer (A1) and the layer (A2) are laminated using a coextrusion lamination method,
  • the present invention also provides a method for producing a heat-resistant olefin-based multilayer film, which comprises applying a polyurethane coating agent (b) on A2).
  • the heat-resistant olefin-based multilayer film of the present invention can be easily obtained by applying a heat-resistant coating agent on the coextruded multilayer film.
  • 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 use of the co-extrusion method can omit the formation process of the anchor layer (primer layer), and there are effects of reducing environmental load and manufacturing time and cost, and it is highly useful.
  • the plastic film functioning as a support for the heat-resistant olefin-based multilayer film of the present invention has a layer (A1) containing at least a polyolefin-based resin (a1) as a main component and an acid-modified olefin-based resin (a2) (A2). ).
  • This layer (A2) has a function as an easily adhesive layer with the heat-resistant coating layer (B) as well as a function as a support.
  • “main component” means that the specific resin is contained in an amount of 80% by mass or more based on the total amount of the resin composition forming the layer, and preferably 85% by mass.
  • the above is a specific resin.
  • “containing” means that the specific resin is contained in an amount of 1% by mass or more with respect to the total amount of the resin composition forming the layer, and preferably 20% by mass or more. Say that it is a specific resin.
  • the opposite side of the surface heat-resistant layer in the heat-resistant olefin-based multilayer film of the present invention is a layer (A1) mainly composed of a polyolefin-based resin (a1).
  • the polyolefin resin (a1) that can be used here 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 (a1) it is preferable to use what has the melting
  • polystyrene resin (a1) for example, any of those known as a polypropylene resin, a polyethylene resin and 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. Can do.
  • 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. Can do.
  • the crystalline propylene-based resin used at this time a highly versatile propylene homopolymer is preferable.
  • the EPR used at this time 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 MFR (190 ° C., 21.18 N) of the polyethylene resin is 2 to 20 g / 10 min from the viewpoint of improving the process stability and the processability when coextruding with the acid-modified olefin resin (a2) described later. It is preferably 3 to 10 g / 10 min.
  • a layer (A1) which has polyolefin resin (a1) as a main component it may be a single layer or may have a multilayer structure of 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 outermost layer on the opposite side of the heat-resistant coating layer (B) is made of 1-butene and propylene as described in JP-A-2006-213065.
  • a heat seal layer containing a 1-butene copolymer as an essential component and a copolymer having propylene and ethylene as essential components an easily openable bag can be obtained.
  • a lid when used as a lid, it can be easily opened by adopting a multilayer structure as described in JP-A-2004-75181 and JP-A-2008-80543. It is.
  • 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.
  • the adhesive film (label) which can be affixed on a signboard, a vehicle, etc. by providing an adhesive layer on a layer (A1) [surface opposite to the layer (A2) mentioned later].
  • 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.
  • the layer (A2) in the present invention is a layer containing the acid-modified olefin resin (a2) as an essential component.
  • the olefin component which is the main component of the acid-modified polyolefin resin (a2) is not particularly limited, but has 2 to 6 carbon atoms such as ethylene, propylene, isobutylene, 2-butene, 1-butene, 1-pentene, 1-hexene and the like. Alkenes are preferred and mixtures of these 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) includes adhesion to the polyurethane coating agent (b) described later, suppression of blocking when winding and storing the multilayer film, polyurethane coating agent (b) It is preferable to use 3 to 40%, preferably 7 to 35%, more preferably 10 to 10% from the viewpoint of excellent balance such as prevention of appearance defects such as film wrinkles in the drying process after coating. Most preferably, it is 30%.
  • the layer (A2) in the present invention may further use other resins in combination.
  • a polyolefin-based resin in combination because it is mixed with the acid-modified olefin-based resin (a2) and can be easily coextruded with the layer (A1).
  • the acid-modified olefin resin (a2) is preferably contained in an amount of 20 parts by mass or more, particularly preferably 25 parts by mass or more in 100 parts by mass of the resin component forming the layer (A2).
  • any of those exemplified for the polyolefin resin (a1) used for the layer (A1) can be suitably used.
  • the polyolefin resin 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.
  • an antifogging agent In each of the layers (A1) and (A2), 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 absorber are added as necessary.
  • Components such as a colorant 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 appropriately add a lubricant, an antiblocking agent, or an antistatic agent to the corresponding resin layer.
  • the total thickness of each of the layers (A1) and (A2) can be appropriately set according to the use of the film.
  • a packaging material bag or lid material
  • 20 to 70 ⁇ m In the case of labels and posters, it is preferably in the range of 70 to 1000 ⁇ m.
  • the ratio of the thickness of the layer (A2) to the total thickness of the layers (A1) and (A2) is in the range of 5 to 50% from the viewpoint of ensuring adhesion with the polyurethane coating agent (b) described later.
  • the thickness of the layer (A2) is preferably in the range of 2 to 40 ⁇ m.
  • the method for laminating the layer (A1) and the layer (A2) is preferably a coextrusion laminating method in which the layer (A1) and the layer (A2) are laminated adjacently.
  • various coextrusion methods such as coextrusion multi-layer die method, feed block method, etc., which are melt-extruded using an extruder of more than one table
  • inflation, T-die -A method of processing into a long wound film by a method such as a chill roll method is particularly preferable, and a coextrusion method using a T-die is most preferable.
  • the surface of the layer (A2) may be continuously subjected to surface treatment using heating or an inert gas atmosphere using corona discharge or plasma discharge.
  • the heat-resistant olefin-based multilayer film of the present invention after coating the polyurethane coating agent (b) on the multilayer film obtained above, volatilizes the medium contained in the polyurethane coating agent (b), A heat-resistant coating layer (B) is formed on a multilayer film.
  • the heat-resistant olefin-based multilayer film of the present invention has a heat-resistant coating layer (B) having a thickness in the range of 1 ⁇ m to 50 ⁇ m in order to maintain heat resistance and transparency characteristics at a practical level and maintain good production efficiency. ) Is preferable, and the film having a heat-resistant coating layer (B) having a thickness in the range of 2 ⁇ m to 30 ⁇ m is more preferable in consideration of the coating on the seal bar and the coating strength of the heat-resistant coating layer (B). .
  • a method for coating the polyurethane coating agent (b) on the film is not particularly limited.
  • a coating machine such as an air knife coater, a blade coater, a roll coater, a gravure coater, a comma coater, or a gate roll coater is used.
  • the method used is simple.
  • the method of volatilizing the medium contained in the coating agent after coating the polyurethane coating agent (b) on the film is not particularly limited, but for example, a method of drying using a dryer. It is common.
  • the drying temperature may be a temperature that can volatilize the medium and does not adversely affect the substrate.
  • the polyurethane coating agent (b) is not particularly limited, and can be appropriately selected according to the drying speed and heat resistance performance of the coating.
  • polyurethane coating agent (b) examples include polyester polyol (b-1) and polyisocyanate (polyisocyanate) obtained by condensing a dicarboxylic acid mainly composed of an aromatic dicarboxylic acid and a polyol. It is preferable that b-2) is used as an essential component and, if necessary, other polyols, polyamines or the like are used as chain extenders and reacted by various methods. Further, a polyurethane coating agent (b) obtained by using at least one of these polyester polyols (b-1), other polyols and polyamines used in combination, if necessary, having an anionic group Water dispersibility can also be imparted to.
  • polyester polyol (b-1) obtained by condensing the dicarboxylic acid mainly composed of the aromatic dicarboxylic acid and the polyol, which is used when the polyurethane coating agent (b) is produced, will be described.
  • the polyester polyol (b-1) can be produced by various methods using various dicarboxylic acids and various polyols.
  • polyester polyol (b-1) examples include terephthalic acid, isophthalic acid, orthophthalic acid, 1,4-naphthalenedicarboxylic acid, and 2,5-naphthalenedicarboxylic acid.
  • Aromatic dicarboxylic acids such as acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-P, P'-dicarboxylic acid and their acid anhydrides or ester-forming properties Derivatives, aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and their ester-forming derivatives, sulfonic acids such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, and 5 [4-sulfophenoxy] isophthalic acid Group-containing aromatic dicarboxylic acids and their ester-forming derivatives It is.
  • aliphatic carboxylic acids and alicyclic carboxylic acids can be used in combination.
  • aliphatic dicarboxylic acids such as succinic acid, succinic anhydride, adipic acid, suberic acid, azelaic acid, sebacic acid, dimer acid, maleic anhydride, fumaric acid, and alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid And anhydrides or ester-forming derivatives thereof. These may be used alone or in combination of two or more.
  • polyester polyol (b-1) examples include aromatic cyclic structures such as bisphenol A, bisphenol S, hydroquinone, bishydroxyethoxybenzene, and alkylene oxide adducts thereof.
  • an aliphatic polyol obtained by ring-opening polymerization of a cyclic ester such as ⁇ -caprolactone or ⁇ -valerolactone in the presence of the polyol and a catalyst can also be used. These may be used alone or in combination of two or more.
  • the polyester polyol (b-1) preferably has a hydroxyl value in the range of 10 to 350, particularly preferably in the range of 20 to 300. When the hydroxyl value is within this range, the resulting polyurethane resin has high cohesive strength, and heat resistance, solvent resistance, water resistance and blocking resistance when used as a coating agent are improved.
  • the polyester polyol (b-1) In order to produce the polyurethane coating agent (b) used in the present invention, among the polyester polyol (b-1), a polyester polyol obtained by condensing a dicarboxylic acid containing an aromatic dicarboxylic acid as a main component and the polyol. In this case, it is preferable to use one in which 70 to 100 mol% of the total amount of the dicarboxylic acid is terephthalic acid and / or isophthalic acid. By using such a polyester polyol, a coating agent capable of forming a coating layer excellent in heat resistance, water resistance, solvent resistance, transparency and the like can be easily obtained.
  • polyurethane coating agent (b) used in the present invention polyols other than the polyester polyol (b-1) described above can be used as long as the heat resistance is not impaired.
  • polyester polyol examples include polyester polyol, polyether polyol, polycarbonate polyol, and the like. These may be used alone or in combination of two or more. In particular, it is preferable to use polyester polyol as a main component from the viewpoint of excellent adhesion to a wide range of substrates and cost.
  • the polyester polyol is exemplified as a compound that can be used in combination with the production of the polyester polyol (b-1), and the aliphatic carboxylic acid or alicyclic carboxylic acid is reacted with various polyols by various methods. Can be manufactured. At this time, monoalcohols such as methanol, ethanol, n-butanol, isopropanol, and n-hexanol may be used in combination as long as the high molecular weight of the polyurethane coating agent (b) is not inhibited.
  • the polyester polyol (b-1) and other polyols as required, and various polyisocyanates (b-2) are previously added to the hydroxyl groups of all polyols.
  • the schocyanate-containing prepolymer is prepared by reacting under the condition that the isocyanate group of the polyisocyanate is excessive, and a low molecular weight polyol or polyamine is reacted with the prepolymer to increase the molecular weight. The method can also be adopted.
  • the low molecular weight polyol includes 2,2′-dimethylolpropionic acid, 2,2′-dimethylolbutanoic acid, 2,2′-dimethylolbutyric acid, 2,2′-dimethylolvaleric acid and the like as hydrophilic groups.
  • Polyols containing carboxyl groups that can be used, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol , Neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propane Aliphatic diols such as diols Alicyclic diols such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and hydrogenated bisphenol A can be used, and polyols such as glycerin, trimethylolpropane and pentaerythritol can be used as polyfunctional
  • polyamine examples include metal salts of N- (2-sulfoethyl) ethylenediamine, diaminosulfonates such as 2- ( ⁇ -aminoalkyl-aminopropionamide) -alkanesulfonate, and aliphatics such as ethylenediamine.
  • amino alcohols having both an amino group and an alcoholic hydroxyl group in the molecule can be used, for example, ethanolamine, N-methyldiethanolamine, propanolamine, N-methyldiisopropanolamine, N-ethyldiethyleneamine, N-ethyldiisopropanolamine, aminoethylethanolamine, diethanolamine and the like can also be used.
  • a polyamine having two or more functional groups it is preferable to use a polyamine having two or more functional groups in order not to impair durability.
  • a polyamine having two or more functional groups may be used alone, or two or more kinds may be used. It may be used in combination with an average functional group number of 2 or more.
  • the amount of polyamine used is preferably 1.9 equivalent ratio or less with respect to the isocyanate group, more preferably 0.6 to The range is 1.0 equivalent ratio. If chain extension is carried out using polyamine within this range, the durability and light resistance of the coating layer (B) obtained using the resulting coating agent can be made excellent.
  • polyisocyanate (b-2) used for producing the polyurethane coating agent (b) used in the present invention various materials can be used.
  • aromatic diisocyanate is desirable particularly when considering the mechanical strength and the like, and when considering the durability and light resistance, the aliphatic or cycloaliphatic diisocyanate compound is particularly desirable. Use is desirable.
  • organic solvent used when producing the polyurethane coating agent (b) it is preferable 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.
  • Examples of the organic solvent having a boiling point of 150 ° C. or lower include 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, or ethyl acetate as a solvent having high solubility for the polyurethane coating agent (b).
  • 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 content of urethane bond units (—NH—COO—) per 1000 g of the polyurethane coating agent (b) is in the range of 1.0 to 4.0 mol, more preferably in the range of 1.5 to 3.0 mol. It is.
  • urethane bond units per 1000 g of the polyurethane coating agent (b) are formed.
  • the total content of —COO—) and urea binding units is in the range of 1.0 to 6.0 mol, more preferably in the range of 1.5 to 4.0 mol. Preferably there is. If it is this range, since the cohesive force of a polyurethane molecule will become high, the hardness of the coat layer obtained will become suitable, and solvent resistance, blocking resistance, and heat resistance can be improved.
  • the content of the aromatic cyclic structural unit in the polyurethane coating agent (b) is preferably in the range of 15 to 40% by mass, and more preferably in the range of 20 to 35% by mass. If it is this range, it will be excellent in the adhesiveness with respect to the multilayer film of the coating agent obtained, and will be excellent in the solvent resistance of the obtained coating layer (B), water resistance, blocking resistance, heat resistance, etc.
  • the polyurethane coating agent (b) preferably has a flow start temperature of 100 ° C. or higher, and more preferably 150 ° C. or higher. If it is this range, it will become the thing excellent in blocking resistance equivalent to the laminate film which uses heat-resistant base materials, such as PET.
  • the polyurethane coating agent (b) preferably has a minimum film-forming temperature of 50 ° C. or lower, and 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.
  • a crosslinking agent such as an amino resin, an epoxy compound, an aziridine compound, a carbodiimide compound, an oxazoline compound, or a polyisocyanate 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% by mass, more preferably 3 to 10% by mass, based on the polyurethane 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 polyurethane 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 polyurethane coating agent (b) may contain an auxiliary agent such as inorganic fine particles (colloidal silica) for improving blocking resistance or slip resistance, and an antistatic agent for improving wettability, if necessary. It can also be blended.
  • an auxiliary agent such as inorganic fine particles (colloidal silica) for improving blocking resistance or slip resistance, and an antistatic agent for improving wettability, if necessary. It can also be blended.
  • the multilayer coating layer (B) is applied by a coating method such as gravure coating method, rod coating method, spray coating method, air knife coating method, roll coating method ( A2) can be applied on top.
  • a coating method such as gravure coating method, rod coating method, spray coating method, air knife coating method, roll coating method ( A2) can be applied on top.
  • the concentration of the resin is preferably adjusted to 0.1 to 40% by mass.
  • the surface of the heat-resistant coating layer (B) may be subjected to continuous surface treatment using corona discharge or plasma discharge under heating or in an inert gas atmosphere during the production of the heat-resistant olefin-based multilayer film.
  • the heat-resistant olefin-based multilayer film of the present invention is obtained as a substantially unstretched multilayer film by the above production method, secondary molding such as deep drawing by vacuum molding, foil pressing, embossing, etc. is also possible. .
  • a surface treatment on the resin layer (B) 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.
  • 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 includes a heat-sealable olefin-based multilayer film layer (A1) of the present invention as a heat seal layer, and the layers (A1) are stacked together to heat-seal, or the layer (A1) and the heat-resistant coat layer (B).
  • It is preferably a packaging bag formed with the layer (A1) on the inside by overlapping and heat-sealing. For example, after cutting out the two multilayer films into the desired size of a packaging bag and overlapping them to heat-seal three sides to form a bag, the contents are filled from one side that is not heat-sealed. It can be used as a packaging bag by heat sealing. Furthermore, it is also possible to form a packaging bag by sealing the upper and lower sides after sealing the end of a roll-shaped film into a cylindrical shape by an automatic packaging machine.
  • a lid of a packaging bag / container / container by heat-sealing with another film, sheet, or container heat-sealable with the layer (A1).
  • 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 coating agent was applied to an A4 size film at 5 g / m 2 with a bar coater, and the number of repellings was visually measured. ⁇ : No repelling. X: There are one or more repels.
  • 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.
  • Shrinkage / Wrinkle Test The appearance of the sealed portion of the flat bag which was subjected to horizontal (gap-attached) seal and vertical seal was evaluated by shrinkage and the state of film fusion to the heat seal bar and the condition of wrinkles. ⁇ : There is no shrinkage of the seal part, fusion to the seal bar and wrinkles, etc. ⁇ : There is some shrinkage of the seal part, fusion to the seal bar and wrinkles, etc. ⁇ : Shrinkage of the seal part, fusion to the seal bar and wrinkles Etc.
  • Preparation Example 2 of polyurethane coating agent (b-2) 1000 parts of the polyester polyol (b-1A) was dehydrated at 100 ° C. under reduced pressure, then cooled to 80 ° C., added with 886 parts of methyl ethyl ketone, sufficiently stirred and dissolved, added with 80 parts of neopentyl glycol, 250 parts of the cyanate was added and reacted at 75 ° C. for 8 hours to carry out the urethanization step.
  • the mixture was cooled to 50 ° C., neutralized with 73 parts of triethylamine, emulsified with 7000 parts of water, 10.6 parts of ethylenediamine and diethylenetriamine.
  • the chain extension was completed by adding 5 parts.
  • the concentration is adjusted by adding water, and it contains an aqueous polyurethane resin having a flow starting temperature of 195 ° C. with a nonvolatile content of 20%.
  • a polyurethane coating agent (b-2) was prepared.
  • 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)
  • a two-layered co-extruded multilayer film was obtained in which the thickness of each layer was 36 ⁇ m / 9 ⁇ m (total 45 ⁇ m).
  • the surface of the (A2) layer of the support was subjected to corona discharge treatment so that the wetting tension was 40 mN / m, and then the polyurethane coating agent (b-1) obtained in Preparation Example 1 was dried to a thickness of 5 ⁇ m.
  • the heat resistant olefin-based multilayer film of Example 1 was produced.
  • Example 2 A heat-resistant olefin-based multilayer film was prepared in the same manner as in Example 1 except that the polyurethane 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 multilayer film was produced in the same manner as in Example 1 except that the polyurethane coating agent (b-1) was applied so that the film thickness after drying was 3 ⁇ 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 multilayer 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 multilayer 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%.
  • Example 7 COPP of the resin layer (A1) of Example 5 was made of high-density polyethylene [density: 0.963 g / cm 3 , MFR: 7 g / 10 min (190 ° C., 21.18 N), melting point 130 ° C .; hereinafter referred to as “HDPE”.
  • a heat-resistant olefin-based multilayer film was produced in the same manner as in Example 5 except that the description was replaced.
  • Example 8 The COPP of the resin layer (A1) of Example 5 was made of low-density polyethylene [density: 0.905 g / cm 3 , MFR: 5.3 g / 10 min (190 ° C., 21.18 N), melting point 100 ° C .; In the same manner as in Example 5, except that the polyurethane coating agent (b-1) was applied so that the film thickness after drying was 10 ⁇ m, a heat-resistant olefin-based multilayer film was produced.
  • 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 No. 2, a heat-resistant olefin-based multilayer film was produced.
  • MA4 ethylene- (meth) acrylic acid copolymer
  • Example 10 A heat-resistant olefin-based multilayer film was produced in the same manner as in Example 1 except that the thickness of each layer of the layer structure (A1) / (A2) of Example 1 was 114 ⁇ m / 6 ⁇ m (total 120 ⁇ m).
  • Example 11 A heat-resistant olefin-based multilayer film was produced in the same manner as in Example 1 except that the thickness of each layer of the layer structure (A1) / (A2) of Example 1 was 90 ⁇ m / 30 ⁇ m (total 120 ⁇ m).
  • Comparative Example 1 An olefin-based multilayer film was produced in the same manner as in Example 1 except that the acid-modified olefin resin in the resin layer (A2) of Example 1 was replaced with COPP.
  • Comparative Example 2 An olefin-based multilayer film was produced in the same manner as in Comparative Example 1, except that the polyurethane coating agent (b-1) in Comparative Example 1 was replaced with the polyurethane coating agents (b-1) and (b-2).
  • Comparative Example 3 An olefin-based multilayer film was produced in the same manner as in Example 1 except that the acid-modified olefin-based resin in the resin layer (A2) of Example 1 was replaced with HDPE.

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Abstract

L'invention concerne une pellicule multicouche à base d'oléfine résistante à la chaleur qui est produite par l'application d'un agent de revêtement résistant à la chaleur sur une pellicule à base d'oléfine non étirée, présente une surface hautement résistante à la chaleur, peut être utilisée seule sans qu'il soit nécessaire d'employer une base étirée quelconque ou similaire et convient particulièrement à une utilisation dans une machine d'emballage, la force d'adhésion entre une couche de revêtement et la pellicule à base d'oléfine étant d'autre part excellente. L'invention concerne également un procédé de production de la pellicule multicouche à base d'oléfine résistante à la chaleur et un matériau d'emballage produit en employant la pellicule multicouche à base d'oléfine résistante à la chaleur. Plus précisément, on emploie une pellicule multicouche à base d'oléfine résistante à la chaleur caractérisée en ce qu'elle est produite en stratifiant une couche (A1) principalement constituée d'une résine de polyoléfine, une couche (A2) comprenant une résine d'oléfine modifiée par un acide et une couche de revêtement résistante à la chaleur (B) dans l'ordre suivant : (A1)/(A2)/(B), le rapport de l'épaisseur de la couche (A2) à l'épaisseur totale des couches (A1) et (A2) étant de 5 à 40 % et la couche de revêtement résistante à la chaleur (B) étant une couche comprenant un agent de revêtement à base de polyuréthane (b).
PCT/JP2012/066144 2011-06-27 2012-06-25 Pellicule multicouche à base d'oléfine résistante à la chaleur, son procédé de production et matériau d'emballage comprenant celle-ci WO2013002176A1 (fr)

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JP2016106063A (ja) * 2013-03-06 2016-06-16 Dic株式会社 積層フィルム及び包装材
JP2019521877A (ja) * 2016-05-31 2019-08-08 ダウ グローバル テクノロジーズ エルエルシー コーティングされたフィルムおよびそれから形成されるパッケージ
WO2022173414A1 (fr) * 2021-02-09 2022-08-18 Amcor Flexibles North America, Inc. Film d'emballage et emballage
WO2023199751A1 (fr) * 2022-04-12 2023-10-19 Dic株式会社 Corps stratifié et matériau d'emballage

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JP7435918B1 (ja) 2022-04-12 2024-02-21 Dic株式会社 積層体、及び包装材

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