JP6451987B2 - Barrier laminate and packaging material using the same - Google Patents

Description

  The present invention is a laminate that can be suitably used as a packaging material, and can effectively suppress the dissolution of mineral oil components, adhesives, and printing ink components into the contents. The present invention relates to a body and a packaging material using the body.

  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 affect human health have been dissolved and transferred to food from specific packaging materials. The detection of printing ink components from foods and the transfer of initiators used in UV curable inks (UV inks) to foods, etc., have raised consumer awareness of the safety and hygiene of packaging materials. .

  In Europe, there are no laws and regulations for inks and adhesives yet, but regulations for packaging materials intended to come into contact with foods are becoming increasingly strict, and the Commission Regulations on Plastic Materials and Products (EU No. 10) / 2011). Here, elution of the chemical substance from the composite plastic film is regulated, and it is necessary to suppress elution from the ink and the adhesive.

  Under such circumstances, research in Europe has found that the mineral oil component contained in the recycled paper used for food packaging has been transferred to the content food. There are examples of animal experiments in which mineral oil affects the liver, heart, immune system, etc., and there are concerns about food packaging using recycled paper. In WHO, ADI is set for some mineral oils as an amount that will not be harmful even if it is consumed every day for the rest of the life. However, the mixing of mineral oil is said to be derived from recycled ink components, and it is difficult to grasp how much and what kind of mineral oil is mixed.

  UV curable inks (UV inks) can be made solvent-free, have the property of being instantly cured, and do not require a drying device or long-term aging, and are therefore environmentally friendly printing methods. In addition, when an ink jet printing method is used, a printing plate such as granvia ink is not required, so that there is a merit that it can efficiently cope with the recent trend toward a large variety of small lots. On the other hand, UV ink is generally composed of a monomer, an oligomer, an initiator, and the like, and an uncured product is expected to remain, and there is a concern about its use in food packaging. In particular, in inkjet printing, a lower molecular weight resin is used from the viewpoint of ensuring stable ejection properties, so there is concern over the remaining of an uncured product, and it is not used in food packaging applications.

  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, there may be a case where sufficient barrier properties, sealing strength as a packaging material, and mechanical strength are not compatible. 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 situation, the problem of the present invention is that Swiss is about elution from a printed and laminated composite plastic film, which is regulated by the Commission Regulations on Plastic Materials and Products (EU No. 10/2011). In the chemical substances regulated by Ordinance SR817.002.21, taking saturated hydrocarbons and aromatic hydrocarbons as examples, while suppressing the shift to foods and making it possible to use recycled paper packaging more safely Another object of the present invention is to provide a laminate having a good balance between low-temperature sealability and mechanical strength, and can be suitably used for packaging materials for foods and pharmaceuticals, and a packaging material using the laminate. Similarly, UV ink and adhesive components regulated by Swiss Ordinance SR817.002.21 are also controlled to below the regulation value, and UV ink can be applied to flexible food packaging. It is another object of the present invention to provide a laminate having both low-temperature sealing properties and strength, and a packaging material using the same.

  As a result of earnest research to solve such problems, the present inventor has a sealing layer mainly composed of an ethylene-based resin or a propylene-based resin having a specific melting point range, and a melting point higher than the melting point of the resin used for the sealing layer. A coating agent containing a cyclic olefin resin having a glass transition temperature Tg of 60 ° C. to 200 ° C. on the intermediate layer of the multilayer film (I) having an intermediate layer mainly composed of an ethylene resin or a propylene resin. A laminate obtained by laminating a coating layer formed by coating and further laminating at least one layer selected from the group consisting of an adhesive layer, a printing layer, or a layer containing mineral oil on the coating layer is the multilayer. Even if the thickness of the film (I) is thin, it is possible to effectively suppress the eluted components and prevent the transfer of the specifically regulated target substance to the contents. , It found that it is possible to express the intensity of the low-temperature sealing properties and packaging materials, and completed the present invention.

That is, the present invention includes a sealing layer (A) mainly composed of an ethylene resin (a1) or a propylene resin (a2) having a melting point in the range of 70 ° C. to 150 ° C.
An intermediate layer (B) mainly composed of an ethylene resin (b1) or a propylene resin (b2) having a melting point in the range of 110 ° C. to 168 ° C.
On the intermediate layer (B) of the multilayer film (I) in which the melting point of the main component resin of the intermediate layer (B) is higher than the melting point of the main component resin of the seal layer (A),
A coating layer (C) formed by applying a coating agent containing a cyclic olefin resin (c1) having a glass transition temperature Tg of 60 ° C. to 200 ° C. is laminated, and an adhesive layer (C) is further formed on the coating layer (C). A barrier laminate comprising at least one layer (D) selected from the group consisting of D1), a printing layer (D2), and a layer (D3) containing mineral oil, and the use thereof A packaging material is provided.

  The barrier laminate of the present invention effectively captures substances that are likely to elute from mineral oil, adhesives, printing ink components, etc. while having appropriate sealing strength and mechanical strength as packaging materials. In addition, the transition to the contents can be suppressed. Therefore, it can be suitably used as an environmentally friendly packaging material containing foods, medicines and the like as contents.

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

  The barrier laminate of the present invention includes a layer (C) containing a cyclic olefin resin on the intermediate layer (B) of the multilayer film (I) having the seal layer (A) and the intermediate layer (B), and An adhesive layer (D1), a printed layer (D2) or a layer (D3) containing mineral oil is laminated on the layer (C), and has a structure of at least four layers. Furthermore, if necessary, a resin layer may be provided between the layers, and an adhesive layer (D1), a printed layer (D2) and a layer (D3) containing mineral oil on the layer (C). It may be a laminate having all of the above.

  The multilayer film (I) contains an ethylene resin or a propylene resin as a main component. In the present invention, the main component means that a specific resin is contained in an amount of 65% by mass or more, preferably 80% by mass or more based on the total amount of resin components forming the layer.

  The sealing layer (A) in the multilayer film (I) is a layer in contact with the contents, and particularly when packaging foods and pharmaceuticals, the viewpoint that it cannot be exposed to high temperatures, or the viewpoint of automatic packaging at a higher speed Therefore, it is essential that a resin having a melting point in the range of 70 ° C. to 150 ° C. is used as a main component in order to exhibit sealing properties at a lower temperature.

  Examples of the ethylene resin (a1) include polyethylene resins such as very low density polyethylene (VLDPE), low density polyethylene (LDPE), and linear low density polyethylene (LLDPE), and ethylene-vinyl acetate copolymer (EVA). These may be used alone or in combination of two or more. Among these, LLDPE is preferable because it has a good balance with film forming properties, adhesives, mineral oil, and suppression of migration of specific components in the printing ink.

  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 laminate strength and anti-blocking property can be obtained.

The density of the ethylene resin (a1) is preferably 0.860 to 0.935 g / cm ³ . If the density is within this range, the melting point is about 70 ° C. to 127 ° C., and an appropriate low temperature sealing property is exhibited. In addition, mechanical strength such as pinhole resistance is excellent, and film film formability and extrusion suitability are improved. The MFR (190 ° C., 21.18N) of the ethylene resin (a1) is preferably 1 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.

  Examples of the propylene resin (a2) include propylene homopolymers, propylene / α-olefin random copolymers such as propylene-ethylene copolymers, propylene-butene-1 copolymers, propylene-ethylene-butene- 1 copolymer, metallocene catalyst type polypropylene, etc. are mentioned. These may be used alone or in combination. From the viewpoint of improving heat sealability at a low temperature, a propylene-α-olefin random copolymer is desirable, and a propylene / α-olefin random copolymer polymerized using a single site catalyst is particularly preferable. The melting point is preferably in the range of 110 ° C. to 150 ° C. from the viewpoint of low temperature heat sealability. When a propylene-α-olefin copolymer having a melting point in this range is used for the sealing layer (A), it exhibits low-temperature sealing properties and is excellent in moderate rigidity and high glossiness, film-forming properties, and an extruder. Aptitude is also improved.

  In addition, these propylene resins have an MFR (230 ° C.) of 0.5 to 30.0 g / 10 minutes, and more preferably an MFR (230 ° C.) of 2.0 to 15.0 g / 10 minutes. When the MFR is within this range, the shrinkage during heat sealing is small, and the film formability is improved.

  The intermediate layer (B) in the multilayer film (I) has an ethylene resin (b1) or a propylene resin (b2) having a melting point in the range of 110 ° C. to 168 ° C. as a main component. Further, it is essential that the resin used for the intermediate layer (B) is higher than the melting point of the resin used for the seal layer (A). By using a resin having a higher melting point for the intermediate layer (B), heat resistance and rigidity are improved, and mechanical suitability and high-speed packaging suitability in automatic packaging are improved. Moreover, the suitability of secondary processing in the coating layer (C), the adhesive layer (D1), and the printing layer (D2) is also improved.

Examples of the ethylene resin (b1) include polyethylene resins such as linear medium density polyethylene (LMDPE) and medium density polyethylene (MDPE), and ethylene-vinyl acetate copolymer (EVA). You may mix and use seeds or more. Among these, mechanical strength of the film (I), interlayer adhesion with the sealing layer (A), suitability for coextrusion processing, and suppression of migration of specific components in adhesives, mineral oil and printing ink to the contents It is preferable to use LMDPE because of its good balance. The density is preferably in the range of 0.915 to 0.965 g / cm ³ . When the density is within this range, the melting point is about 110 ° C. to 130 ° C., the film has excellent heat resistance and rigidity, and film film formability and extrusion suitability are also improved.

  Examples of the propylene resin (b2) include propylene homopolymers, propylene / α-olefin random copolymers such as propylene-ethylene copolymers, propylene-butene-1 copolymers, propylene-ethylene-butene- 1 copolymer, metallocene catalyst type polypropylene, etc. are mentioned. These may be used alone or in combination. From the viewpoint of heat resistance and rigidity, it is preferably a propylene homopolymer or a propylene-α-olefin random copolymer, and in particular, the propylene-α-olefin random copolymer is polymerized using a single site catalyst. Is preferred. When these propylene-based resins are used as the intermediate layer (B), the heat resistance is improved and the softening temperature can be increased. Therefore, boiling at 100 ° C. or lower, hot filling, or retort at 100 ° C. or higher. It can be suitably used as a lid material excellent in steam and high-pressure heat sterilization characteristics such as sterilization.

  In addition, these propylene resins preferably have an MFR (230 ° C.) of 0.5 to 30.0 g / 10 minutes and a melting point of 140 to 168 ° C., more preferably an MFR (230 ° C.) of 2 0.0-15.0 g / 10 min, melting point 150-165 ° C. If MFR and melting | fusing point are this range, it will be excellent in the heat resistance and rigidity of a film, there will be little shrinkage | contraction at the time of heat sealing, and also the film-forming property of a film and extrusion suitability will improve.

  As described above, the multilayer film (I) has the sealing layer (A) and the intermediate layer (B), but the coating agent contains the cyclic olefin resin (c1) on the intermediate layer (B). From the viewpoint of the purpose of, for example, improving the adhesion with the coating agent when the coating layer (C) formed by coating is further laminated, other resins may be used in combination. Other resins that can be used at this time include ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), and ethylene-methyl acrylate (EMA). Copolymers, ethylene-based copolymers such as ethylene-ethyl acrylate-maleic anhydride copolymer (E-EA-MAH), ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMAA) Further, it has a cyclic olefin structure such as an ionomer of an ethylene-acrylic acid copolymer, an ionomer of an ethylene-methacrylic acid copolymer, or a norbornene-based monomer that can be used as a resin for a coating layer (C) described later. Examples include monomers and copolymers of ethylene, etc. A mixture of two or more may be used.

  The thickness ratio of the sealing layer (A) to the total thickness of the multilayer film (I) is preferably 1 to 40%. By setting it as such a thin sealing layer, the whole thickness as multilayer film (I) can also be made thin, and the workability as a laminated body becomes favorable. On the other hand, from the viewpoint of sealing strength, the thickness of the sealing layer (A) is preferably 1 μm or more, and therefore the total thickness of the multilayer film (I) is preferably in the range of 15 to 100 μm.

  Moreover, as a thickness ratio of the intermediate | middle layer (B) in multilayer film (I), it is preferable that it is the range of 60 to 99% from a viewpoint of maintaining the mechanical strength as a laminated body.

  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. Therefore, the total thickness of the multilayer film (I) in the present invention is preferably in the range of 15 to 150 μm, particularly preferably in the range of 20 to 100 μm.

  The coating layer (C) used in the present invention is a layer formed by applying a coating agent containing a cyclic olefin resin (c1) having a glass transition temperature Tg of 60 ° C. to 200 ° C. By providing a layer containing such a specific cyclic olefin-based resin, a sufficient barrier property can be exhibited in the laminate.

  The coating layer (C) in the multilayer film (I) used in the present invention preferably has a thickness of 0.5 to 3.0 μm from the viewpoint of developing sufficient barrier properties. In applications where the demand for thinning is high, the effect of the present invention is not impaired even when the thickness is 5 μm or less.

  As described above, the resin used for the coating layer (C) contains the cyclic olefin-based resin (c1), but it is preferably contained at 70% by mass or more in the nonvolatile content in the coating agent. Particularly preferably, the content is 90% by mass or more.

  The cyclic olefin resin (c1) is not particularly limited in its structure as long as the glass transition temperature Tg is in the range of 60 ° C. to 200 ° C. For example, norbornene polymer, vinyl alicyclic Examples thereof include 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”). 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.

  In addition, the glass transition temperature Tg of the cyclic olefin resin (c1) is indispensable to be in the range of 60 to 200 ° C. in order to develop sufficient barrier properties in the obtained laminate. It is preferable that it is 130 degrees C or less from a viewpoint that the laminated body to form can be formed easily. In addition, the glass transition temperature Tg or melting | fusing point in this invention is a value obtained by measuring by DSC. The target multilayer film (I) is a norbornene polymer having a melt flow rate MFR (230 ° C., 21.18 N) of the cyclic olefin resin (c1) of 0.2 to 17 g / 10 min. Can be easily formed, and is excellent in balance with the barrier property.

  As a commercially available product that can be used as the cyclic olefin resin (c1), examples of the ring-opening polymer (COP) of the norbornene monomer include “ZEONOR” manufactured by Nippon Zeon Co., Ltd. Examples of the system copolymer (COC) include “Appel” manufactured by Mitsui Chemicals, Inc., “TOPAS” manufactured by Polyplastics Co., Ltd., and the like.

  The cyclic olefin resin (c1) is preferably contained in the coating layer (C) at 70% by mass or more as a resin component, but as other components, an olefin resin having no cyclic structure is used in combination. Also good.

  Examples of the olefin resin include ethylene resins and propylene resins, and any of those exemplified as resins that can be used for the seal layer (A) and the intermediate layer (B) can be used.

  The coating agent used to form the coating layer (C) may be any one containing the cyclic olefin resin (c1) having a glass transition temperature Tg of 60 ° C. to 200 ° C. as described above. Uniformly dissolved in an organic solvent such as tetrahydrofuran, hexane, cyclohexane, toluene, benzene, etc., and conventionally known coating methods such as roll coating, die coating, spin coating, lip coating, comma coating, Using a method such as a bar coating method, a dip coating method, a casting film forming method, or a gravure coating method, it is applied onto the intermediate layer (B) of the multilayer film (I) and dried.

  The sealing layer (A), the intermediate layer (B), and the coating layer (C) of the multilayer film (I) used in the present invention are within the range that does not impair the effects of the present invention. Components such as a stabilizer, a nucleating agent, an antioxidant, a lubricant, an antiblocking agent, a release agent, an ultraviolet absorber, and a colorant can be added. In particular, in order to impart processing suitability at the time of film forming and packaging suitability of the filling machine, the coefficient of friction of the surface of the multilayer film (I) is preferably 1.5 or less, more preferably 1.0 or less. In the intermediate layer corresponding to the surface layer, a lubricant, an antiblocking agent or an antistatic agent is preferably added as appropriate.

  Moreover, in the multilayer film (I) used by this invention, it is preferable to process the surface of an intermediate | middle layer and to make the surface tension of a surface into 35-45 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, the coating property when the coating agent is applied to the multilayer film (I) is improved, the adhesiveness is excellent, and it is easy to avoid problems such as dropout and delamination. . Furthermore, as a method for improving the adhesion to the coating agent, a receiving agent for various inks and an anchor coating agent may be applied on the intermediate layer (B) of the multilayer film (I).

  The method for producing the multilayer film (I) used in the present invention is not particularly limited. For example, the resin or resin mixture used for each layer of the multilayer film (I) is heated and melted in separate extruders, and co-extrusion is performed. Examples thereof include a coextrusion method in which a film is laminated in a molten state by a method such as a multilayer die method or a feed block 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. In addition, when the difference in melting point and Tg from the resin or resin mixture used in the seal layer (A) and intermediate layer (B) used in the present invention is large, the film appearance deteriorates during coextrusion processing, or a uniform layer It may be difficult to form a configuration. 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 the multilayer air-cooled inflation method is used as the method for producing the multilayer film (I), 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 using an ethylene-based resin, an ethylene-based resin having the above-described density range and composition can be used, but MFR (190 ° C., 21.18N) is preferably 0.1 to 5 g / 10 minutes in terms of bubble stability. 0.5 to 4 g / 10 min is more preferable. Similarly, in the case of the propylene-based resin, MFR (230 ° C., 21.18N) is preferably 0.1 to 5 g / 10 minutes, and more preferably 0.5 to 4 g / 10 minutes.

  The film (I) of the present invention may be stretched in at least one axial direction. As the stretching method, a known method such as longitudinal or lateral uniaxial stretching, sequential biaxial stretching, simultaneous biaxial stretching, or tubular method biaxial stretching can be employed. Further, the stretching process may be inline or offline. The stretching method for uniaxial stretching may be a proximity roll stretching method or a rolling method. The stretching ratio of uniaxial stretching is preferably 1.1 to 10 times in the longitudinal or lateral direction, more preferably 1.2 to 6 times. On the other hand, the stretch ratio of biaxial stretching is preferably 1.2 to 70 times in terms of area ratio, more preferably 4 to 6 times in length, 5 to 9 times in width, and 20 to 54 times in area ratio.

  In addition, the longitudinal or lateral stretching step is not necessarily limited to one-stage stretching, and may be multi-stage stretching. In particular, in longitudinal uniaxial stretching such as longitudinal uniaxial roll stretching and longitudinal uniaxial rolling stretching in sequential biaxial stretching, it is preferable to perform multistage stretching in view of thickness, uniformity of physical properties, and the like. Further, in the proximity roll stretching, either the flat method or the cross method may be used, but multistage proximity cross stretching that can reduce width shrinkage is more preferable. Moreover, you may provide a pre-heating part before an extending process, and a heat setting part after an extending process suitably. The preheating temperature and the stretching temperature may be appropriately set in a stable temperature range based on the characteristics of the main raw material of the film (I).

  The laminate obtained by laminating the coating layer (C) on the multilayer film (I) obtained above may be used by being bonded to another base film (II). Other base film (II) that can be used at this time is not particularly limited, but from the viewpoint of easily manifesting the effects of the present invention, it is a plastic base, particularly biaxially stretched. It is preferable to use a resin film. For applications that do not require transparency, aluminum foil or recycled paper can be used alone or in combination.

  Examples of the stretched resin film include coextrusion using, as a central layer, biaxially stretched polyester (PET), biaxially stretched polypropylene (OPP), biaxially stretched polyamide (PA), and ethylene vinyl alcohol copolymer (EVOH). Examples thereof include 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.

  Paper products used for food packaging can be divided into new pulp products made from wood and recycled paper (recycled paper) products made using all or part of waste paper. It is also widely used in food applications such as pasta boxes and fast food containers. In the recycled paper, after the pulp is extracted in the disaggregation process, foreign matters and printing ink are removed through the deinking process, but organic components of the ink, particularly mineral oil, often remains. For this reason, the German Federal Institute for Risk Assessment has recommended standards for its application to food packaging and must be used with caution. In Japan, the Ministry of Health, Labor and Welfare provides guidelines on the use of recycled paper in food packaging.

  One aspect | mode of the barriering laminated body of this invention contains mineral oil on the coating layer (C) layer of the laminated body which has the multilayer film (I) obtained by said manufacturing method, and a coating layer (C). The layer (D3) to be provided is provided. The layer (D3) containing the mineral oil may be on the coating layer (C). For example, when the base film (II) is used, a printing layer is laminated on one surface of the coating layer (C). It is preferable that the base film (II) and the multilayer film (I) are laminated on each other via an adhesive layer, and in particular, the base film (II) is printed and the coating layer (C) When it is bonded to the printed surface of the base film (II) through the adhesive layer provided in the above, the appearance of the packaging body is improved, which is preferable. At this time, a printing layer (D2) or an adhesive layer (D1) containing a mineral oil component may be used.

  As a method of bonding a general sealant film such as a non-stretched polyethylene film or a non-stretched polypropylene film, and various stretched base films, two processing methods are mainly used. One is to apply an anchor coating agent to the printed surface of the base film as necessary, and heat and melt the polymer film (polyethylene, polypropylene, etc.) between the unstretched film and the printed surface of the base film. It is an extrusion laminating method in which it is extruded and pressed and laminated. The other is a dry laminating method in which an unstretched film and a substrate film are pressure-bonded and laminated after an adhesive is applied to the printing surface.

  In the present invention, when the base film (II) is bonded to the coating layer (C), the surface of the base film (II) is printed with printing ink, and then an adhesive is applied to the printing surface. The dry laminating method in which the coating layer (C) is pressed and laminated is preferable.

  The adhesive layer (D1) may be formed using an adhesive, and examples thereof 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 multilayer film. However, with the advent of transparent vapor deposition technology, various transparent vapor deposition films that have both barrier properties and transparency are commercially available, and in addition to the demand for improved visibility of contents, transparent vapor deposition films and multilayer 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 the multilayer film 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 methacrylsilane-based silane coupling agents such as 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycid Examples thereof include xylpropyltriethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

  When the barrier laminate of the present invention has a layer (D3) containing mineral oil, the layer (D3) containing mineral oil may be an adhesive layer (D1) or a printed layer (D2). Alternatively, recycled paper may be used instead of the base film (II) described above. There may be a plurality of layers (D3) containing mineral oil.

  In the barrier laminate of the present invention, the printing layer (D2) may be a printing layer made of an active energy ray-curable printing ink. The printing ink that can be used here is not particularly limited, and various commercially available inks can be used as they are, or inks that have been adjusted according to curing conditions or printing methods can be used. Good. In particular, it is preferable to apply an ink jet printing method from the viewpoint of being able to cope with a small lot.

  The active energy ray-curable printing ink contains a compound that is cured and polymerized by active energy rays (hereinafter referred to as an active energy ray polymerizable compound).

  For example, among the active energy ray polymerizable compounds, examples of low molecular weight monomers called polymerizable monomers include (meth) acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate; 2 -Hydroxyalkyl (meth) acrylates such as hydroxyethyl acrylate and 2-hydroxypropyl acrylate; alkoxyalkyl (meth) acrylates such as butoxyethyl acrylate and methoxybutyl (meth) acrylate; polyethylene glycol mono (meth) acrylate, methoxydiethylene glycol (Meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, polypropylene glycol Poly (alkylene glycol) (meth) acrylates such as poly (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, and nonylphenoxypolypropylene glycol (meth) acrylate; cyclohexyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, isobornyl Cycloalkyl (meth) acrylates such as (meth) acrylate;

  (Meth) acrylates such as benzyl (meth) acrylate, 2-hydroxyethyl (meth) acryloyl phosphate, tetrahydrofurfuryl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate; ) (Meth) acrylamides such as acrylamide and acryloylmorpholine; unsaturated carboxylic acid esters such as methyl crotonic acid, methyl cinnamate, dimethyl itaconate, dimethyl maleate, dimethyl fumarate; (meth) acrylonitrile, nitrile crotonic acid Unsaturated nitriles such as dinitrile maleate; vinyl carboxylic acid esters such as vinyl acetate and vinyl propionate; ethyl vinyl ether, isobutyl vinyl ether, 2-ethylhexylbi Alkyl vinyl ethers and cycloalkyl vinyl ethers such as ruether and cyclohexyl vinyl ether; Hydroxyl-containing vinyl ethers such as 2-hydroxyethyl vinyl ether and 3-hydroxypropyl vinyl ether; Hydroxyl groups such as 2-hydroxyethyl allyl ether and 4-hydroxybutyl allyl ether Allyl ethers; N-vinyl lactams and N-vinyl alkylamides such as N-vinyl-2-pyrrolidone, N-vinylcaprolactam, N-vinylacetamide, (meth) acrylic acid 2- (2-vinyloxyethoxy) And monomers containing both a vinyl ether group such as ethyl and a (meth) acryloyl group.

  Examples of the polyfunctional (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and polyethylene glycol di (meth). Acrylate, tripropylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 3-methyl 1,5-pentanediol diacrylate, 1,6 -Alkylene glycol di (meth) acrylates such as hexanediol di (meth) acrylate and neopentyl glycol di (meth) acrylate; trimethylolpropane di (meth) acrylate, trimethylolpropa Tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolpropane trihydroxyethyl tri (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate Poly (meth) acrylates of polyhydric alcohols such as hydroxypivalic acid neopentyl glycol di (meth) acrylate;

  Poly (meth) acrylates of isocyanurates such as isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate; Poly (meth) acrylates of cycloalkanes such as cyclodecanediyldimethyldi (meth) acrylate; di (meth) acrylates of ethylene oxide adducts of bisphenol A, di (meth) acrylates of propylene oxide adducts of bisphenol A, bisphenols Di (meth) acrylate of alkylene oxide adduct of A, di (meth) acrylate of ethylene oxide adduct of hydrogenated bisphenol A, di (meth) acrylate of propylene oxide adduct of hydrogenated bisphenol A ( A) (meth) acrylate derivatives of bisphenol A such as (meth) acrylate obtained from acrylate, di (meth) acrylate of hydrogenated bisphenol A alkylene oxide adduct, bisphenol A diglycidyl ether and (meth) acrylic acid; And alkylene glycol divinyl ethers such as ethylene glycol divinyl ether. Two or more of these can be used in combination.

  Among these, when dipropylene glycol diacrylate is used in combination, the reactivity can be improved without increasing the viscosity of the composition, the adhesion is not impaired, and the odor can be further reduced, which is preferable.

  In applications where low viscosity is not desired, a polymerizable oligomer such as a (meth) acrylate oligomer having a high molecular weight can also be used. Examples of the polymerizable oligomer include polyurethane (meth) acrylate, polyester (meth) acrylate, polyacryl (meth) acrylate, epoxy (meth) acrylate, polyalkylene glycol poly (meth) acrylate, and polyether (meth) acrylate. Two or more types can be used in combination.

  Among these, from the viewpoint of ink ejection reliability, a combination of polyfunctional (meth) acrylate and monofunctional (meth) acrylate is preferable, and a combination of bifunctional (meth) acrylate and monofunctional (meth) acrylate, monofunctional (meth) acrylate A combination alone is still preferred.

  Although the said active energy ray polymeric compound is based also on the printing method and apparatus to be used, the viscosity after mix | blending each monomer is 45 degreeC, and about 1-100 mPa. It is preferable to design so that it may become s.

  In the present invention, when ultraviolet rays are used as active energy rays, it is preferable to use a photopolymerization initiator. As the photopolymerization initiator, a radical polymerization type photopolymerization initiator is used.

  Specifically, benzoin isobutyl ether, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, benzyl, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-2- Dimethylamino-1- (4-morpholinophenyl) -butan-1-one, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, etc. are preferably used, and other than these As the molecular cleavage type, 1-hydroxycyclohexyl phenyl ketone, benzoin ethyl ether, benzyldimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2 - Roxy-2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, etc. may be used in combination, and hydrogen abstraction type photopolymerization initiator Benzophenone, 4-phenylbenzophenone, isophthalphenone, 4-benzoyl-4′-methyl-diphenyl sulfide and the like can be used in combination.

  In particular, when an LED is used, it is preferable to select a photopolymerization initiator in consideration of the emission peak wavelength of the LED. For example, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino)-is suitable as a photopolymerization initiator when using a UV-LED. 2-[(4-methylphenyl) methyl] -1- (4-morpholinophenyl) -butan-1-one), bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6 -Trimethylbenzoyl-diphenyl-phosphine oxide, 2,4-diethylthioxanthone, 2-isopropylthioxanthone and the like.

  For the above photopolymerization initiator, for example, trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N An amine that does not cause an addition reaction with the polymerizable component, such as dimethylbenzylamine and 4,4′-bis (diethylamino) benzophenone, can also be used in combination.

  In the active energy ray curable printing ink, a polymerization inhibitor such as hydroquinone, methoquinone, di-t-butylhydroquinone, P-methoxyphenol, butylhydroxytoluene, or nitrosamine salt is added to the ink in order to enhance the storage stability of the ink. You may add in 0.01-2 mass%.

  The active energy ray-curable printing ink used in the present application can also be applied to an ink such as a varnish that does not contain a color material. On the other hand, a colorant may be used depending on the purpose. The colorant to be used may be either a dye or a pigment, but it is preferable to use a pigment from the viewpoint of durability of the printed matter.

  Examples of the dye include direct dyes, acid dyes, food dyes, basic dyes, reactive dyes, disperse dyes, vat dyes, soluble vat dyes, reactive disperse dyes, and various dyes that are usually used in inkjet recording. It is done.

  As the pigment, an inorganic pigment or an organic pigment can be used. As the inorganic pigment, titanium oxide or iron oxide, or carbon black produced by a known method such as a contact method, a furnace method, or a thermal method can be used. Organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazines). Pigments, thioindigo pigments, isoindolinone pigments, quinofullerone pigments, etc.), dye chelates (for example, basic dye chelate, acid dye chelate, etc.), nitro pigments, nitroso pigments, aniline black, and the like.

  Specific examples of the pigment include carbon black, No. manufactured by Mitsubishi Chemical Corporation. 2300, no. 900, MCF88, No. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, no. 2200B, etc. are Raven 5750, 5250, 5000, 3500, 1255, 700, etc. made by Columbia, and Regal 400R, 330R, 660R, Mogu L, 700, Monarch 800, 880, made by Cabot, 900, 1000, 1100, 1300, 1400, etc. are Degussa Color Black FW1, FW2, FW2V, FW18, FW200, ColorBlack S150, S160, S170, Printex 35, U, the same V, the same 140 U, the Special Black 6, the same 5, the same 4 A, the same 4, and the like.

  Examples of pigments used in yellow ink include C.I. I. Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 109, 110, 114, 120, 128, 129, 138, 150, 151, 154, 155, 180, 185, 213 and the like.

  Examples of pigments used for magenta ink include C.I. I. Pigment Red 5, 7, 12, 48 (Ca), 48 (Mn), 57 (Ca), 57: 1, 112, 122, 123, 168, 184, 202, 209, C.I. I. Pigment violet 19 and the like.

  Examples of pigments used for cyan ink include C.I. I. And CI Pigment Blue 1, 2, 3, 15: 3, 15: 4, 60, 16, and 22.

  Examples of white pigments used in white ink include titanium oxide, zinc sulfide, lead white, zinc white, lithbon, antimony white, basic lead sulfate, basic lead silicate, barium sulfate, calcium carbonate, gypsum, And silica.

  The average particle size of the pigment is preferably in the range of 10 to 200 nm, more preferably about 50 to 150 nm. Further, in order to obtain the addition amount of the colorant, sufficient image density, and light fastness of the printed image, it is preferably contained in the range of 1 to 20% by mass of the total amount of the ink.

  Further, when the active energy ray-curable printing ink contains a colorant, the ink composition containing the colorant may have a plurality for each color. For example, in addition to the basic four colors of yellow, magenta, cyan, and black, when adding the same series of dark and light colors for each color, in addition to magenta, light light magenta, dark red, and cyan In addition to light-colored light cyan, dark blue, and black, light gray, light black, and dark matte black can be used.

  In addition to this, when performing printing by inkjet, a surfactant, leveling additive, matting agent, polyester-based resin for adjusting film physical properties, and polyurethane based on the range in which the ejection stability is not impaired. Resins, vinyl resins, acrylic resins, rubber resins, and waxes can be added.

  The pigment preferably uses a pigment dispersant for the purpose of enhancing dispersion stability with respect to the active energy ray polymerizable compound or the like. Specifically, Ajinomoto Fine Techno Co., Ltd. Ajisper PB821, PB822, PB817, Avisia Corp. Solspurs 24000GR, 32000, 33000, 39000, Enomoto Kasei Co., Ltd. Disparon DA-703-50, DA-705, DA-725 However, it is not limited to these. In addition, the amount of the pigment dispersant used is preferably in the range of 10 to 80% by mass, particularly preferably in the range of 20 to 60% by mass, based on the balance between the dispersion stability and the viscosity of the printing ink. .

  For the purpose of imparting adhesiveness to the substrate to be printed, non-reactive resins such as acrylic resins, epoxy resins, terpene phenol resins, rosin esters, and the like can be blended.

  When an active energy ray-curable printing ink is produced, the mixture containing the pigment and the active energy ray polymerizable compound, if necessary, a pigment dispersant, and a resin is added to the pigment using a normal dispersing machine such as a bead mill. Can be prepared by adding a photopolymerization initiator and, if necessary, adding an additive such as a surface tension adjuster and stirring and dissolving. Prepare a high-concentration pigment dispersion (mill base) using an ordinary dispersing machine such as a bead mill in advance, and then stir and mix the active energy ray-polymerizable compound in which the photopolymerization initiator is dissolved and additives. You can also.

  As the agitation / dispersion device for dispersing the pigment, various dispersions such as an ultrasonic homogenizer, a high-pressure homogenizer, a paint shaker, a ball mill, a roll mill, a sand mill, a sand grinder, a dyno mill, a disperse mat, an SC mill, and a nanomizer can be used. You can use the machine.

  The active energy ray-curable printing ink undergoes a curing reaction by irradiation with light of active energy rays, preferably ultraviolet rays. As a light source such as an ultraviolet ray, a light source usually used for UV curable ink, for example, a metal halide lamp, a xenon lamp, a carbon arc lamp, a chemical lamp, a low pressure mercury lamp, a high pressure mercury lamp, etc., can be cured without problems. For example, a commercially available product such as an H lamp, D lamp, or V lamp manufactured by Fusion System can be used.

  When an active energy ray-curable printing ink having good sensitivity is used, it can be cured by an ultraviolet light emitting semiconductor element such as a UV-LED or an ultraviolet light emitting semiconductor laser.

  Any conventionally known method can be used as the ink jet recording method. For example, a method of ejecting droplets using vibration of a piezoelectric element (a recording method using an ink jet head that forms ink droplets by mechanical deformation of an electrostrictive element) or a method of using thermal energy can be given.

<Regulations in Europe>
In Switzerland, Swiss Ordinance SR817.023.21 regulates the amount of elution with respect to inks and coating agents that do not come into contact with food, and is currently the only positive list (PL) of non-food 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. Similarly, regarding the monomers and photopolymerization initiators contained in the printing ink, if the toxicity data is unknown, the SML is less than 10 μg / kg-food.

  As for mineral oil, C10-C35 mineral oils are targeted by the European Food Safety Agency (EFSA), and absorption exceeding C35 is considered negligible. In Swiss Ordinance SR817.023.21, the SML of mineral oils is less than 0.6 mg / kg-food. Moreover, about white mineral oil, it is set as less than 0.01 mg / kg-food.

  The barrier 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, printed layer, laminated recycled paper, etc. 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 material is heat-sealed by overlaying the inner surface (seal layer) of the barrier laminate of the present invention, or by heat-sealing the seal layer and the surface layer opposite to the seal layer in the laminate, A packaging bag formed with the inner surface as the inner side is preferred. 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.

  Furthermore, it can also be used as a food barrier outer material disposed on the inner surface of a carton box printed with printing ink.

  In the packaging material using the barrier laminate of the present invention, in order to weaken the initial tearing strength and improve the openability, any tears such as V-notch, I-notch, perforation, and micro-porosity are started in the seal portion. A part 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 introduction tube, rectification tube, water separator, etc., 10.0 parts by weight of ethylene glycol, 21.1 parts by weight of neopentyl glycol, 10- 1,6-hexanediol 0.0 parts by weight, 8.0 parts by weight of Tsunodim 216, 21.5 parts by weight of isophthalic acid, 21.5 parts by weight of terephthalic acid, 23.4 parts by weight of adipic acid and 0.006 parts by weight of a titanium catalyst The internal temperature was maintained at 240 ° C. by gradually heating so that the tube upper temperature did not exceed 100 ° C. 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 by mass of the obtained intermediate polyester polyol, 8.9 parts by mass 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. Obtained. This was diluted with 111.9 parts by mass 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% by mass.

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.

Preparation Example 3 [Preparation of UV-curable inkjet ink composition]
Cyanine pigment manufactured by DIC Corporation: 1.8 parts by mass, epoxy acrylate manufactured by DIC Corporation: Unidic V-5530; 10 parts by mass, ethylene oxide-added trimethylolpropane triacrylate manufactured by BIGEN: Miramar M3110; 25 parts by mass, beauty Source dipropylene glycol diacrylate: Miramar M222; 50 parts by mass, Isooctyl acrylate: IO-AA; 15 parts by mass, BASF Photopolymerization initiator: Irgacure 819; 6 parts by mass, Shin-Etsu Chemical Poly Ether-modified silicone oil: KF-351; 0.2 parts by mass is mixed, sufficiently stirred and dissolved, and then filtered using a 1.2 μm membrane filter to obtain an ink composition for an ultraviolet curable inkjet printer. Obtained.

Adjustment Example 4 [Coating agent]
An ethylene-norbornene copolymer (COC) having various Tg was dissolved and stirred uniformly in tetrahydrofuran to adjust the solid content concentration to 15% by mass.

Example 1
As the resin for the sealing layer (A), a propylene-ethylene copolymer having a melting point of 127 ° C. and MFR of 7 g / 10 minutes (230 ° C., 21.18N) was used. As the resin for the intermediate layer (B), a melting point of 164 ° C., MFR of 8 g / A 10 minute (230 ° C., 21.18 N) propylene homopolymer was used. These resins are respectively supplied to an extruder for sealing layer (A) (caliber 40 mm) and an extruder for intermediate layer (B) (caliber 50 mm) and melted at 200 to 250 ° C., and the melted resin is fed into a block. Co-extrusion multilayer film manufacturing apparatus (feed block and T-die temperature: 250 ° C.) with T-die / chill roll method, and co-melt extrusion is performed, and the layer structure of the film is two layers of seal layer / intermediate layer With the configuration, a multilayer film (I) having a total thickness of 30 μm and a thickness ratio of each layer of 20/80% was obtained. Moreover, the surface of the intermediate layer was subjected to corona treatment online.

Subsequently, the coating agent produced using the COC of Tg80 degreeC by the adjustment example 4 was apply | coated to the surface which gave the corona treatment so that the thickness after drying might be set to 2 micrometers. Further, the coated surface was subjected to corona treatment after drying. Further, Preparation Examples 1 and 2, aromatic polyisocyanate (KW-75 manufactured by DIC Corporation), saturated hydrocarbon (n-pentadecane, cholestane), and aromatic hydrocarbon (biphenyl, 2,6-diisopropylnaphthalene) are shown in Table 1. The adhesive composition containing a mineral oil having a solid content of 30% was prepared. With respect to the obtained adhesive composition, it was applied to an aluminum foil having a thickness of 12 μm so that the coating amount was 2.2 g / m ^2, and the coating layer (C) was laminated to form a laminated body. A dissolution test was performed. Moreover, the elution test of the epoxy silane was done simultaneously with the same sample.

Example 2
As the resin for the sealing layer (A), an ethylene-α olefin copolymer having a density of 0.900 g / cm ³ , an MFR of 3.5 g / 10 minutes (190 ° C., 21.18 N), and a melting point of 90 ° C. is used. ), An ethylene-α olefin copolymer having a density of 0.943 g / cm ³ , MFR 2.5 g / 10 min (190 ° C., 21.18 N) and a melting point of 130 ° C. was used. These resins were supplied to a seal layer (A) extruder (caliber 50 mm) and an intermediate layer (B) extruder (caliber 50 mm), respectively, and melted at 180 to 210 ° C. 200 mm, lip 3 mm spiral-type multilayer die equipped with air-cooled inflation method coextrusion multilayer film manufacturing equipment is supplied and co-melt extrusion is performed, and the layer structure of the film is a two-layer structure of seal layer / intermediate layer, A multilayer film having a total thickness of 50 μm and a thickness of each layer of 30/70% was obtained. Moreover, the surface of the coating layer was subjected to corona treatment online. Using this, a sample for elution of mineral oil and epoxysilane was obtained in the same manner as in Example 1 except that the thickness of COC was 2 μm after drying.

Example 3
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 resin for the sealing layer (A), and a melting point of 164 ° C. and MFR of 8 g / 10 min ( A multilayer film was obtained in the same manner as in Example 1 using a propylene homopolymer at 230 ° C. and 21.18 N). Subsequently, the coating agent created using COC of Tg80 degreeC by the adjustment example 4 was apply | coated to the surface which gave the corona treatment so that the thickness after drying might be set to 2 micrometers. Further, the coated surface was subjected to corona treatment after drying. The UV curable ink jet printer ink prepared in Preparation Example 3 was applied to a biaxially stretched polyester film so that the thickness after curing was 8 μm, and then passed through a UV irradiation device to cure the ink. Next, with the composition shown in Table 1, a polyol resin solution U, an aromatic polyisocyanate (KW-75 manufactured by DIC Corporation), and a silane compound were blended to prepare an adhesive blend having a solid content of 30%. About the obtained adhesive composition, it apply | coated to the printing surface of the printed biaxially-stretched polyester film so that an application quantity might be 2.2 g / m < ² >, and it bonded together with the coating layer, and obtained the laminated body.

Example 4
A COC coated film was obtained in the same manner as in Example 3. Using this, the ultraviolet curable ink jet printer ink prepared in Preparation Example 3 was applied to the coating layer so that the thickness after curing was 8 μm, and then the ink was cured by passing through a UV irradiation device to obtain a laminate. Got.

Example 5
As the resin for the sealing layer (A), an ethylene-α olefin copolymer having a density of 0.900 g / cm ³ , an MFR of 3.5 g / 10 minutes (190 ° C., 21.18 N), and a melting point of 90 ° C. is used. ) As a resin for use, an ethylene-α olefin copolymer having a density of 0.938 g / cm ³ , MFR 3.5 g / 10 min (190 ° C., 21.18 N) and a melting point of 127 ° C. was used in the same manner as in Example 1. A multilayer film was obtained. Subsequently, the coating agent produced using the COC of Tg80 degreeC by the adjustment example 4 was apply | coated to the surface which gave the corona treatment so that the thickness after drying might be set to 2 micrometers. Further, the coated surface was subjected to corona treatment after drying. The ultraviolet curable ink jet printer ink prepared in Preparation Example 3 was applied to a biaxially stretched polyester film so that the thickness after curing was 8 μm, and then passed through a UV irradiation device to cure the ink. Next, with the composition shown in Table 1, a polyol resin solution U, an aromatic polyisocyanate (KW-75 manufactured by DIC Corporation), and a silane compound were blended to prepare an adhesive blend having a solid content of 30%. About the obtained adhesive composition, it apply | coated to the printing surface of the printed biaxially-stretched polyester film so that an application quantity might be 2.2 g / m < ² >, and it bonded together with the coating layer, and obtained the laminated body.

Example 6
A COC coated film was obtained in the same manner as in Example 5. Using this, the UV curable ink jet printer ink prepared in Adjustment Example 3 was applied to the coating layer so that the thickness after curing was 8 μm, and then the ink was cured by passing through a UV irradiation device to be laminated. Got the body.

Comparative Example 1
A film having a total thickness of 30 μm made of a propylene homopolymer (MFR 7.0 g / 10 min, melting point 162 ° C.) was obtained. Table 1 shows Preparation Examples 1 and 2, aromatic polyisocyanate (KW-75 manufactured by DIC Corporation), saturated hydrocarbon (n-pentadecane, cholestane), and aromatic hydrocarbon (biphenyl, 2,6-diisopropylnaphthalene). An adhesive composition containing a mineral oil having a solid content of 30% was prepared with the composition shown. Regarding the obtained adhesive composition, it was applied to an aluminum foil having a thickness of 12 μm so that the coating amount was 2.2 g / m ^2, and the film coating layer was laminated to form a laminate, so that mineral oil was eluted. A test was conducted. Moreover, the elution test of the epoxy silane was done simultaneously with the same sample.

Comparative Example 2
Minerals were used in the same manner as in Comparative Example 1 except that a 30 μm thick film made of an ethylene-α-olefin copolymer having a density of 0.938 g / cm ³ and MFR of 3.5 g / 10 min (190 ° C., 21.18 N) was used. Samples for elution of oil and epoxysilane were obtained.

Comparative Example 3
As the resin for the surface layer and the sealing layer, an ethylene-α olefin copolymer having a density of 0.920 g / cm ³ and MFR of 3.8 g / 10 min (190 ° C., 21.18 N) was used. As an intermediate layer resin, a saponified ethylene-vinyl acetate copolymer (EVOH) having an ethylene content of 32 mol% was used. As the adhesive layer resin, acid-modified polyethylene (M503) manufactured by Mitsubishi Chemical Corporation was used. These resins were respectively supplied to the surface layer, the seal layer extruder (caliber 50 mm), the adhesive layer extruder (caliber 40 mm), and the intermediate layer extruder (caliber 40 mm) and melted at 200 to 230 ° C., The melted resin is supplied to a T-die / chill roll co-extrusion multi-layer film manufacturing apparatus (feed block and T-die temperature: 250 ° C.) having a feed block, and co-melt extrusion is performed. A multilayer film having a layer / adhesive layer / intermediate layer / adhesive layer / seal layer having a thickness of 16/5/8/5/16 μm (total thickness 50 μm) was obtained. The surface of the surface layer was subjected to corona treatment online. Using this, a sample for elution of mineral oil and epoxysilane was obtained in the same manner as in Example 1.

Comparative Example 4
A mineral oil and epoxysilane elution sample was obtained in the same manner as in Comparative Example 3 except that nylon 6 having a specific gravity of 1.14 was used as the intermediate layer resin.

Comparative Example 5
A film having a total thickness of 30 μm made of a propylene homopolymer (MFR 7.0 g / 10 min, melting point 162 ° C.) was used. The UV curable ink jet printer ink prepared in Preparation Example 3 was applied to a biaxially stretched polyester film so that the thickness after curing was 8 μm, and then passed through a UV irradiation device to cure the ink. Next, with the composition shown in Table 1, a polyol resin solution U, an aromatic polyisocyanate (KW-75 manufactured by DIC Corporation), and a silane compound were blended to prepare an adhesive blend having a solid content of 30%. About the obtained adhesive composition, it apply | coated to the printing surface of the printed biaxially-stretched polyester film so that an application quantity may be 2.2 g / m < ² >, and it bonds together with the corona treatment surface of a film, and a laminated body is attached. Obtained.

Comparative Example 6
A laminate was obtained in the same manner as in Comparative Example 5 except that the same film as in Comparative Example 3 was used.

Comparative Example 7
A laminate was obtained in the same manner as in Comparative Example 5 except that the same film as in Comparative Example 4 was used.

Test method (1) Elution of mineral oil <Conforming to EN13130>
Using a laminate obtained by laminating a 12 μm thick aluminum foil and a multilayer film, a pouch is prepared so that the contact area with the contents is 200 cm ^2, and 100 ml of 95% ethanol is filled and sealed.
The filled and sealed pouch is stored at 60 ° C. for 10 days, 95% ethanol is concentrated from 100 ml to 5 ml, and quantified by gas chromatography mass spectrometry (GC-MS). The evaluation is performed based on the elution ratio with respect to the theoretical content blended in the adhesive in a model manner.
GC-MS: Shimadzu GC2100A

(2) Suppression of adhesive component (epoxysilane) elution <conforming to EN13130>
A pouch was prepared using a laminate obtained by laminating a 12 μm thick aluminum foil and a multilayer film so that the contact area with the contents was 200 cm ^2, and 100 ml of 95% ethanol was filled and sealed.
After storing the filled and sealed pouch at 60 ° C. for 10 days, 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

(3) Suppression of elution of ink component for ultraviolet curable ink jet printer The film prepared by applying the ink composition for an ultraviolet curable ink jet printer prepared as described above was attached to a single-side elution device. (Inside surface area 100 cm ² ) A single-side elution apparatus was fully filled with 100 ml of 98% ethanol as a food pseudo-solvent. After storage at 60 ° C. for 10 days, the content of 98% ethanol from 100 ml, gas chromatograph mass spectrometry (GC-MS), and liquid chromatograph mass spectrometry (LC-MS) are used for photoinitiator and monomer. Quantify ingredients.
The results evaluated above are summarized below.

Claims (12)

A sealing layer (A) mainly composed of an ethylene-based resin (a1) or a propylene-based resin (a2) having a melting point in the range of 70 ° C. to 150 ° C .;
An intermediate layer (B) mainly composed of an ethylene resin (b1) or a propylene resin (b2) having a melting point in the range of 110 ° C. to 168 ° C.
On the intermediate layer (B) of the multilayer film (I) in which the melting point of the main component resin of the intermediate layer (B) is higher than the melting point of the main component resin of the seal layer (A),
A coating layer (C) obtained by applying a coating agent containing a cyclic olefin resin (c1) having a glass transition temperature Tg of 60 ° C. to 200 ° C. is laminated, and on the coating layer (C),
A barrier laminate, wherein at least one layer (D) selected from the group consisting of an adhesive layer (D1), a printed layer (D2), and a layer (D3) containing mineral oil is laminated. The total thickness of the multilayer film (I) is 15 to 150 μm, the thickness ratio of the intermediate layer (B) in the multilayer film (I) is 60 to 99%, and the thickness of the sealing layer (A) is 1 μm or more. Item 10. The barrier laminate according to Item 1. The barrier laminate according to claim 1 or 2, wherein the cyclic olefin resin (c1) is a norbornene polymer having a melt flow rate MFR (230 ° C, 21.18N) of 0.2 to 17 g / 10 min. The barrier packaging material according to any one of claims 1 to 3, wherein the multilayer film (I) is laminated by a coextrusion lamination method. The barrier laminate according to any one of claims 1 to 4, further comprising a layer made of the base film (II) on the layer (D). The barrier laminate according to any one of claims 1 to 5, wherein the printing layer (D2) is a printing layer made of an active energy ray-curable printing ink. The elution test based on the regulation of Swiss Ordinance SR817.023.21 suppresses elution of the monomer and initiator contained in the active energy ray-curable printing ink to less than 10 µg / kg-food. Barrier laminate. The barrier laminate according to any one of claims 1 to 5, wherein the layer (D3) containing mineral oil is an adhesive layer or ink layer containing mineral oil, or a layer made of recycled paper. The layer (D) is a layer (D3) containing mineral oil,
In the dissolution test based on the regulation of Swiss Ordinance SR817.023.21, elution of saturated hydrocarbons or aromatic hydrocarbons contained in mineral oil is suppressed to less than 0.6 mg / kg-food. The barrier laminate according to any one of 5 and 8. The layer (D) is an adhesive layer (D1) and is formed using an adhesive containing a silane compound,
The barrier laminate according to any one of claims 1 to 5, wherein elution of the silane compound is suppressed to less than 10 µg / kg-food in an elution test based on the regulation of Swiss Ordinance SR817.023.21. A packaging material using the barrier laminate according to any one of claims 1 to 10. The packaging material according to claim 11, which is used for food or medicine.