JPWO2015029877A1 - Barrier laminate and packaging material using the same - Google Patents

Abstract

Provided are a barrier laminate formed by laminating a sealant film and a base material and a packaging material using the same, which can suppress elution of adhesive components that are specifically regulated while maintaining seal strength To do. Specifically, in the laminate having the structure of the base material / adhesive layer / sealant film, the sealant film comprises a cyclic olefin resin (a1) having a Tg of 160 ° C. or less and an MFR of 0.5 to 30 g / 10 minutes. The thickness which consists of a resin composition which contains an olefin resin (a2) and contains (a1) at 30 mass% or more in the total mass of (a1) and (a2) is in the range of 0.5 to 20 μm. A film having one or more layers (A), and in the layer (A), (a1) and (a2) form a layered phase separation structure, or a continuous layer of (a1) In addition, a barrier laminate is used in which a phase separation structure in which (a2) is dispersed in an island shape is formed.

Description

  The present invention provides a barrier laminate capable of effectively suppressing elution of components such as an adhesive and printing ink into contents in a laminate comprising a base material and a sealant film bonded together, It is related with the packaging material which uses this.

  Flexible packaging using plastic materials is used worldwide as a packaging material for food, and it is showing an increasing trend as it spreads to emerging countries. On the other hand, there have been reports of cases where substances that are likely to have health effects on humans are dissolved and transferred to food from specific packaging materials. The elution of bisphenol A due to the inner surface paint of dishes and cans, the elution of printing ink components, and the elution of mineral oil mixed in the carton box, etc., have increased consumer awareness of the safety and hygiene of packaging materials. Yes.

  In Europe, regulations on packaging materials that come into contact with foods are becoming increasingly strict, and regulations have been revised as the Commission Regulations on Plastic Materials and Products (EU No. 10/2011), and complete construction will take place over the next few years. It is supposed to be. In addition, research on the elution and safety of printing inks and laminating adhesives that are not in direct contact with food is being conducted, and in the future, such non-contact materials will be regulated. According to the rules of the committee on plastic materials and products, elution from a plastic film as a composite bonded with an adhesive is also restricted, and consideration for non-contact materials is also necessary. In Switzerland, there is an elution regulation for components such as ink and adhesive as Swiss SR SR817.023.21, and the necessity of complying with regulations is already increasing in sales activities in Europe.

  Under such circumstances, a composite film obtained by laminating a sealant film using a blend resin of a cyclic olefin copolymer and a sealant polymer on a substrate by various methods has been proposed as a low-elution packaging material (for example, see Patent Document 1).

  However, depending on the combination of the cyclic olefin copolymer and the sealant polymer and the blend ratio thereof, sufficient barrier properties and sealing strength as a packaging material may not be exhibited. Further, in the examples, the thickness of the resin layer is 60 μm, an excessive cost is expected, and the overall thickness of the packaging material also increases, which can be said to be an environmentally friendly packaging material. is not.

  In addition, the low-elution packaging material is sealed with water, extracted under specific conditions, concentrated, and evaluated as a low molecular weight substance based on the peak area of UV absorption spectrum and gas chromatograph mass spectrometry (GC-MS). However, the eluted substances are unknown, and there is no mention of suppression of substances that are specifically regulated in Europe.

JP 2000-343648 A

  In view of the above circumstances, an object of the present invention is to provide a sealant film and a substrate that can suppress elution of adhesive components that are specifically regulated while maintaining the sealing strength necessary for general laminate packaging materials. Is to provide a barrier laminate and a packaging material using the same.

  As a result of intensive studies to solve such problems, the present inventor has found that in the laminate having the structure of the base material / adhesive layer / sealant film, the sealant film includes a specific cyclic olefin resin and a specific olefin resin. Since a layer using a resin mixture that is formulated with a specific ratio spontaneously forms a phase separation structure, it is possible to effectively suppress the elution component from the adhesive layer, and specifically regulate The present invention has been completed by finding that it is possible to prevent the transferred target substance from being transferred to the contents.

  That is, the present invention provides a laminate having a structure of a base material / adhesive layer / sealant film, wherein the sealant film includes at least a cyclic olefin resin (a1) having a glass transition temperature Tg of 160 ° C. or less, and a melt flow rate. MFR (230 degreeC, 21.18N) contains the olefin resin (a2) which does not have a cyclic structure of 0.5-30 g / 10min, The said cyclic olefin resin (a1) and the said olefin resin ( A film having one or more layers (A) having a thickness in the range of 0.5 to 20 μm comprising a resin composition containing 30% by mass or more of the cyclic olefin-based resin (a1) in the total mass of a2). And in the layer (A), the cyclic olefin resin (a1) and the olefin resin (a2) form a layered phase separation structure, or A barrier laminate having a phase-separated structure in which the olefin resin (a2) is dispersed in an island shape in a continuous layer of the cyclic olefin resin (a1), and using the same A packaging material is provided.

  The laminate of the present invention effectively captures a substance that is likely to be eluted from the adhesive and suppresses the shift to the contents while having an appropriate sealing strength as a packaging material even if it is a thin film. be able to. Therefore, it can be suitably used as an environmentally friendly packaging material containing foods, medicines and the like as contents.

2 is a transmission micrograph of the cross section of the sealant film obtained in Example 1. FIG. 6 is a transmission micrograph of the cross section of the sealant film obtained in Example 5. FIG.

  Below, each part which comprises the laminated body of this invention is explained in full detail.

  The laminate of the present invention has a configuration of base material / adhesive layer / sealant film. This sealant film is formed in advance as a single-layer or multilayer film, and is obtained by laminating it with another substrate by various methods.

  In the present invention, at least the cyclic olefin resin (a1) having a glass transition temperature Tg of 160 ° C. or lower and the melt flow rate MFR (230 ° C., 21.18 N) are 0.5 to 30 g / 10 min. The olefin-based resin (a2) having no cyclic structure, and 30 masses of the cyclic olefin-based resin (a1) in the total mass of the cyclic olefin-based resin (a1) and the olefin-based resin (a2). % Or more of a layer (A) having a thickness in the range of 0.5 to 20 μm, and the cyclic olefin resin (a1) in the layer (A). ) And the olefin resin (a2) form a layered phase separation structure, or the olefin resin (a2) in a continuous layer of the cyclic olefin resin (a1). It is essential that but has a layer which forms a phase separation structure which is dispersed like islands.

  That is, if two or more kinds of resins are blended to give a barrier property, and a layered or sea-island structure can be spontaneously formed, low molecular weight components contained in an adhesive or the like can be effectively captured. Alternatively, based on the assumption that the transition to the contents can be suppressed by the maze effect, as a result of examining the combination of resin types forming the target phase separation structure, the specific cyclic olefin resin and the cyclic structure The combination with the olefin resin which does not have was discovered.

  Increasing the thickness of the film is effective for exhibiting barrier properties, but on the other hand, there are problems with cost and productivity. Furthermore, a thick laminate is formed into a secondary shape or a bag shape. There is also a problem that the formability at the time is inferior. In particular, food packaging materials often become waste immediately without being reused, and the use of packaging materials made of thick films has been avoided from the viewpoint of environmental protection. From these viewpoints, the demand for thin packaging materials is also high, and balancing the barrier properties and thin film properties is the most important requirement item on the market.

  The layer (A) in the sealant film of the present invention must have a thickness of 0.5 to 20 μm from the above viewpoint, and even a resin layer thinner than the conventional one is effective. It is characterized by having a barrier property. In applications where the demand for thinning is high, the effect of the present invention is not impaired even if the thickness is 10 μm or less.

  The resin composition used for the layer (A) is required to contain the cyclic olefin resin (a1) at 30% by mass or more in the composition.

  The cyclic olefin resin (a1) is not particularly limited in its structure as long as the glass transition temperature Tg is 160 ° C. or lower. For example, a norbornene polymer, a vinyl alicyclic hydrocarbon polymer 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”). Furthermore, COP and COC hydrogenates are particularly preferred. The weight average molecular weight of the cyclic olefin resin is preferably 5,000 to 500,000, more preferably 7,000 to 300,000. The 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 a 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, and examples of such 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.

  Further, the glass transition temperature Tg of the cyclic olefin resin (a1) is a layered structure or a phase separation structure having a sea-island structure spontaneously in a combination with the olefin resin (a2) described later in the obtained layer (A). From the viewpoint of forming the film, it is essential that the temperature is 160 ° C. or lower, and particularly preferably from 130 ° C. or lower from the viewpoint of easily forming the target phase separation structure. In addition, the glass transition temperature Tg in this invention is a value obtained by measuring by DSC. In addition, the target phase separation structure is easy when the cyclic olefin resin (a1) is a norbornene polymer having a melt flow index MFR (230 ° C., 21.18 N) of 0.2 to 17 g / 10 min. Is more preferable than

  As a commercially available product that can be used as the cyclic olefin resin (a1), examples of the ring-opening polymer (COP) of the norbornene monomer include “ZEONOR” manufactured by Nippon Zeon Co., Ltd., and norbornene. Examples of the system copolymer (COC) include “Appel” manufactured by Mitsui Chemicals, Inc., “TOPAS” manufactured by Polyplastics Co., Ltd., and the like.

  The olefin resin (a2) having no cyclic structure used in combination with the cyclic olefin resin (a1) has a melt flow rate MFR (230 ° C., 21.18 N) of 0.5 to 30 g / 10 min. This is essential, and in particular, from the viewpoint of good film formability, it is preferably 2 to 20 g / 10 minutes. Furthermore, when the difference from the MFR (230 ° C., 21.18N) of the cyclic olefin-based resin (a1) is 5 g / 10 min or more, it is preferable from the viewpoint that the phase separation structure is more easily developed. .

  The olefin resin (a2) may be any homopolymer or copolymer of olefin having no cyclic structure, and examples thereof include ethylene resins and propylene resins.

  Examples of the ethylene resin 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. Methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate (EMA) copolymer, ethylene-ethyl acrylate-maleic anhydride copolymer (E-EA-MAH), Ethylene copolymers such as ethylene-acrylic acid copolymer (EAA) and ethylene-methacrylic acid copolymer (EMAA); further, ionomer of ethylene-acrylic acid copolymer, ionomer of ethylene-methacrylic acid copolymer Used alone or in combination of two or more. And it may be.

  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.

  As LLDPE, an ethylene monomer is the main component by a low-pressure radical polymerization method using a single site catalyst, and an α-olefin such as butene-1, hexene-1, octene-1, 4-methylpentene is used as a comonomer. Are copolymerized. As a comonomer content rate in LLDPE, it is preferable that it is the range of 0.5-20 mol%, and it is more preferable that it is the range of 1-18 mol%.

  Examples of the single-site catalyst include various single-site catalysts such as metallocene catalyst systems such as combinations of metallocene compounds of Group IV or V transition metals and organoaluminum compounds and / or ionic compounds. In addition, 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 0.880 to 0.948 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. Moreover, it is preferable that melting | fusing point is lower than Tg of the said cyclic olefin resin (a1), Although the range of a preferable melting | fusing point is determined by the cyclic olefin resin to be used, Generally 60-130 It is preferable that it is the range of degreeC, and 70-120 degreeC is more preferable. When the melting point is within this range, the processing stability and coextrusion processability with the cyclic olefin resin are improved, and further, there is flexibility, so that the pinhole resistance is also improved.

  Examples of the propylene resin include propylene homopolymer, propylene / α-olefin random copolymer, such as propylene-ethylene copolymer, propylene-butene-1 copolymer, propylene-ethylene-butene-1 copolymer. Examples include coalesced metallocene catalyst polypropylene. These may be used alone or in combination. Desirably, it is a propylene-α-olefin random copolymer, and a propylene / α-olefin random copolymer polymerized using a metallocene catalyst as described above is particularly preferable. When these propylene-based resins are used, the heat resistance of the film is improved and the softening temperature can be increased, so that steam such as boiling at 100 ° C. or lower, hot filling, or retort sterilization at 100 ° C. or higher is used. -It can also be used as a packaging material with excellent high-pressure heat sterilization characteristics.

  These propylene resins preferably have an MFR (230 ° C.) of 0.5 to 30.0 g / 10 minutes and a melting point of 110 to 165 ° C., more preferably an MFR (230 ° C.) of 2 0.0-15.0 g / 10 min, melting point is 115-162 ° C. If MFR and melting | fusing point are this range, the film-forming property of a film will improve. Of course, the melting point is selected in relation to the glass transition temperature Tg of the cyclic olefin resin, as described for the ethylene resin.

  Among these, by forming a film by mixing with the cyclic olefin-based resin (a1), a melting point of 120 ° C. or higher, a melt flow rate MFR (230 ° C.) from the viewpoint of easily developing a layered or sea-island phase separation structure. 21.18N) is preferably a propylene-based resin of 0.5 to 30 g / 10 min.

  Moreover, in the layer (A) in the sealant film of the present invention, the cyclic olefin resin (a1) is 30% by mass or more in the total mass of the cyclic olefin resin (a1) and the olefin resin (a2). It is essential that the resin composition is contained, and it is particularly preferable that the resin composition is contained in the range of 30 to 70% by mass from the viewpoint of easily expressing the target phase separation structure.

  In the present invention, the cyclic olefin resin (a1) and the olefin resin (a2) form a layered phase separation structure, or the olefinic resin is formed in a continuous layer of the cyclic olefin resin (a1). Whether or not the resin (a2) forms a phase-separated structure in which islands are dispersed is confirmed by observing the cross section of the film in the state of a sealant film or a laminate with a transmission electron microscope. Is possible. When dispersed in a layered manner, the thickness of one layer is about 20 to 100 nm, and by forming a plurality of such extremely thin layers, a barrier property is obtained when a laminated body is formed. Can be considered a thing.

  In addition, the phase separation structure in which the olefin resin (a2) is dispersed in an island shape in the continuous layer of the cyclic olefin resin (a1) has a relatively high blending ratio of the cyclic olefin resin (a1). Specifically, it is easy to develop when the cyclic olefin resin (a1) is 60% by mass or more in the total mass of the cyclic olefin resin (a1) and the olefin resin (a2). One size of the olefin-based resin (a2) dispersed in islands in the cyclic olefin-based resin (a1) is about 30 to 180 nm as the longest portion, and the longitudinal direction when processed as a sealant film It is preferable to obtain a bar-like shape that extends slightly. By forming such phase separation, it can be considered that the barrier property is expressed by the so-called maze effect that prevents the substance eluted from the adhesive layer from passing through.

  In the laminate of the present invention, the layer (A) having the specific phase separation structure described above may be a sealant film composed of a single layer film having at least one layer, but various performances as a packaging material (rigidity, sealability) Etc.) is preferably a multilayer film having at least one layer (A), and in particular, it is a multilayer film having at least three layers from the viewpoint of excellent balance between productivity, film formability and barrier property. A multilayer film having a layer mainly composed of an olefin resin having no cyclic structure on both sides of the layer (A) is preferable.

  At this time, the resin for forming the layer laminated on both sides of the layer (A) is not particularly limited as long as it can maintain interlayer adhesion with the layer (A). From the viewpoint of producing the multilayer film, the above-mentioned ethylene-based resin or propylene-based resin is preferable, in particular, a so-called linear low-density polyethylene which is a copolymer of ethylene and a small amount of other olefins, or A propylene resin produced with a metallocene catalyst is preferred. The resin forming the layer laminated on both sides of the layer (A) may be the same as or different from the olefin resin (a2) used for the layer (A), and two or more olefins may be used. It may be a mixed resin of a series resin.

  When the sealant film in the present invention is a single-layer film composed of the layer (A), the thickness thereof is in the range of 0.5 to 20 μm as described above. As described above, when a multilayer film is used, the thickness of the layer (A) can be reduced, which is advantageous from the viewpoint of cost. The total thickness of the film in this case is preferably in the range of 15 to 150 μm from the viewpoint of ease of use as a packaging material, and in particular in the range of 20 to 100 μm, film formation is easy. It is more preferable than the point.

  Further, from the viewpoint of obtaining an appropriate seal strength when using the laminate as a packaging material and effectively expressing the barrier property, when the sealant film is a multilayer film, the total thickness of the layer (A) It is preferable that the ratio to is in the range of 10 to 70%.

  The layer (A) and a layer composed of an olefin-based resin laminated on both sides as necessary are provided with an antifogging agent, an antistatic agent, a thermal stabilizer, a nucleating agent, an oxidation, within a range not impairing the effects of the present invention. Components such as an inhibitor, a lubricant, an antiblocking agent, a release agent, an ultraviolet absorber, and a colorant can be added. In particular, the coefficient of friction of the surface of the sealant film is preferably 1.5 or less, and more preferably 1.0 or less in order to impart processing suitability during film forming and packaging suitability of the filling machine. It is preferable to add a lubricant, an antiblocking agent or an antistatic agent to the resin layer corresponding to the surface layer as appropriate.

  In the sealant film used in the present invention, it is preferable to treat the surface (one side and / or both sides) of the surface resin layer so that the surface tension of the surface is 35 to 45 mN / m. Examples of such 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. By performing such a surface treatment, when the post-process such as printing or adhesive application is applied to the sealant film, the coating property of the ink and the adhesive is improved, and the adhesion with the ink and the adhesive is improved. It is excellent and it becomes easy to avoid problems such as dropout and delamination.

  The method for producing the sealant film used in the present invention is not particularly limited. For example, a resin or a resin mixture used for each layer of the multilayer film is heated and melted in separate extruders, and a co-extrusion multilayer die method or a feed block is used. Examples thereof include a coextrusion method in which a film is laminated in a molten state by a method such as a method and then formed into a film shape by inflation, a T-die / chill roll method, or the like. This coextrusion method is preferable because the thickness ratio of each layer can be adjusted relatively freely, and a film having excellent hygiene and cost performance can be obtained. Further, when ethylene resin is used for both outer surface layers of the layer (A) containing the cyclic olefin resin used in the present invention, the difference between the melting point and Tg is large between the two, so that the film during coextrusion processing The appearance may be deteriorated, and it may be difficult to form a uniform layer structure. In order to suppress such deterioration, a T-die / chill roll method that can perform melt extrusion at a relatively high temperature is preferable.

  When a multilayer air-cooled inflation method is used as a method for producing a sealant film, an apparatus generally used in the market may be used. General air-cooled inflation equipment consists of an extruder, annular die, cooling ring, blower, guide plate, pinch roll, corona treatment device, winding device, etc. Equipped with multi-layer die. The production conditions by the multi-layer inflation method are not particularly limited as long as the characteristics of the present invention are not impaired, but it is preferable to use a resin having characteristics that can maintain the stability of bubbles when extruded from an annular die. When forming layers on both sides of the layer (A), an ethylene resin or a propylene resin similar to the olefin resin (a2) described above can be used, but a specific MFR is used in terms of bubble stability. It is desirable to use this resin. In the case of an ethylene-based resin, MFR (190 ° C., 21.18 N) is preferably 0.1 to 5 g / 10 minutes, and more preferably 0.5 to 4 g / 10 minutes. In the case of a propylene-based resin, MFR (230 ° C., 21.18 N) is preferably 0.1 to 5 g / 10 minutes, and more preferably 0.5 to 4 g / 10 minutes. If the MFR of the resin used for both surface layers is within this range, even if the cyclic olefin resin (a1) is used as it is, the bubbles are stable and the extrusion moldability is improved.

  Also, after laminating a three-layer multilayer structure using the above-described coextrusion lamination method, if high heat seal strength, hot tackiness or high packaging speed is required, the side to be further bonded to the substrate On the opposite surface, apply a special heat-sealable resin that satisfies the above performance, or laminate a film with a special heat-sealable resin to form a heat-seal layer, or a film with a special heat-sealable resin May be extrusion laminated to form a heat seal layer.

  The sealant film obtained above is used by being bonded to another base material, but the other base material that can be used at this time is not particularly limited. From the viewpoint of easily exhibiting the effect, it is preferable to use a plastic substrate, particularly a biaxially stretched resin film. For applications that do not require transparency, aluminum foils can be used alone or in combination.

  Examples of the stretched resin film include biaxially stretched polyester (PET), biaxially stretched polyester (PET), biaxially stretched polypropylene (OPP), biaxially stretched polyamide (PA), and ethylene vinyl alcohol copolymer (EVOH). ) Is a coextruded biaxially stretched polypropylene, biaxially stretched ethylene vinyl alcohol copolymer (EVOH), and coextruded biaxially stretched polypropylene coated with polyvinylidene chloride (PVDC). These may be used alone or in combination.

  The laminate of the present invention is a film obtained by laminating the base material on the sealant film obtained by the above production method. Examples of the lamination method include dry lamination, wet lamination, non-solvent lamination, extrusion lamination, and the like. It laminates | stacks through an adhesive layer by the method of.

  Examples of the adhesive used in the dry lamination include a polyether-polyurethane adhesive and a polyester-polyurethane adhesive. Various pressure-sensitive adhesives can be used, but a pressure-sensitive pressure-sensitive adhesive is preferably used. Examples of the pressure-sensitive adhesive include, for example, a polyisobutylene rubber, a butyl rubber, a rubber adhesive in which a mixture thereof is dissolved in an organic solvent such as benzene, toluene, xylene, hexane, or a bisethylene acid rosin in the rubber adhesive. A blend of tackifiers such as ester, terpene / phenol copolymer, terpene / indene copolymer, or 2-ethylhexyl acrylate / n-butyl acrylate copolymer, 2-ethylhexyl acrylate / ethyl acrylate / Examples thereof include an acrylic pressure-sensitive adhesive prepared by dissolving an acrylic copolymer having a glass transition point of −20 ° C. or less such as a methyl methacrylate copolymer in an organic solvent.

  The adhesive for laminating is generally cured by polyol / isocyanate and is often used for high-functional applications such as retort applications. Conventionally, the bonding is generally a combination of an aluminum foil and a sealant film. However, with the advent of transparent vapor deposition technology, various transparent vapor deposition films that have both barrier properties and transparency have become commercially available, and in addition to the demand for improved visibility of contents, transparent vapor deposition films and sealant films Bonding is increasing.

  Therefore, it is common to add a silane coupling agent such as epoxy silane or aminosilane silane to the adhesive in order to provide adhesion between these films and the deposited film.

  However, if the amount of epoxy silane is increased in order to maintain adhesion, the dissolution of epoxy silane into the food will increase. Further, when the same adhesive is used for laminating a film without vapor deposition, the silane coupling agent is eluted more than in the vapor deposition configuration, and the configuration requires the replacement of the adhesive.

  As a polyol used for the adhesive for laminating, for example, a polyol itself described later, or a polyester polyol obtained by reacting a polyol with a polycarboxylic acid described later, or ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Ethylene oxide, propylene oxide, butylene starting from compounds having two active hydrogen atoms such as trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc. Examples thereof include polyethers obtained by addition polymerization of monomers such as oxide, styrene oxide, epichlorohydrin, tetrahydrofuran and cyclohexylene.

  Examples of the polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 1,6-hexane. Diol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1 , 4-cyclohexanedimethanol, triethylene glycol, polycaprolactone diol, dimer diol, bisphenol A, hydrogenated bisphenol A, and other glycols Polyesters obtained by ring-opening polymerization reaction of cyclic ester compounds such as propiolactone, butyrolactone, ε-caprolactone, δ-valerolactone, β-methyl-δ-valerolactone, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol , Ethylene oxide, propylene oxide, starting with compounds having two active hydrogen atoms such as trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc. Examples include polyethers obtained by addition polymerization of monomers such as butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexylene.

  Examples of the polycarboxylic acids include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid. Acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p , P'-dicarboxylic acids and anhydrides or ester-forming derivatives of these dicarboxylic acids; p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, ester-forming derivatives of these dihydroxycarboxylic acids, dimer acids, etc. Of the polybasic acids.

  Examples of the polyisocyanate include organic compounds having at least two isocyanate groups in the molecule. Examples of the organic polyisocyanate include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), lysine diisocyanate, trimethylhexamethylene diisocyanate, 1 , 3- (isocyanatomethyl) cyclohexane, 1,5-naphthalene diisocyanate, polyisocyanate such as triphenylmethane triisocyanate; adducts of these polyisocyanates, burettes of these polyisocyanates, or of these polyisocyanates Derivatives (modified products) of polyisocyanates such as isocyanurates are exemplified.

  Moreover, you may use what reacted the said isocyanate and the said polyol with the mixing ratio from which an isocyanate group becomes excess.

  In the adhesive, the equivalent ratio polyol / isocyanate of the hydroxyl group equivalent of the polyol and the isocyanate equivalent of the polyisocyanate is preferably 0.5 to 5.0.

  Examples of the epoxy silane include methacrylic silane coupling agents such as 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycid Examples thereof include xylpropyltriethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

<Regulations in Europe>
In Switzerland, Swiss Ordinance SR817.002.21 has legalized elution regulations for inks and coating agents that do not come into contact with food, and is currently the only positive list (PL) of food non-contact materials in the world. This PL is classified according to whether the toxicity data of the substance is known or unknown, and is provided with a specific migration limit (SML).

  Epoxysilane has unknown toxicity data, and SML is considered to be less than 10 μg / kg-food.

  The laminate of the present invention can be preferably used as various packaging materials. Examples of the packaging material include packaging bags, containers, container lids, and the like used for foods, medicines, cosmetics, sanitary products, industrial parts, miscellaneous goods, magazines, and the like. In particular, elution from the adhesive layer to the contents can be effectively suppressed, and contamination to the contents can be prevented, so that it can be suitably used for foods and pharmaceuticals.

  The packaging bag is a packaging bag in which the inner surface (surface opposite to the base material) of the laminate of the present invention is overlapped and heat-sealed, or the inner surface and base material are overlapped and heat-sealed, so that the inner surface is the inner side. Preferably there is. For example, after cutting out the two laminated bodies into the desired size of the 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 end of a roll-shaped film into a cylindrical shape by an automatic packaging machine and then sealing the top and bottom.

  It is also possible to form a lid of a packaging bag / container / container by heat-sealing with another film, sheet or container that can be heat-sealed with the inner surface layer. In that case, as another film to be used, a film or sheet of LDPE, EVA, polypropylene or the like having relatively low mechanical strength can be used.

  In the packaging material using the laminate of the present invention, in order to weaken the initial tear strength and improve the openability, the seal portion has an arbitrary tear start portion such as a V notch, an I notch, a perforation, and a micropore. It may be formed.

  Next, the present invention will be described in more detail with reference to examples and comparative examples.

<Adhesive>
Preparation Example 1 [Main agent preparation example]
In a polyester reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, rectification tube, moisture separator, etc., 10.0 parts of ethylene glycol, 21.1 parts of neopentyl glycol, 10.0 of 1,6-hexanediol Part, 8.0 parts of Tsunodim 216, 21.5 parts of isophthalic acid, 21.5 parts of terephthalic acid, 23.4 parts of adipic acid and 0.006 parts of titanium catalyst, the upper temperature of the rectifying tube exceeds 100 ° C The internal temperature was kept at 240 ° C. by gradually heating so as not to occur. The reaction was further continued until the acid value became 2 mgKOH / g or less. The pressure was reduced to 10 mmHg or less and held for 1.5 hours to complete the esterification reaction, and an intermediate polyester polyol having a hydroxyl value of 28 was obtained. To 100 parts of the obtained intermediate polyester polyol, 8.9 parts of isophorone diisocyanate was added and heated to 120 ° C. to carry out a urethanization reaction until NCO% was 3.1 to obtain a polyester urethane polyisocyanate. . This was diluted with 111.9 parts of ethyl acetate and then the temperature was lowered to 40 ° C. and kept at 50 ° C. for about 1 hour to obtain a polyurethane polyester polyol resin solution U having a nonvolatile content of 60%.

Adjustment Example 2 [Additive]
Epoxysilane is 3-glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Silicone), aminosilane is 3-aminopropyltrimethoxysilane (KBM-903 manufactured by Shin-Etsu Silicone), and phosphoric acid is manufactured by Wako Pure Chemical Industries, Ltd. 85. As the% phosphoric acid, styrene-maleic anhydride copolymer (SMA), a reagent of Mw 7,500 manufactured by Wako Pure Chemical Industries, Ltd. was used.

Example 1
As a resin for the layer (A), a melting point of 164 ° C., an MFR of 8 g / 10 min (230 ° C., 21.18 N), 60% by mass of a propylene homopolymer, an MFR of 11 g / 10 min (230 ° C., 21.18 N), a glass transition temperature (Tg) A resin mixture of 40% by mass of a ring-opening polymer of a norbornene monomer at 80 ° C. or lower was used. A propylene homopolymer having a melting point of 164 ° C. and an MFR of 8 g / 10 min (230 ° C., 21.18 N) was used as the layer resin on the adhesive layer side of the layer (A). As the resin for the surface layer (seal layer) on the opposite surface, a propylene-ethylene copolymer having a melting point of 127 ° C. and MFR of 7 g / 10 minutes (230 ° C., 21.18 N) was used.

  These resins are respectively supplied to an extruder for layer (A) (caliber 50 mm), an extruder for adhesive layer side layer (laminate layer) (caliber 50 mm), and an extruder for seal layer extruder (caliber 50 mm). The melted resin is melted at 200 to 250 ° C., and the melted resin is supplied to a T-die / chill roll co-extruded multilayer film production apparatus (feed block and T-die temperature: 250 ° C.) having a feed block to perform co-melt extrusion. Thus, a sealant film having a total thickness of 30 μm in which the layer structure of the film was a three-layer structure of laminate layer / layer (A) / sealing layer and the thickness ratio of each layer was 20/60/20% was obtained.

About the obtained film, the TEM observation was performed about the cross section perpendicular | vertical to a flow direction, and a horizontal direction, and the dispersion state was observed. Moreover, with the composition shown in Table 1, polyurethane polyester polyol resin solution U, aromatic polyisocyanate (DIC Corporation KW-75), and a silane compound were blended to prepare an adhesive blend with a solid content of 30%. About the obtained adhesive compound, it apply | coated so that application quantity might be set to 2.2 g / m < ² >, the 12-micrometer-thick aluminum foil and sealant film were bonded together, and it was set as the laminated body, and the elution test was done. Similarly, a biaxially stretched polyester film having a thickness of 12 μm and a sealant film were bonded together to measure the seal strength.

Example 2
As a resin for the layer (A), a melting point of 164 ° C., an MFR of 8 g / 10 min (230 ° C., 21.18 N), 60% by mass of a propylene homopolymer, an MFR of 11 g / 10 min (230 ° C., 21.18 N), a glass transition temperature (Tg) A resin mixture of 40% by mass of a ring-opening polymer of a norbornene monomer at 80 ° C. or lower was used. An ethylene-hexene copolymer (linear polyethylene) having a density of 0.938 g / cm ³ , a melting point of 127 ° C., and an MFR of 3.5 g / 10 minutes (190 ° C., 21.18 N) was used as the resin for the laminate layer. An ethylene-hexene copolymer (linear polyethylene) having a density of 0.918 g / cm ³ , a melting point of 115 ° C., and an MFR of 3.5 g / 10 minutes (190 ° C., 21.18 N) was used as the sealing layer resin. In the same manner as in Example 1, a sealant film having a total thickness of 30 μm and a thickness ratio of laminate layer / layer (A) / seal layer of 63/7/30% was obtained. A laminate was obtained in the same manner as in Example 1 using the obtained sealant film.

Example 3
As a resin for the layer (A), a melting point of 164 ° C., an MFR of 8 g / 10 min (230 ° C., 21.18 N), 60% by mass of a propylene homopolymer, an MFR of 1 g / 10 min (230 ° C., 21.18 N), a glass transition temperature (Tg) A resin mixture of 40% by mass of a ring-opening polymer of a norbornene monomer at 160 ° C. was used. As a resin for the laminate layer, a propylene homopolymer having a melting point of 164 ° C. and an MFR of 8 g / 10 minutes (230 ° C., 21.18 N) was used. As the resin for the sealing layer, a propylene-ethylene copolymer having a melting point of 127 ° C. and MFR of 7 g / 10 minutes (230 ° C., 21.18 N) was used. In the same manner as in Example 1, a sealant film having a total thickness of 30 μm and a thickness ratio of laminate layer / layer (A) / seal layer of 20/60/20% was obtained. A laminate was obtained in the same manner as in Example 1 using the obtained sealant film.

Example 4
As a resin for the layer (A), a melting point of 127 ° C., an MFR of 7 g / 10 min (230 ° C., 21.18 N), 60% by mass of a propylene homopolymer, an MFR of 11 g / 10 min (230 ° C., 21.18 N), a glass transition temperature (Tg) A resin mixture of 40% by mass of a ring-opening polymer of a norbornene monomer at 80 ° C. or lower was used. As a resin for the laminate layer, a propylene homopolymer having a melting point of 164 ° C. and an MFR of 8 g / 10 minutes (230 ° C., 21.18 N) was used. As the resin for the sealing layer, a propylene-ethylene copolymer having a melting point of 127 ° C. and MFR of 7 g / 10 minutes (230 ° C., 21.18 N) was used. In the same manner as in Example 1, a sealant film having a total thickness of 30 μm and a thickness ratio of laminate layer / layer (A) / seal layer of 20/60/20% was obtained. A laminate was obtained in the same manner as in Example 1 using the obtained sealant film.

Example 5
As a resin for the layer (A), a melting point of 164 ° C., an MFR of 8 g / 10 min (230 ° C., 21.18 N), 20% by mass of a propylene homopolymer, an MFR of 11 g / 10 min (230 ° C., 21.18 N), a glass transition temperature (Tg) A resin mixture of 80% by mass of a ring-opening polymer of norbornene-based monomer at 80 ° C. or lower was used. As a resin for the laminate layer, a propylene homopolymer having a melting point of 164 ° C. and an MFR of 8 g / 10 minutes (230 ° C., 21.18 N) was used. As the resin for the sealing layer, a propylene-ethylene copolymer having a melting point of 127 ° C. and MFR of 7 g / 10 minutes (230 ° C., 21.18 N) was used. In the same manner as in Example 1, a sealant film having a total thickness of 30 μm and a thickness ratio of laminate layer / layer (A) / seal layer of 63/7/30% was obtained. A laminate was obtained in the same manner as in Example 1 using the obtained sealant film.

Example 6
As a resin for the layer (A), a density of 0.943 g / cm ³ , an MFR of 2.5 g / 10 minutes (190 ° C., 21.18 N) of ethylene-hexene copolymer (linear polyethylene) of 70% by mass, an MFR of 11 g / A resin mixture of 30% by mass of a ring-opening polymer of a norbornene monomer having a glass transition temperature (Tg) of 80 ° C. or lower for 10 minutes (230 ° C., 21.18 N) was used. An ethylene-hexene copolymer (linear polyethylene) having a density of 0.943 g / cm ³ and an MFR of 2.5 g / 10 min (190 ° C., 21.18 N) was used as the resin for the laminate layer. An ethylene-hexene copolymer (linear polyethylene) having a density of 0.918 g / cm ³ , a melting point of 115 ° C., and an MFR of 3.5 g / 10 minutes (190 ° C., 21.18 N) was used as the sealing layer resin. In the same manner as in Example 1, a sealant film having a total thickness of 30 μm and a thickness ratio of laminate layer / layer (A) / seal layer of 30/60/10% was obtained. A laminate was obtained in the same manner as in Example 1 using the obtained sealant film.

Example 7
As a resin for the layer (A), 65% by mass of a propylene-ethylene copolymer having a melting point of 140 ° C. and an MFR of 3.0 g / 10 minutes (230 ° C., 21.18 N) and an MFR of 11 g / 10 minutes (230 ° C., 21.18 N) A resin mixture of 35% by mass of a ring-opening polymer of norbornene monomer having a glass transition temperature (Tg) of 80 ° C. or lower was used. As a resin for the laminate layer, a propylene homopolymer having a melting point of 164 ° C. and an MFR of 8 g / 10 minutes (230 ° C., 21.18 N) was used. As the resin for the sealing layer, a propylene-ethylene copolymer having a melting point of 140 ° C. and MFR of 3.0 g / 10 min (230 ° C., 21.18 N) was used. In the same manner as in Example 1, a sealant film having a total thickness of 30 μm and a thickness ratio of laminate layer / layer (A) / seal layer of 30/60/10% was obtained. A laminate was obtained in the same manner as in Example 1 using the obtained sealant film.

Example 8
As a resin for the layer (A), 30% by mass of a propylene-ethylene copolymer having a melting point of 140 ° C. and MFR of 8 g / 10 minutes (230 ° C., 21.18 N), MFR of 1 g / 10 minutes (230 ° C., 21.18 N), glass A resin mixture containing 70% by mass of a ring-opening polymer of a norbornene monomer having a transition temperature (Tg) of 160 ° C. was used. A propylene homopolymer having a melting point of 164 ° C. and an MFR of 8 g / 10 min (230 ° C., 21.18 N) was used as the resin for the laminate layer. A propylene-ethylene copolymer having a melting point of 140 ° C. and MFR of 8 g / 10 min (230 ° C., 21.18 N) was used as the intermediate layer resin. A propylene-ethylene copolymer having a melting point of 127 ° C. and MFR of 7 g / 10 min (230 ° C., 21.18 N) was used as the sealing layer resin. In the same manner as in Example 1, a sealant film having a total thickness of 30 μm and a thickness ratio of laminate layer / intermediate layer / layer (A) / seal layer of 23/40/7/30% was obtained. A laminate was obtained in the same manner as in Example 1 using the obtained sealant film.

Example 9
As a resin for the layer (A), a melting point of 140 ° C., MFR 3.5 g / 10 min (230 ° C., 21.18 N) of propylene-ethylene copolymer 60% by mass, MFR 11 g / 10 min (230 ° C., 21.18 N) A resin mixture of 40% by mass of a ring-opening polymer of norbornene monomer having a glass transition temperature (Tg) of 80 ° C. or lower was used. A propylene homopolymer having a melting point of 160 ° C. and an MFR of 2.5 g / 10 min (230 ° C., 21.18 N) was used as a resin for the layer (laminate layer) on the adhesive layer side of the layer (A). As the resin for the surface layer (seal layer) on the opposite side, a propylene-ethylene copolymer having a melting point of 140 ° C. and an MFR of 3.5 g / 10 minutes (230 ° C., 21.18 N) was used.

  These resins are supplied to a layer (A) extruder (caliber 50 mm), an adhesive layer side (laminate layer) extruder (caliber 50 mm), and a seal layer extruder (caliber 50 mm), respectively, 180 to 210. The melted resin was supplied to a co-extrusion multi-layer film manufacturing apparatus of an air-cooled inflation method equipped with a spiral three-layer die having a diameter of 200 mm and a lip of 3 mm, and co-melt extrusion was carried out to form a layer structure of the film. However, a three-layer structure of laminate layer / layer (A) / seal layer was obtained, and a thickness of each layer was 20/60/20%, and a sealant film having a total thickness of 30 μm was obtained. Using this, a laminate was obtained in the same manner as in Example 1.

Example 10
As a resin for the layer (A), 40% by mass of an ethylene-α-olefin copolymer having a density of 0.943 g / cm ³ and MFR of 2.5 g / 10 minutes (190 ° C., 21.18 N) and MFR of 11 g / 10 minutes (230 ° C. 21.18 N), and a resin mixture of 60% by mass of a ring-opening polymer of norbornene monomer having a glass transition temperature (Tg) of 80 ° C. or lower was used. 90% by mass of ethylene-α-olefin copolymer having a density of 0.943 g / cm ³ and MFR of 2.5 g / 10 minutes (190 ° C., 21.18 N) as a resin for the layer (laminate layer) on the adhesive layer side of the layer (A) A mixed resin of 10% by mass of low density polyethylene having a density of 0.920 g / cm ³ and MFR of 0.5 g / cm ³ was used. As the resin for the surface layer (seal layer) on the opposite surface, an ethylene-α-olefin copolymer of 90% by mass with a density of 0.918 g / cm ³ and an MFR of 3.5 g / 10 minutes (190 ° C., 21.18 N) has a density of 0 A mixed resin of 10% by mass of low-density polyethylene of 920 g / cm ³ and MFR of 0.5 g / min was used.

  These resins are supplied to a layer (A) extruder (caliber 50 mm), an adhesive layer side (laminate layer) extruder (caliber 50 mm), and a seal layer extruder (caliber 50 mm), respectively, 180 to 210. The melted resin was supplied to a co-extrusion multi-layer film manufacturing apparatus of an air-cooled inflation method equipped with a spiral three-layer die having a diameter of 200 mm and a lip of 3 mm, and co-melt extrusion was carried out to form a layer structure of the film. However, a sealant film having a three-layer structure of laminate layer / layer (A) / seal layer, each layer having a thickness of 8/14/8 μm (total thickness of 30 μm) was obtained. Using this, a laminate was obtained in the same manner as in Example 1.

Comparative Example 1
As a resin for the layer (A ′), a melting point of 164 ° C., an MFR of 8 g / 10 min (230 ° C., 21.18 N), 80% by mass of a propylene homopolymer, an MFR of 11 g / 10 min (230 ° C., 21.18 N), a glass transition A resin mixture of 20% by mass of a ring-opening polymer of norbornene monomer having a temperature (Tg) of 80 ° C. or lower was used. As a resin for the laminate layer, a propylene homopolymer having a melting point of 164 ° C. and an MFR of 8 g / 10 minutes (230 ° C., 21.18 N) was used. As the resin for the sealing layer, a propylene-ethylene copolymer having a melting point of 127 ° C. and MFR of 7 g / 10 minutes (230 ° C., 21.18 N) was used. In the same manner as in Example 1, a sealant film having a total thickness of 30 μm and a thickness ratio of laminate layer / layer (A ′) / seal layer of 20/60/20% was obtained. A laminate was obtained in the same manner as in Example 1 using the obtained sealant film.

Comparative Example 2
A laminate is obtained in the same manner as in Example 1 except that a single-layer film (total thickness: 30 μm) made of a propylene homopolymer having a melting point of 164 ° C. and MFR of 8 g / 10 min (230 ° C., 21.18 N) is used as the sealant film. It was.

Comparative Example 3
Except that a single-layer film (total thickness 50 μm) made of an ethylene-α-olefin copolymer having a melting point of 127 ° C., MFR 3.5 (190 ° C., 21.18 N), and a density of 0.938 g / cm 3 is used as the sealant film. 1 to obtain a laminate.

Test Method (1) Suppression of Adhesive Component (Epoxysilane) <Conforming to EN13130>
-Laminate aluminum foil # 12 and sealant film with a specific adhesive containing epoxy silane. Aging of adhesive application amount 2.2 g / m ² , 40 ° C. × 24 hours.
A pouch was prepared so that the contact area with the contents was 200 cm ² and filled with 100 ml of 95% ethanol as a food pseudo-solvent and sealed.
After storing the prepared pouch at 60 ° C. for 5 days, the content of 95% ethanol is concentrated from 100 ml to 5 ml, and the silane compound is quantified by gas chromatography mass spectrometry (GC-MS).
GC-MS: Shimadzu GC2100A
Column: Polydimethylsiloxane

(2) Seal strength A sealant film and PET # 12 (E5102, manufactured by Toyobo Co., Ltd.) were dry laminated in the same manner as described above using a specific adhesive containing epoxysilane. The obtained laminate film was heat-sealed with a heat sealer according to the film composition at a temperature of 100 to 180 ° C., a pressure of 0.2 MPa, and a time of 1 second, and the peak strength when peeled at 90 ° was evaluated.

(3) Dispersion state It observed with the STEM (Scanning Transmission Electron Microscope) function attached to JEOL 7500FA.

The results evaluated above are summarized below.

Claims (11)

In the laminate having the structure of base material / adhesive layer / sealant film, the sealant film includes at least a cyclic olefin resin (a1) having a glass transition temperature Tg of 160 ° C. or lower, and a melt flow rate MFR (230 ° C., 21 .18N) contains an olefin resin (a2) having no cyclic structure of 0.5 to 30 g / 10 min, and is in the total mass of the cyclic olefin resin (a1) and the olefin resin (a2). A film having at least one layer (A) having a thickness in the range of 0.5 to 20 μm, comprising a resin composition containing 30% by mass or more of the cyclic olefin-based resin (a1). In (A), the cyclic olefin resin (a1) and the olefin resin (a2) form a layered phase separation structure, or the cyclic olefin. Barrier laminate, wherein the olefin resin in a continuous layer of the resin (a1) (a2) forms a phase separation structure which is dispersed like islands. The barrier laminate according to claim 1, wherein the cyclic olefin resin (a1) is a norbornene polymer having a melt flow rate MFR (230 ° C, 21.18N) of 0.2 to 17 g / 10 min. The barrier property according to claim 1 or 2, wherein the olefin resin (a2) is a propylene resin having a melting point of 120 ° C or higher and a melt flow rate MFR (230 ° C, 21.18N) of 0.5 to 30 g / 10 min. Laminated body. The barrier laminate according to any one of claims 1 to 3, wherein a proportion of the cyclic olefin resin (a1) used in the resin composition forming the layer (A) is in the range of 30 to 70 mass%. . The said sealant film is a multilayer film of at least 3 layers, Comprising: It has a layer which has as a main component the olefin resin which does not have a cyclic structure on both surfaces of the said layer (A). The barrier laminate according to the description. The barrier laminate according to claim 5, wherein the total thickness of the sealant film is 15 to 150 µm, and the ratio of the layer (A) to the total thickness is in the range of 10 to 70%. The barrier laminate according to claim 5 or 6, wherein the sealant film is laminated by a coextrusion lamination method. The barrier laminate according to any one of claims 1 to 7, wherein the adhesive layer is an adhesive layer formed using an adhesive containing epoxysilane. The barrier laminate according to claim 8, wherein elution of the silane compound is suppressed to less than 10 µg / kg-food in an elution test based on a regulation of Swiss Ordinance SR817.023.21. A packaging material comprising the barrier laminate according to any one of claims 1 to 9. The packaging material according to claim 10, which is used for food or medicine.

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