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
  • B32B27/06—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
  • B32B27/10—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 paper or cardboard
• • 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
  • B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
• • 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
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/582—Tearability
• • 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
  • B32B2307/70—Other properties
  • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
  • B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
• • 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
  • B32B2307/70—Other properties
  • B32B2307/732—Dimensional properties
  • B32B2307/734—Dimensional stability
• • 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
• • 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
  • B32B2439/70—Food packaging
• • 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
  • B32B2439/80—Medical packaging

Definitions

• the present invention relates to a laminate comprising a paper base material that can be suitably used as a packaging material for pharmaceuticals, foods, industrial parts, cosmetics, sanitary products, miscellaneous goods, etc.
• the present invention relates to a laminate obtained by heat-sealing a multilayer film and a paper base material, which is good and has good openability, printability, laminateability, moisture resistance, packaging machineability, curl resistance and the like.
• a bag made of a laminate of cellophane / polyethylene or cellophane / aluminum foil / polyethylene has been put to practical use as a packaging material with good hand tearability that can be easily opened by tearing by hand, which does not require special processing.
• cellophane is hygroscopic, so the physical properties change due to humidity is large, dimensional stability is inferior, curling, blocking, etc. are suitable for laminating, printing, bag making, packaging machinery, etc. There was a problem.
• a part of a bag made of a laminate of cellophane / polyethylene, cellophane / aluminum foil / polyethylene, etc. is attached to the exterior paper.
• Simple packaging is used. In a form in which a packaging bag is formed in units of several or several tablets and sold separately, there is no space for describing the above-mentioned medicinal ingredients, food ingredients, usage methods, etc., and therefore an outer paper is essential.
• the adhesion between cellophane and paper may be by adhesive or sealant coating or by thermal fusion, but thermal fusion is often used because of cost and environmental considerations.
• thermal fusion is often used because of cost and environmental considerations.
• cellophane has heat resistance, high-temperature heating is necessary, adhesion to paper by heat melting is very difficult, and strength is weak. Further, in order to increase the strength, high heat and high pressure are required as sealing conditions. As a result, the fused portion is dirty, looks bad, causes a reduction in commercial value, and improvement is required.
• Polyester films have been proposed as an alternative to cellophane (see, for example, Patent Document 1).
• Patent Document 1 Since the initial tear strength is high, special processing such as cutting of V notches and fine continuous holes is essential. .
• a packaging bag made of a syndiotactic polystyrene resin layer has also been proposed (see, for example, Patent Document 2).
• polystyrene is generally poor in moisture resistance, and packaging of contents with high hygroscopicity such as powders and tablets causes discoloration, deterioration of contents components, and the like, so that the storage period is limited.
• a method of providing an intermediate layer made of polyethylene resin without using an adhesive is provided (for example, see Patent Document 3).
• the sealant film and the paper base material can be bonded without having an adhesive application step, and the adhesive strength with the paper base material can be maintained even when the fusing temperature is relatively low.
• the surface of a resin layer made of a polyethylene resin is generally not printable, and the printed surface is often peeled off over time, which is not suitable as a packaging material.
• the paper base material's easy-opening properties are hindered, resulting in the need to form notches for opening and the like. It is not a thing with.
• the present invention has been made in view of the above problems, and is a packaging material that has good adhesiveness to paper and can be easily opened by tearing by hand without requiring special processing.
• a multilayer film and a paper base material that can be suitably used as a packaging material that has little change in physical properties due to humidity, no curling, excellent dimensional stability, and good laminating, printing, and packaging machine suitability. It is providing the laminated body of this, and a packaging material using the same.
• the present inventors have identified a cyclic olefin resin (a resin layer mainly composed of a cyclic olefin resin and a resin layer mainly composed of an olefin resin other than the cyclic olefin.
• the present inventors have found that the above-mentioned problems can be solved by using a multilayer film laminated so as to have a configuration, and have completed the present invention.
• the present invention provides a resin layer (A1) mainly composed of a cyclic olefin resin (a1) having a glass transition temperature Tg of 130 ° C. or higher, and a resin mainly composed of an olefin resin (b1) not containing a cyclic structure.
• a multilayer film (I) having a multilayer structure in which a layer (B1) and a resin layer (A2) mainly composed of a cyclic olefin resin (a2) are laminated in the order of (A1) / (B1) / (A2)
• a laminate obtained by thermally fusing the resin layer (A1) and the paper substrate (II), and a packaging material using the laminate are provided.
• the laminate of the present invention can be easily opened by tearing by hand without special processing, and can provide a packaging material with good hand cutting properties.
• heat sealing heat sealing
• the multilayer film used for the laminate does not change in physical properties due to humidity, curling can be suppressed, dimensional stability is excellent, and blocking is difficult to occur. From these things, it is excellent in laminating, printing, and packaging machine suitability, and content deterioration due to moisture absorption can be suppressed. Further, it has an appropriate heat seal strength and can be suitably used for pharmaceuticals, foods, industrial materials and the like.
• the multilayer film (I) used in the present invention comprises a resin layer (A1) mainly composed of a cyclic olefin resin (a1) having a glass transition temperature Tg of 130 ° C. or higher, and an olefin resin (b1) not containing a cyclic structure.
• a multilayer structure in which a resin layer (B1) having a main component and a resin layer (A2) having a cyclic olefin resin (a2) as a main component are laminated in the order of (A1) / (B1) / (A2). It is essential to have other layers, and other layers may be further laminated on the resin layer (A2).
• “main component” means that the specific resin is contained in an amount of 50% by mass or more based on the total mass of the resin components used for forming the resin layer. Means to contain at 60 mass% or more.
• the resin used for the resin layers (A1) and (A2) on both surfaces is described later.
• the cyclic olefin-based resin may be a main component, and both layers may be made of the same material or different resin species. Moreover, the same kind of resin in which only the glass transition temperature is different may be used.
• the cyclic olefin-based resins (a1) and (a2) may be described without distinction.
• Examples of the cyclic olefin-based resin that is the main component of the resin layers (A1) and (A2) in the present invention include, for example, norbornene-based polymers, vinyl alicyclic hydrocarbon polymers, and cyclic conjugated diene polymers. Among these, 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”).
• 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 glass transition temperature Tg of the cyclic olefin-based resin can be easily adjusted depending on the type of monomer used, the type and ratio of other monomers used for copolymerization, the molecular weight, and the like.
• the norbornene monomer used as the raw material for the norbornene polymer is an alicyclic monomer having a norbornene ring.
• Examples of such norbornene-based monomers include norbornene, tetracyclododecene, ethylidene norbornene, vinyl norbornene, ethylidetetracyclododecene, dicyclopentadiene, dimethanotetrahydrofluorene, phenyl norbornene, methoxycarbonyl norbornene, methoxy And carbonyltetracyclododecene. 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.
• the glass transition temperature Tg of the cyclic olefin-based resin (a1) needs to maintain the viewpoint and rigidity for heat-sealing the resin layer (A1) of the resulting multilayer film (I) and the paper substrate,
• the temperature is 130 ° C. or higher, and the multilayer film (I) can be produced by the coextrusion lamination method, and an industrial raw material.
• Tg is preferably 200 ° C. or lower.
• the temperature is particularly preferably 130 ° C to 180 ° C.
• the content ratio of the norbornene monomer is preferably in the range of 40 to 90% by weight, more preferably 50 to 90% by weight, still more preferably 60 to 85%. % By weight.
• the glass transition temperature Tg in this invention is a value obtained by measuring by DSC.
• the resin layer (A1) when the bag is made and the contents are filled, the inner layer is sealed with the resin layer (A1) outside. Considering packaging suitability, the resin layer (A1) needs to have heat resistance. Therefore, it is desirable to use a norbornene polymer in which the Tg of the cyclic olefin resin (a1) used for the resin layer (A1) is 150 ° C. or higher. .
• norbornene copolymers with a high glass transition temperature Tg have low tensile strength, and are extremely easy to break and tear easily. It is also possible to blend a low Tg product with a glass transition temperature of less than 100 ° C.
• a norbornene-based copolymer with a Tg of less than 100 ° C By blending the coalescence, the falling bag strength and heat sealability can be improved. It is also effective to blend a polyolefin resin, an elastomer resin, or the like, such as a polypropylene resin or a polyethylene resin that is compatible with COC and does not contain a cyclic structure.
• the cyclic olefin resin (a1) used for the resin layer (A1) which is the outermost surface the cyclic olefin resin (a1) having a Tg of 130 ° C. or more as described above is used.
• A2) is a low-Tg resin when a cyclic olefin-based resin having a Tg of 100 ° C. or less is used alone or when a cyclic olefin-based resin having a Tg of 100 ° C. or more and a resin having a Tg of 100 ° C. or less are mixed. It is preferable to use the compound in an increased amount.
• the multilayer film (I) having a multilayer structure in which another resin layer is further laminated as described later on the resin layer (A2) is also effective in controlling the drop strength.
• examples of the ring-opening polymer (COP) of the norbornene-based monomer include “ZEONOR” manufactured by Nippon Zeon Co., Ltd.
• examples of the coalescence (COC) include “Appel” manufactured by Mitsui Chemicals, Inc. and “TOPAS” manufactured by Polyplastics.
• the surface of the resin layer containing the cyclic olefin-based resin as a main component has excellent surface gloss and can maintain a high quality as a packaging material. Moreover, since transparency is also favorable, it can be used as a packaging material having contents visibility.
• Examples of the olefin resin (b1) that does not include a cyclic structure, which is the main component of the resin layer (B1) in the present invention, include various ethylene resins and propylene resins, and the resin layer (A1) and the resin layer. from adhesion and hand cutting property of the control of the cycloolefin resin used as a main component of (A2), the density of the olefin resin (b1) is 0.88 g / cm 2 or more 0.940 g / cm 2 less than A propylene- ⁇ -olefin random copolymer polymerized using an ethylene resin and / or a metallocene catalyst is preferred.
• ethylene resin examples include polyethylene resins such as very low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), and low density polyethylene (LDPE), ethylene-vinyl acetate copolymer (EVA), and ethylene-methyl.
• VLDPE very low density polyethylene
• LLDPE linear low density polyethylene
• LDPE low density polyethylene
• EVA ethylene-vinyl acetate copolymer
• ethylene-methyl ethylene-methyl
• Methacrylate copolymer EMMA
• ethylene-ethyl acrylate copolymer EAA
• EMA ethylene-methyl acrylate copolymer
• E-EA-MAH ethylene-ethyl acrylate-maleic anhydride copolymer
• Ethylene copolymers such as ethylene-acrylic acid copolymer (EAA) and ethylene-methacrylic acid copolymer (EMAA); further, ionomers of ethylene-acrylic acid copolymers and ionomers of ethylene-methacrylic acid copolymers Alone or in combination of two or more. It may be.
• VLDPE, LDPE, and LLDPE are preferable because of a good balance between sealing properties and hand cutting properties.
• the LDPE may be a branched low density polyethylene obtained by a high pressure radical polymerization method, and is preferably a branched low density polyethylene obtained by homopolymerizing ethylene by a high pressure radical polymerization method.
• LLDPE is a low-pressure radical polymerization method using a single-site catalyst, with ethylene monomer as the main component, and comonomer as an ⁇ -olefin such as butene-1, hexene-1, octene-1, 4-methylpentene. Are copolymerized.
• the comonomer content in LLDPE is preferably in the range of 0.5 to 20 mol%, more preferably in the range of 1 to 18 mol%.
• the single site catalyst examples include various single site catalysts such as a metallocene catalyst system such as a combination of a metallocene compound of Group IV or V transition metal of the periodic table and an organoaluminum compound and / or an ionic compound.
• the single-site catalyst has a uniform active site, so the molecular weight distribution of the resulting resin is sharper than a multi-site catalyst with a non-uniform active site. This is preferable because a resin having physical properties excellent in stability of sealing strength and anti-blocking property can be obtained.
• the density of the ethylene-based resin is preferably 0.88 to 0.94 g / cm 3 . If the density is within this range, it has moderate rigidity, excellent mechanical strength such as heat seal strength and pinhole resistance, and film film formability and extrusion suitability are improved.
• the melting point is preferably lower than the Tg of the cyclic olefin resin (a1), and the preferred melting point range is determined depending on the cyclic olefin resin used. It is preferably in the range of 0 ° C., more preferably 70 to 120 ° C. If melting
• the MFR (190 ° C., 21.18 N) of the ethylene resin is preferably 2 to 20 g / 10 minutes, and more preferably 3 to 10 g / 10 minutes. When the MFR is within this range, the extrusion moldability of the film is improved.
• propylene resin examples include propylene homopolymer, propylene / ⁇ -olefin random copolymer, such as propylene-ethylene copolymer, propylene-butene-1 copolymer, propylene-ethylene-butene-1 copolymer.
• propylene resin examples include propylene homopolymer, propylene / ⁇ -olefin random copolymer, such as propylene-ethylene copolymer, propylene-butene-1 copolymer, propylene-ethylene-butene-1 copolymer.
• coalesced metallocene catalyst polypropylene These may be used alone or in combination. Desirable is a propylene- ⁇ -olefin random copolymer, and a propylene / ⁇ -olefin random copolymer polymerized using a metallocene catalyst as described above is particularly preferable.
• the heat resistance of the film is improved and the softening temperature can be increased, so that boiling at 100 ° C. or lower, hot filling, or 100 ° C. or higher is achieved. It can also be used as a packaging material having excellent steam / high pressure heat sterilization characteristics such as retort sterilization.
• these propylene resins preferably have an MFR (230 ° C.) of 0.5 to 30.0 g / 10 min and a melting point of 110 to 165 ° C., more preferably an MFR (230 ° C.) of 2
• the melting point is 115 to 162 ° C. at 0 to 15.0 g / 10 min. If MFR and melting
• the melting point is selected in relation to the glass transition temperature Tg of the cyclic olefin resin, as described for the ethylene resin.
• the resin layer (A1), the resin layer (B1), and the resin layer (A2) are in the order of (A1) / (B1) / (A2). It has a multi-layer structure laminated on each other. That is, by sandwiching a resin layer mainly composed of an olefin resin between resin layers mainly composed of a cyclic olefin resin, a film having both hand cutting properties, moisture resistance and suitability for packaging machinery is obtained.
• the film has a higher level of rigidity, hand cutting property and moisture resistance, and also has packaging machine characteristics.
• the thickness of the resin layer (B1) is preferably 30 to 80% of the total thickness of the multilayer film (I), and laminated so as to be 40 to 70%. Is more preferable.
• the multilayer film (I) having only the multilayer structure (A1) / (B1) / (A2) is used as the laminate of the present invention, particularly when it is heat-sealed to form a bag or the like, heat-sealing
• the Tg of the cyclic olefin resin used for the resin layer (A1) and the resin layer (A2) is different.
• the cyclic olefin resin used for the heat-sealing resin layer (A2) is a low Tg product
• the cyclic olefin resin used for the outermost resin layer (A1) is a high Tg product, Good suitability for packaging machines such as bag making and filling packaging.
• any of those described for the resin layer (B1) can be preferably used, and the preferred resin types are the same. It is.
• the resin type used for the resin layer (B1) disposed between the resin layer (A1) and the resin layer (A2) is the same as the resin type used for the resin layer (B2) laminated on the resin layer (A2). It may be different or different.
• a four-layer multilayer film (I) having the structure of (A1) / (B1) / (A2) / (B2), which has a higher level of film rigidity, hand cutting and moisture resistance, and a packaging machine
• the total thickness of the resin layer (B1) and the resin layer (B2) is preferably 40 to 95% of the total thickness of the multilayer structure, and 50 to 90 It is more preferable to laminate so that it may become%.
• Each of the resin layers (A1), (B1), (A2), and (B2) laminated as necessary includes an antifogging agent, an antistatic agent, a thermal stabilizer, a nucleating agent, an antioxidant, and a lubricant.
• an anti-blocking agent, a release agent, an ultraviolet absorber and a colorant can be added within a range not impairing the object of the present invention.
• the outermost resin layer (A1) and the outermost resin layer (A2) in the case of a multilayer film having a three-layer structure, a four-layer structure The friction coefficient of the outermost resin layer (B2) in the case of the multilayer film is preferably 1.5 or less, and more preferably 1.0 or less. Therefore, the resin layer corresponding to the surface layer of the multilayer film (I) It is preferable to add a lubricant, an antiblocking agent and an antistatic agent as appropriate.
• the multilayer film (I) used in the present invention preferably has a film thickness of 15 to 100 ⁇ m, more preferably 20 to 90 ⁇ m. If the thickness of the film is within this range, stable hand cutting properties, laminating suitability, packaging machine suitability, excellent moisture resistance, heat sealability, and the like are easily obtained.
• the surface (one side and / or both sides) of the surface resin layer is treated so that the surface tension of the surface is 40 dyne / cm or more, preferably 42 dyne / cm or more.
• treatment methods 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 resin layer containing a cyclic olefin-based resin is less likely to deteriorate with the lapse of time in corona treatment, and has good printability on the surface of the resin layer (A2) in the case of a resin film (A1) or a multilayer film having a three-layer structure.
• aluminum deposition on the resin layer (A2), application of an anchor coating agent, and the like are also good.
• multilayer film (I) used by this invention
• a method such as a coextrusion multilayer die method or a feed block method.
• co-extrusion method in which the film is formed into a film by inflation or T-die / chill roll method.
• This coextrusion method is preferable because the thickness ratio of each layer can be adjusted relatively freely, and a multilayer film excellent in hygiene and cost performance can be obtained.
• the difference between the melting point and the Tg is large between them.
• the film appearance deteriorates and it is difficult to form a uniform layer structure.
• a T-die / chill roll method that can perform melt extrusion at a relatively high temperature is preferable.
• the resin layer (B2) is laminated on the resin layer (A2) as described above.
• Applies various laminating methods such as dry lamination that is bonded by applying an adhesive, thermal lamination that is bonded by thermocompression of a heating roll, and extrusion lamination, and (A1) / (B1) / (A2) / It is also possible to form a multilayer structure (B2).
• thermoplastic resin films can be further laminated to provide further moisture resistance and barrier properties, or to provide light shielding properties to suppress the photodegradation of the contents.
• a special heat seal resin satisfying the above performance is further applied to the surface opposite to the resin layer (A1).
• a film having a special heat-sealable resin may be laminated to form a heat-seal layer, or a film having a special heat-sealable resin may be laminated by extrusion to form a heat-seal layer.
• the multilayer film (I) used in the present invention is obtained as a substantially unstretched multilayer film by the above production method, secondary molding such as deep drawing molding or embossing by vacuum molding becomes possible.
• the multilayer film (I) used in the present invention uses a cyclic olefin resin as a component of the resin layer, thereby preventing adsorption of volatile components from the contents to the film (I) and providing a water vapor barrier property. Also have. From this, it can be suitably used as a packaging material used for foods, medicines, industrial parts, cosmetics, sanitary, miscellaneous goods, etc., and in particular, a packaging bag with good hand-cutability that can be easily opened by tearing by hand. Can be provided. Multilayer film (I) itself has little change in physical properties due to humidity, curling can be suppressed, dimensional stability is excellent, and blocking is difficult to occur, so it can be laminated and printed, and is suitable for packaging machinery. In addition, it can be suitably used for pharmaceuticals, foods, and the like from the viewpoint of excellent heat seal strength.
• the laminated body of the present invention forms a packaging bag in which the above-described multilayer film (I) is formed with the resin layer (A1) surface-treated as necessary as the outermost layer and the opposite resin layer as the inner side. It is preferable that the paper base (II) is heat-sealed to the resin layer (A1) which is the surface. For example, after cutting out the two sheets of the multilayer film (I) into a desired size of a packaging bag, overlapping them and heat-sealing three sides to form a bag, the contents from one side not heat-sealed Fill and heat seal.
• the paper substrate (II) is heat-sealed at the same or different part from the place to be heat-sealed. If the paper base material (II) is heat-sealed so as not to overlap the contents, it is possible to prevent the contents from being thermally deteriorated and poorly sealed.
• the paper base material (II) can be made into a packaging bag in which efficacy and the like are described by preliminarily describing matters relating to the contents by printing or hand-drawing.
• the resin layer (A1) that is the outermost surface of the multilayer film (I) is subjected to matters relating to the contents and various designs by printing, etc. By heat-sealing, a packaging material with a larger amount of information can be obtained.
• the paper substrate (II) used in the present invention is not particularly limited, and coated paper, art paper, high-quality paper, Kent paper, inkjet paper, rayon paper, synthetic paper, and the like can be used.
• An anti-blocking agent may be applied or embossed to improve printability and packaging suitability.
• the thickness is preferably in the range of 0.07 mm to 0.3 mm, and more preferably in the range of 0.09 to 0.2 mm from the viewpoint of good handling.
• Example 1 As a resin for the surface resin layer (A1), a ring-opening polymer of a norbornene-based monomer [“Apel APL6015T” manufactured by Mitsui Chemicals, MFR: 10 g / 10 min (260 ° C., 21.18 N), glass transition temperature: 145 ° C .; hereinafter referred to as “COC (1)”. ] was used.
• a resin for the opposite resin layer (A2) a ring-opening polymer of a norbornene-based monomer [“Apel APL8008T” manufactured by Mitsui Chemicals, Inc., MFR: 15 g / 10 min (260 ° C., 21.18 N), glass transition temperature: 70 ° C .; hereinafter referred to as “COC (4)”.
• COC (4) glass transition temperature
• linear medium density polyethylene [density: 0.930 g / cm 3 , melting point 125 ° C., MFR: 5 g / 10 min (190 ° C., 21.18 N); " ] was used.
• These resins were respectively supplied to an extruder for a surface resin layer (A1) (A2) (caliber 40 mm) and an extruder for a resin layer (B1) (caliber 50 mm) and melted at 200 to 270 ° C.
• the resin is supplied to a T-die / chill roll co-extrusion multi-layer film production apparatus (feed block and T-die temperature: 250 ° C.) having a feed block, and co-melt extrusion is performed.
• the layer structure of the film is (A1) /
• a coextruded multilayer film (X1) having a three-layer configuration of (B1) / (A2) and a thickness of each layer of 2 ⁇ m / 16 ⁇ m / 2 ⁇ m (total 20 ⁇ m) was obtained.
• the surface of the resin layer (A1) was subjected to corona treatment, and the surface tension by the wetting reagent was 45 dyne / cm.
• Example 2 As a resin for the resin layer (A1), a ring-opening polymer of a norbornene-based monomer [“TOPAS 6017” manufactured by Polyplastics Co., Ltd., MFR: 10 g / 10 minutes (260 ° C., 21.18 N), glass transition temperature: 170 ° C. Hereinafter referred to as “COC (2)”. ] 90 parts by mass and linear low density polyethylene [density: 0.900 g / cm 3 , melting point 85 ° C., MFR: 5 g / 10 min (190 ° C., 21.18 N); hereinafter referred to as “LLDPE”. 10 parts by mass of a resin mixture was used.
• LLDPE linear low density polyethylene
• the resin for the resin layer (A2) a resin mixture of 50 parts by mass of COC (1) and 50 parts by mass of COC (4) was used. Moreover, LMDPE was used as resin for resin layers (B1). Co-extruded multilayer in the same manner as in Example 1 so that the layer structure of the film is (A1) / (B1) / (A2), and the thickness of each layer is 2 ⁇ m / 16 ⁇ m / 2 ⁇ m (total 20 ⁇ m). A film (X2) was obtained. The surfaces of the resin layers (A1) and (A2) were subjected to corona treatment, and the surface tension by the wetting reagent was 45 dyne / cm.
• Low density polyethylene (density: 0.920 g / cm 3 ) in which 2% of an antistatic agent (“Elester Master” manufactured by Kao) is blended on the resin layer (A2) of the coextruded multilayer film (X2) obtained above. , Melting point 115 ° C., MFR: 10 g / 10 min (190 ° C., 21.18 N); hereinafter referred to as “LDPE”. ] was subjected to extrusion lamination of 20 ⁇ m by melt extrusion.
• Elester Master manufactured by Kao
• Example 3 LLDPE was used as the resin for the resin layer (B1).
• a coextruded multilayer film was produced in the same manner as in Example 2 so that the thickness of each layer of the film was 4 ⁇ m / 12 ⁇ m / 4 ⁇ m (total 20 ⁇ m), to obtain a coextruded multilayer film (X3).
• the surfaces of the resin layers (A1) and (A2) were subjected to corona treatment, and the surface tension by the wetting reagent was 45 dyne / cm.
• Example 4 As the resin for the resin layers (A1) and (A2), a resin mixture of 50 parts by mass of COC (1) and 50 parts by mass of COC (4) was used. Moreover, LMDPE was used as resin for the resin layer (B1). LLDPE was used as the resin for the resin layer (B2). The resin layer (B2) was supplied to an extruder (40 mm in diameter), and the other resin layer resins were supplied in the same manner as in Example 1. The resin was melted at 200 to 270 ° C., and the melted resin was fed with a T having a feed block.
• Co-extrusion extrusion is carried out by supplying each to a die-chill roll co-extrusion multilayer film production apparatus (feed block and T-die temperature: 250 ° C.), and the layer structure of the film is (A1) / (B1) / (A2)
• a coextruded multilayer film (X4) having a four-layer structure of / (B2) and a thickness of each layer of 6 ⁇ m / 15 ⁇ m / 6 ⁇ m / 3 ⁇ m (total 30 ⁇ m) was obtained.
• the surface of the resin layer (A1) was subjected to corona treatment, and the surface tension by the wetting reagent was 45 dyne / cm.
• Example 5 A resin mixture of 70 parts by mass of COC (1) and 30 parts by mass of COC (4) was used as the resin for the resin layer (A1) on the surface, and MRCP was used as the resin for the resin layer (B1) of the inner layer. COC (4) was used for the inner resin layer (A2).
• a coextruded multilayer film was produced in the same manner as in Example 1 so that the thickness of each layer of the film was 2 ⁇ m / 16 ⁇ m / 2 ⁇ m (total 20 ⁇ m), to obtain a coextruded multilayer film (X5).
• the surface resin layers (A1) and (A2) were subjected to corona treatment, and the surface tension by the wetting reagent was 45 dyne / cm.
• the resin layer (A2) of the coextruded multilayer film (X5) obtained above was dry-laminated with an aluminum foil (thickness 12 ⁇ m) coated with a urethane-based adhesive to 3 g / m 2 , and a laminated film (Y5 ) Furthermore, a urethane adhesive was applied to the aluminum side of the Y5 film to 3 g / m 2, and after drying, an LDPE film (melting point: 110 ° C., manufactured by Phutamura Chemical Co., Ltd., hereinafter referred to as LLDPE-1) was subjected to a dry lamination of 20 ⁇ m. (Z5) was obtained.
• Example 6 COC (1) as the resin for the resin layer (A1) on the surface, ring-opening polymer of norbornene monomer as the resin for the resin layer (A2) on the inner layer [“APEL AP6013T” manufactured by Mitsui Chemicals, MFR: 15 g / 10 min (260 ° C., 21.18 N), glass transition temperature: 125 ° C .; hereinafter referred to as “COC (3)”. ] was used.
• LLDPE was used as the resin for the resin layer (B1).
• a coextruded multilayer film was produced in the same manner as in Example 1 so that the thickness of each layer of the film was 2.5 ⁇ m / 20 ⁇ m / 2.5 ⁇ m (total 25 ⁇ m), to obtain a coextruded multilayer film (X6).
• the resin layers (A1) and (A2) were subjected to corona treatment, and the surface tension by the wetting reagent was 45 dyne / cm.
• the resin layer (A2) of the coextruded multilayer film (X6) obtained above was dry laminated with aluminum foil in the same manner as in Example 5 to obtain a laminated film (Y6).
• Example 7 As the resin for the resin layers (A1) and (A2), a resin mixture of 50 parts by mass of COC (2) and 50 parts by mass of COC (4) was used. Moreover, LLDPE was used as resin for the resin layer (B). A coextruded multilayer film was produced in the same manner as in Example 1 so that the thickness of each layer of the film was 8 ⁇ m / 9 ⁇ m / 8 ⁇ m (total 25 ⁇ m), to obtain a coextruded multilayer film (X7). The resin layers (A1) and (A2) were subjected to corona treatment, and the surface tension by the wetting reagent was 43 dyne / cm.
• the resin layer (A2) of the coextruded multilayer film (X7) obtained above was dry laminated with aluminum foil in the same manner as in Example 5 to obtain a laminated film (Y7).
• Low density polyethylene density: 0.920 g / cm 3
• 2% of an antistatic agent (“Elester Master” manufactured by Kao) is blended in the resin layer (A2) of the coextruded multilayer film (Y2) obtained above.
• LDPE-1 Low density polyethylene
• Example 8 As a resin for the resin layer (A1) on the surface, 70 parts by mass of COC (2) and high-density polyethylene [density: 0.960 g / cm 3 , melting point 128 ° C., MFR: 10 g / 10 min (190 ° C., 21.18 N) Hereinafter referred to as “HDPE”. 30 parts by mass of a resin mixture was used. Moreover, LLDPE was used as resin for the resin layer (B1). As the resin for the inner resin layer (A2), a resin mixture of 50 parts by mass of COC (1) and 50 parts by mass of COC (4) was used.
• a coextruded multilayer film was produced in the same manner as in Example 1 so that the thickness of each layer of the film was 9 ⁇ m / 12 ⁇ m / 9 ⁇ m (total 30 ⁇ m), to obtain a coextruded multilayer film (X8).
• the surface resin layers (A1) and (A2) were subjected to corona treatment, and the surface tension by the wetting reagent was 41 dyne / cm.
• the resin laminate (A2) of the coextruded multilayer film (X8) obtained above was subjected to extrusion lamination of 20 ⁇ m by melt extrusion of LDPE containing 0.2% of an antistatic agent.
• Example 9 As a resin for the resin layer (A1) on the surface, a resin mixture of 80 parts by mass of COC (1), 10 parts by mass of LLDPE and 10 parts by mass of HDPE was used. COC (4) was used as the resin for the inner resin layer (A2). LMDPE was used as the resin for the intermediate resin layer (B1). Furthermore, VLLDPE was used as the resin for the resin layer (B2) laminated on the inner resin layer (A2). A coextruded multilayer film was produced in the same manner as in Example 1 so that the thickness of each layer of the film was 18 ⁇ m / 40 ⁇ m / 18 ⁇ m / 14 ⁇ m (total 90 ⁇ m), to obtain a coextruded multilayer film (X9).
• the surface resin layer (A1) was subjected to corona treatment, and the surface tension by the wetting reagent was 45 dyne / cm.
• Example 10 As the resin for the resin layers (A1) and (A2), a resin mixture of 50 parts by mass of COC (1) and 50 parts by mass of COC (4) was used. LMDPE was used as the resin for the intermediate resin layer (B1). VLLDPE was used as the resin for the outermost resin layer (B2). A coextruded multilayer film was produced in the same manner as in Example 1 so that the thickness of each layer of the film was 10 ⁇ m / 25 ⁇ m / 10 ⁇ m / 5 ⁇ m (total 50 ⁇ m), to obtain a coextruded multilayer film (X10).
• the surface resin layer (A1) was subjected to corona treatment, and the surface tension by the wetting reagent was 43 dyne / cm.
• Example 11 As the resin for the resin layers (A1) and (A2), a resin mixture of 50 parts by mass of COC (1) and 50 parts by mass of COC (4) was used.
• LMDPE was used as the resin for the intermediate resin layer (B1).
• LLDPE was used as the resin for the outermost resin layer (B2).
• a coextruded multilayer film was produced in the same manner as in Example 1 so that the thickness of each layer of the film was 6 ⁇ m / 15 ⁇ m / 6 ⁇ m / 3 ⁇ m (total 30 ⁇ m), to obtain a coextruded multilayer film (X11).
• the surface resin layer (A1) was subjected to corona treatment, and the surface tension by the wetting reagent was 43 dyne / cm.
• the resin layer (B2) of the coextruded multilayer film (X11) obtained above was dry-laminated with aluminum foil and LLDPE-1 in the same manner as in Example 5 to obtain a laminated film (Z6).
• Comparative Example 1 COC (1) was used as the resin for the surface resin layer.
• As an intermediate layer resin homopolypropylene [density: 0.900 g / cm 3 , melting point 160 ° C., MFR: 7 g / 10 min (230 ° C., 21.18 N); hereinafter referred to as “PP”. ] was used.
• a coextruded multilayer film was produced in the same manner as in Example 1 so that the thickness of each layer of the film was 10 ⁇ m / 10 ⁇ m (total 20 ⁇ m), and a coextruded multilayer film was obtained.
• the surface resin layer was subjected to corona treatment, and the surface tension by the wetting reagent was 40 dyne / cm.
• the LDPE blended with 0.2% of an antistatic agent as a heat-sealable resin in the intermediate resin layer of the coextruded multilayer film obtained above was subjected to extrusion lamination of 20 ⁇ m by melt extrusion.
• Comparative Example 2 COC (3) was used as the resin for the surface resin layer.
• LMDPE was used as the intermediate layer resin.
• a coextruded multilayer film was produced in the same manner as in Example 1 so that the thickness of each layer of the film was 36 ⁇ m / 4 ⁇ m (total 40 ⁇ m), to obtain a coextruded multilayer film (Y2).
• the surface resin layer was subjected to corona treatment, and the surface tension by the wetting reagent was 40 dyne / cm.
• Comparative Example 3 COC (3) was used as the resin for the surface resin layer.
• VLDPE was used as the intermediate layer resin.
• a coextruded multilayer film was produced in the same manner as in Example 1 so that the thickness of each layer of the film was 0.5 ⁇ m / 19 ⁇ m / 0.5 ⁇ m (total 20 ⁇ m), to obtain a coextruded multilayer film (Y2).
• the surface resin layer was subjected to corona treatment, and the surface tension by the wetting reagent was 40 dyne / cm.
• Comparative Example 4 COC (1) was used as the resin for the surface resin layer.
• LMDPE was used as the intermediate layer resin.
• a coextruded multilayer film was produced in the same manner as in Example 2 so that the thickness of each layer of the film was 4 ⁇ m / 36 ⁇ m (total 40 ⁇ m), to obtain a coextruded multilayer film (Y2).
• the surface resin layer was subjected to corona treatment, and the surface tension by the wetting reagent was 40 dyne / cm.
• Comparative Example 5 HDPE was used as the resin for the surface resin layer.
• LMDPE was used as the intermediate layer resin.
• a coextruded multilayer film was produced in the same manner as in Example 1 so that the thickness of each layer of the film was 4 ⁇ m / 100 ⁇ m (total 104 ⁇ m), to obtain a coextruded multilayer film (Y3).
• the surface resin layer was subjected to corona treatment, and the surface tension by the wetting reagent was 38 dyne / cm.
• the extrusion lamination of 20 ⁇ m was carried out by melt extrusion using MRCP containing 0.2% of an antistatic agent on the intermediate layer side of the coextruded multilayer film (Y3) obtained above.
• Comparative Example 6 LDPE blended with 0.2% of an antistatic agent as a heat-sealable resin on Cellophane (# 300) manufactured by Futamura Chemical Co., Ltd. was subjected to extrusion lamination of 20 ⁇ m by melt extrusion.
• Packing machine suitability under high humidity
• the film before thermal fusion with the paper base material prepared in the examples and comparative examples is subjected to vertical pillow packaging at 33 ° C and 80% humidity under the following conditions using an automatic packaging machine. Done and made a bag.
• Packaging machine Rika Kaken Co., Ltd. Unipacker NUV472
• Horizontal seal speed 30 bags / min, vertical heat seal temperature 150 ° C, air gauge pressure 4kg / cm 2 , resin layers that have not been surface-treated while changing from horizontal heat seal temperature 120 ° C to 160 ° C in increments of 10 ° C Sealed.
• 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. ⁇ : No shrinkage of seal part, fusion to seal bar, wrinkles, etc. ⁇ : Some shrinkage of seal part, fusion to seal bar, wrinkles, etc. Etc.
• Adhesiveness with paper substrate Coated paper 0.1 mm was used as a paper substrate.
• the multilayer films obtained in the above Examples and Comparative Examples were sealed with a paper base material at a seal temperature of 230 ° C., a seal pressure of 0.4 MPa, and a seal time of 1 second.
• the seal shape was a two-wire seal with a width of 0.2 mm.
• the film sealed under the above conditions was naturally cooled at 23 ° C., and then a test piece was cut into a strip shape having a width of 15 mm.
• the test piece was peeled 90 ° at a rate of 300 mm / min using a tensile tester (manufactured by A & D Co., Ltd.) in a thermostatic chamber at 23 ° C. and 50% RH, and the heat seal strength was measured.
• the heat sealability was evaluated according to the following criteria from the obtained heat seal strength value.
• ⁇ Heat seal strength is 50 g / 15 mm width or more.
• X Heat seal strength is less than 50 g / 15 mm width.

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