JP6089463B2 - LAMINATE, MANUFACTURING METHOD THEREOF AND PACKAGE BODY USING THE SAME - Google Patents

Description

  The present invention relates to a laminate formed by laminating a resin film and paper having different properties and a package obtained by processing the laminate, and more specifically, a resin film and a paper using an amorphous cyclic polyolefin resin. The present invention relates to a laminated body that can be suitably used as a packaging body for packaging food, a method for producing the same, and a packaging body for containers such as cups and trays and lids using the laminated body. .

  Conventionally, packaging materials such as cups and trays for dry foods such as instant noodles, soups, miso soup, etc. have been required to have various performances such as moisture resistance, sealing properties, and barrier properties to prevent migration of odor components from the outside. In general, a laminate in which a coating layer such as a resin film is provided on a paper substrate is used. As these laminated bodies, for example, an olefin-based laminated body in which a polyolefin layer such as polyethylene or polypropylene is provided on a paper base material is known. However, this olefin-based laminate has insufficient moisture resistance and migration barrier properties for external odor components. As a method for solving this problem, a laminated body comprising a barrier layer, that is, a paper substrate / intermediate resin (polyethylene) layer / barrier layer / sealant layer has been provided (for example, see Patent Document 1). However, in Patent Document 1, a barrier film, that is, a uniaxially stretched or biaxially stretched polyethylene terephthalate (PET) film, a polyamide film or the like is singly or further laminated with an inorganic compound on the film. It is necessary to bond these barrier films to a base paper consisting of a paper base material / intermediate resin layer, and an olefin resin layer that functions as a sealant layer, for the use of adhesives and anchor coating agents. Or, as the number of manufacturing steps increases, productivity is poor and costs are increased. Moreover, there exists a problem that the component contained in an adhesive agent or an anchor coat agent transfers to a content, and the flavor of a content is impaired.

  In addition, as a laminate including a paper base material particularly excellent in aroma retention, a laminate comprising kraft paper / low density polyethylene / linear low density polyethylene / adhesive resin / EVOH / adhesive resin / linear low density polyethylene is used. It is disclosed (for example, see Patent Document 2). This laminate is made by utilizing the fact that EVOH is inherently excellent in gas barrier properties and scent retention, and is superior in performance to prevent migration of odor components from the outside, but moisture absorption of EVOH, which is a contradictory performance. As a result, the moisture resistance of the laminate is insufficient.

Japanese Patent Laid-Open No. 2003-221024 JP 2002-068283 A

  The object of the present invention has been made in view of the above problems, is relatively inexpensive for foods, etc., has particularly good moisture resistance and barrier properties, and is molded into containers such as cups and trays. It is providing the laminated body which is excellent in a characteristic, its manufacturing method, and a package using this.

  As a result of diligent research to solve the above problems, the present inventors have found that a film having a resin layer containing an amorphous cyclic polyolefin and a polyolefin resin and a paper base material are anchored by a melt extrusion laminating method. The present inventors have found that the above-mentioned problems can be solved by using a laminated body that is laminated without interposing any of the above, and have completed the present invention.

  That is, the present invention is a film having a resin layer (C) containing a paper base (A), an adhesive resin (B), an amorphous cyclic polyolefin resin (c1), and a polyolefin resin (c2). (I) has a multilayer structure in which (A) / (B) / (I) are stacked in this order, a method for manufacturing the same, and cups, trays, and the like formed by molding the same The package is provided.

  The laminate of the present invention is obtained by laminating a film having excellent moisture resistance and barrier properties to a versatile paper base material, and can easily impart moisture resistance and barrier. The secondary processed product of the paper laminate of the present invention is excellent in easy-opening property (easy tearing property), and is suitably applied to a cup for receiving dried food such as instant noodles, soup, miso soup, trays and the like. be able to.

  The laminate of the present invention comprises a film (I) having a resin layer (C) containing an amorphous cyclic polyolefin resin (c1) and a polyolefin resin (c2) as a paper substrate (A) and an adhesive resin. (B) is laminated. The film (I) may be a single-layer film composed only of the resin layer (C) or a multilayer film laminated with other resin layers.

  Examples of the amorphous cyclic polyolefin resin (c1) that is the main component of the resin layer (C) include norbornene polymers, vinyl alicyclic hydrocarbon polymers, and cyclic conjugated diene polymers. Among these, norbornene-based polymers are preferable. The norbornene-based polymer includes a ring-opening polymer of a norbornene-based monomer (hereinafter referred to as “COP”), a norbornene-based copolymer obtained by copolymerizing a norbornene-based monomer and an olefin such as ethylene (hereinafter, referred to as “COP”). , “COC”). Furthermore, COP and COC hydrogenates are particularly preferred. The weight average molecular weight of the amorphous cyclic polyolefin resin (c1) is preferably 5,000 to 500,000, more preferably 7,000 to 300,000.

  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.

  Moreover, it is preferable that the glass transition point (Tg) of the said amorphous cyclic polyolefin resin (c1) is 70 degreeC or more from the point of the heat resistance of the film (I) obtained, and high rigidity, and it is mentioned later. When the multilayer film (I) is used, it is preferable that Tg is 200 ° C. or less from the viewpoint of production by a coextrusion laminating method and industrial raw material availability. The temperature is particularly desirably 80 ° C to 180 ° C. As the amorphous cyclic polyolefin-based resin (c1) having such Tg, the content ratio of the norbornene monomer is preferably in the range of 20 to 90% by mass, more preferably 25 to 90% by mass, More preferably, it is 30-85 mass%. When the content ratio is within this range, the heat resistance, rigidity, moisture resistance, and processing stability are improved. In addition, the glass transition point (Tg) in this invention is a value obtained by measuring by DSC.

  On the other hand, norbornene copolymers with a high glass transition point (Tg) have low tensile strength, are too rigid, and are extremely easy to break and tear easily. In consideration of handleability, it is also possible to blend a high Tg product and a low Tg product having a glass transition point of less than 100 ° C.

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

  As the resin layer (C) of the film (I) used in the present invention, the amorphous cyclic polyolefin-based resin (c1) is one component, and further, the moisture resistance is improved, the cost is reduced, and the rigidity is too high. From the viewpoint of compatibility with the amorphous cyclic polyolefin-based resin (c1), it is essential to use the polyolefin-based resin (c2) together with the point that it becomes difficult to handle, the viewpoint of being easily torn, and the petroleum resin, coumarone. -You may use together 1 or more types of resin (c3) chosen from the group which consists of indene resin, terpene resin, rosin resin, and these hydrogenated products.

  The polyolefin resin (c2) may be any olefin homopolymer or copolymer having no cyclic structure. For example, as the polyethylene resin (c2-1), very low density polyethylene (VLDPE), wire Polyethylene resin such as low density polyethylene (LLDPE), low density polyethylene (LDPE), high density polyethylene (HDPE), ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), Ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate (EMA) copolymer, ethylene-ethyl acrylate-maleic anhydride copolymer (E-EA-MAH), ethylene-acrylic acid copolymer (EAA) ), Ethylene-methacrylic acid copolymer (EMAA), etc. Emissions copolymer; more ethylene - ionomer of acrylic acid copolymer, ethylene - mentioned ionomer methacrylic acid copolymer, and, alone, may be used by mixing two or more kinds. Among these, HDPE, VLDPE, LDPE, LLDPE from the viewpoints of moisture resistance when made into a laminate, processability when forming the laminate (film formability), and formability when secondary processing is performed. Is preferably used.

Examples of the polyethylene resin (c2-1), density be used 0.88 g / cm ² or more 0.970 g / cm ² less than the polyethylene-based resin, from the viewpoint of moisture resistance, among others high density polyethylene (HDPE ) Is preferred.

  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. The storage stability (physical property stability) is improved.

As described above, the density of the polyethylene resin (c2-1) is preferably 0.88 to 0.97 g / cm ³ . If the density is within this range, it has appropriate rigidity, excellent mechanical strength such as pinhole resistance, and film film formability and extrusion suitability are improved. Moreover, it is preferable that melting | fusing point is generally the range of 60-130 degreeC, and 70-120 degreeC is more preferable. If melting | fusing point is this range, processing stability and coextrusion workability with an amorphous cyclic polyolefin resin (c1) will improve. Moreover, it is preferable that it is 2-20 g / 10min, and, as for MFR (190 degreeC, 21.18N) of the said polyethylene-type resin, it is more preferable that it is 3-10 g / 10min. When the MFR is within this range, the extrusion moldability is improved.

  Further, as the polyolefin resin (c2), as the polypropylene resin (c2-2), for example, a propylene homopolymer, a propylene / α-olefin random copolymer, such as a propylene-ethylene copolymer, propylene-butene- 1 copolymer, propylene-ethylene-butene-1 copolymer, metallocene catalyst-based polypropylene and the like. These may be used alone or in combination. A propylene-α-olefin random copolymer is desirable, and a propylene / α-olefin random copolymer polymerized using a metallocene catalyst is particularly preferable. When these polypropylene resins are used, the heat resistance of the obtained film (I) is improved, and the softening temperature can be increased.

  In addition, these polypropylene resins (c2-2) 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 MFR ( 230 ° C.) is 2.0 to 15.0 g / 10 min, and the melting point is 115 to 162 ° C. If MFR and melting | fusing point are this range, the dimensional stability of the film (I) obtained will be favorable, and the film-forming property at the time of setting it as a film will also improve.

  The proportion of the polyolefin-based resin (c2) used is preferably in the range of 5 to 50% by mass with respect to the total mass of the resin that forms the resin layer (C).

  Further, the resin (c3) to be used in combination is petroleum resin, coumarone-indene resin, terpene resin, rosin resin such as polymerized rosin, or hydrogenated products thereof. In particular, from the viewpoint of moisture resistance and moldability, it is preferable to use the resin (c3) in combination, and the use ratio thereof is in the range of 3 to 50% by mass with respect to the total mass of the resin forming the resin layer (C). It is preferable that

  Examples of petroleum resins include alicyclic petroleum resins obtained by polymerizing cyclopentadiene or its dimer, aromatic petroleum resins obtained by polymerizing C9 component, and the like. Examples of the terpene resin include a terpene-phenol resin obtained by polymerizing β-pinene. Examples of rosin resins include rosin resins such as gum rosin and wood rosin, and esterified rosin resins modified with glycerin, pentaerythritol, and the like. Specific examples include Alcon (trade name: manufactured by Arakawa Chemical Co., Ltd.), Clearon (trade name: manufactured by Yasuhara Chemical Co., Ltd.), and the like. These may be used alone or in combination of two or more.

  In addition, the film (I) used in the present invention may be a single-layer film composed only of the resin layer (C). However, from the viewpoint of cost reduction and the balance between rigidity, tearability and the like as described above. Thus, a multilayer film in which the resin layer (D) containing the polyolefin resin (d) as a main component is laminated on one side or both sides of the resin layer (C) may be used. In the present invention, the main component means that the specific resin is contained in an amount of 50% by mass or more based on the total mass of the resin components used for forming the resin layer. Means to contain at 60 mass% or more.

  As the resin for forming the resin layer (D) to be laminated on the resin layer (C), a polyethylene resin and / or a polypropylene resin is used from the viewpoint of compatibility with the amorphous cyclic polyolefin resin (c1). preferable. The resin layer (D) may be a single layer or a laminate of two or more layers.

  The polyethylene-based resin and / or polypropylene-based resin used for the resin layer (D) is the same as the above-described polyolefin-based resin (c2), and preferable ones are also the same. The polyethylene resin and polypropylene resin used together in the resin layer (C) and the polyethylene resin and polypropylene resin used as the main component of the resin layer (D) are different even if the same one is used. May be used.

  Furthermore, as the film (I) used in the present invention, the amorphous cyclic polyolefin-based resin (c1) is formed on the resin layer (D) for the purpose of further imparting moisture resistance or improving moldability. A layer corresponding to the resin layer used alone or the resin layer (C) containing this and the polyolefin resin (c2) is laminated, and (C) / (D) / (C), (D) / ( It may have a multilayer structure such as C) / (D) / (C).

  The thickness of the film (I) used in the present invention is preferably in the range of 15 to 100 μm, particularly in the range of 20 to 90 μm, from the viewpoint of the balance between moisture resistance, barrier properties and processability. preferable.

  For each of the resin layers (C) and (D), an antifogging agent, an antistatic agent, a thermal stabilizer, a nucleating agent, an antioxidant, a lubricant, an antiblocking agent, a release agent, Components such as an ultraviolet absorber and a colorant can be added as long as the object of the present invention is not impaired. In particular, it is possible to make the content opaque or white due to the concealability of the contents and the print appearance characteristics.

  In the film (I) used in the present invention, the surface of the outermost resin layer laminated with the adhesive resin (B) is treated, and the surface tension of the outermost surface is 38 mN / m or more, preferably 40 mN / m or more. can do. 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, it is possible to ensure interlayer adhesion even in the case of extrusion lamination.

  Although it does not specifically limit as a manufacturing method of the film (I) used by this invention, For example, when setting it as a multilayer structure, the resin or resin mixture used for each resin layer is heat-melted with a respectively separate extruder, Examples thereof include a coextrusion method in which a desired multilayer structure is laminated in a molten state by a method such as a coextrusion multilayer die method or a feed block method, and then formed into a film 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 multilayer film excellent in hygiene and cost performance can be obtained. In addition, when a resin layer (C) mainly composed of an amorphous cyclic polyolefin resin used in the present invention and a polyethylene resin or acid-modified polyethylene are used as the resin layer (D), the melting point between them is Since the difference from Tg may be large, the appearance of the film may be deteriorated during co-extrusion, or 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.

As a paper base material (A) used by this invention, it is preferable to select and use a thing with a basic weight of about 200-500 g / m < ² >. When the basis weight is less than 200 g / m ² , there is a possibility that sufficient waist and strength as a container may not be obtained, and when it exceeds 500 g / m ² , the processability when forming into a container is inferior and economical. Further, it is not preferable.

  In the present invention, the above-mentioned film (I) and paper substrate (A) are bonded together. As the adhesive resin (B) used for this purpose, LLDPE, LDPE, acid-modified olefin resin, or the like can be used. These may be used alone or in combination of two or more. Any of the above-mentioned LLDPE and LDPE can be used.

  The olefin component which is the main component of the acid-modified polyolefin is not particularly limited, but preferably an alkene having 2 to 6 carbon atoms such as ethylene, propylene, isobutylene, 2-butene, 1-butene, 1-pentene, 1-hexene, Mixtures of these may be used. Among these, alkene having 2 to 4 carbon atoms such as ethylene, propylene, isobutylene and 1-butene is more preferable, ethylene and propylene are further preferable, and ethylene is most preferable. Moreover, it is preferable that the acid-modified polyolefin contains a (meth) acrylic acid ester component. (Meth) acrylic acid ester components include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic acid Examples include octyl, decyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and the like. From the viewpoint of easy availability and adhesiveness, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and hexyl acrylate are more preferable, and methyl acrylate and ethyl acrylate are more preferable. The (meth) acrylic acid ester component may be copolymerized with the olefin component, and the form thereof is not limited. Examples of the copolymerization state include random copolymerization, block copolymerization, and graft copolymerization. (Graft modification) and the like. (In addition, "(meth) acrylic acid ~" means "acrylic acid ~ or methacrylic acid ~".) Specifically, as an ethylene- (meth) acrylic acid ester copolymer, for example, Elvalloy ( Product name: Mitsui-DuPont Polychemical Co., Ltd.), Aklift (trade name: Sumitomo Chemical Co., Ltd.), etc. These may be used alone or in combination of two or more.

  The acid-modified polyolefin may be one that has been acid-modified with an unsaturated carboxylic acid component. Examples of unsaturated carboxylic acid components include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, and the like, as well as unsaturated dicarboxylic acid half esters and half amides. It is done. Of these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable, and acrylic acid and maleic anhydride are particularly preferable. The unsaturated carboxylic acid component may be copolymerized with the olefin component, and the form thereof is not limited. Examples of the copolymerization state include random copolymerization, block copolymerization, and graft copolymerization (grafting). Modification). Specifically, examples of the ethylene-acrylic acid copolymer include Nucrel (trade name: Mitsui / DuPont Polychemical Co., Ltd.). Examples of the ethylene- (meth) acrylic acid ester-maleic anhydride copolymer include bondine (trade name: manufactured by Tokyo Materials Co., Ltd.). These may be used alone or in combination of two or more.

  Furthermore, as the acid-modified polyolefin, ethylene-vinyl acetate copolymer (EVA), or this EVA as a base resin, rosin, hydrogenated rosin, rosin ester derivative, polymerized rosin, terpene, modified terpene resin, aliphatic petroleum Modified EVA obtained by mixing and modifying one or more of resins and styrene resins is preferable, and modified EVA is particularly preferable. Specific examples of the modified EVA include modified polyethylene VMI- manufactured by Mitsubishi Chemical Corporation and Mersen manufactured by Tosoh Corporation.

  Since the film (I) used in the present invention is obtained as a substantially unstretched film by the above-described production method, after drawing and pasting with the paper substrate (A), deep drawing or foil pressing by vacuum forming or the like. Secondary molding is also possible. Bonding with the paper substrate (A) can be easily performed by extrusion lamination of the adhesive resin (B).

  Although the laminated body of this invention is secondary-processed and used as various packaging bodies, it does not restrict | limit especially as the shaping | molding method. In general, various types of paper cup molding, press molding, vacuum molding, pressure molding and the like can be mentioned.

  The scope of application of the laminate of the present invention is not particularly limited, and includes cups, trays, containers, etc. used for foods, pharmaceuticals, industrial parts, etc. Especially, instant noodles, soup, miso soup, etc. It can be suitably used as a cup.

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

Example 1
As a resin for the resin layer (C), a ring-opening polymer of a norbornene-based monomer [“Apel APL8008T” manufactured by Mitsui Chemicals, MFR: 15 g / 10 min (260 ° C., 21.18 N), glass transition temperature: 70 ° C .; Hereinafter, it is referred to as “COC (1)”. ] 70 parts by mass and high density polyethylene [density: 0.960 g / cm ³ , melting point 128 ° C., MFR: 10 g / 10 minutes (190 ° C., 21.18 N); hereinafter referred to as “HDPE”. 30 parts by mass of a resin mixture was used. This resin is supplied to a resin layer (C) extruder (40 mm in diameter) and melted at 200 to 230 ° C., and the melted resin is a T-die / chill roll co-extruded multilayer film production apparatus (with a feed block) ( The film was supplied to a feed block and a T-die temperature: 250 ° C. and melt-extruded to obtain a film (I-1) having a film thickness of 20 μm. The surface of the resin layer (C) was subjected to corona treatment, and the surface tension with a wetting reagent was 40 mN / m. Linear medium density polyethylene [density: 0.930 g / cm ³ , melting point as an adhesive resin between the treated surface of the obtained film (I-1) and a base paper (A1) having a basis weight of 300 g / m ² 125 ° C., MFR: 5 g / 10 min (190 ° C., 21.18 N); hereinafter referred to as “LMDPE”. ] Was laminated by melt extrusion to prepare a laminate. The thickness of the layer made of adhesive resin is 20 μm.

Example 2
As the resin for the resin layer (C), a resin mixture of 70 parts by mass of COC (1) and 30 parts by mass of HDPE was used. Moreover, LMDPE was used as resin for resin layers (D). These resins are respectively supplied to an extruder for resin layer (C) (caliber 40 mm) and an extruder for resin layer (D) (caliber 50 mm) and melted at 200 to 230 ° C., and the melted resin is fed into the feed block Co-extrusion multilayer film production apparatus (feed block and T-die temperature: 250 ° C.) of T-die / chill roll method having co-extrusion is performed, and the film layer structure is (C) / (D) A co-extruded multilayer film (I-2) having a two-layer structure in which the thickness of each layer was 20 μm / 10 μm (total 30 μm) was obtained. The surface of the resin layer (C) was subjected to corona treatment, and the surface tension by the wetting reagent was 40 mN / m. In the same manner as in Example 1, LMDPE was laminated by melt extrusion between the (C) side (treated surface) of the film (I-2) and the cup base paper (A) to prepare a laminate.

Example 3
As the resin for the resin layers (C-1) and (C-2), a resin mixture of 70 parts by mass of COC (1) and 30 parts by mass of HDPE was used. Moreover, LMDPE was used as resin for resin layers (D). These resins are respectively supplied to the resin layer (C-1) and (C-2) extruder (caliber 40 mm) and the resin layer (D) extruder (caliber 50 mm) and melted at 200 to 230 ° C. The melted resin is supplied to a T-die / chill roll co-extrusion multilayer film production apparatus having a feed block (feed block and T-die temperature: 250 ° C.), and co-melt extrusion is performed. A coextruded multilayer film (I-3) having a three-layer structure of (C-1) / (D) / (C-2) and having a thickness of 10 μm / 10 μm / 10 μm (total 30 μm) was obtained. One side of the resin layer (C-1) was subjected to corona treatment, and the surface tension with a wetting reagent was 40 mN / m. The treated surface of the film (I-3), the cup base paper (A), and LMDPE were laminated in the same manner as in Example 1 to prepare a laminate.

Example 4
As the resin for the resin layer (C), a resin mixture of 70 parts by mass of COC (1) and 20 parts by mass of HDPE and 10 parts by mass of a petroleum resin (“Arcon P-125” softening point 125 ° C. manufactured by Arakawa Chemical Industries) was used. LMDPE was used as the resin for the resin layer (D). In the same manner as in Example 2, a coextruded multilayer film (I-4) having a two-layer structure (C) / (D) and a thickness of each layer of 20 μm / 10 μm (total 30 μm) was obtained. Obtained. The surface of the resin layer (C) was subjected to corona treatment, and the surface tension with the wetting reagent was 45 mN / m. The treated surface side of the film (I-4), the cup base paper (A), and LMDPE were laminated in the same manner as in Example 1 to obtain a laminate.

Example 5
As the resin for the resin layers (C-1) and (C-2), a resin mixture of 70 parts by mass of COC (1), 20 parts by mass of HDPE, and 10 parts by mass of petroleum resin was used. LMDPE was used as the resin for the resin layer (D). In the same manner as in Example 3, the layer structure of the film is a three-layer structure of (C-1) / (D) / (C-2), and the thickness of each layer is 10 μm / 10 μm / 10 μm (total 30 μm). A coextruded multilayer film (I-5) was obtained. The surface of the resin layer (C-1) was subjected to corona treatment, and the surface tension with a wetting reagent was 40 mN / m. The treated surface side of the film (I-5), the cup base paper (A), and LMDPE were laminated in the same manner as in Example 1 to prepare a laminate.

Example 6
As the resin for the resin layers (C-1) and (C-2), a resin mixture of 70 parts by mass of COC (1) and 30 parts by mass of HDPE was used. Further, as a resin for the resin layer (D), a propylene-α-olefin random copolymer polymerized using a metallocene catalyst [density: 0.900 g / cm ³ , melting point 135 ° C., MFR: 4 g / 10 min (230 ° C, 21.18 N); hereinafter referred to as “MRCP”. ) Was used. In the same manner as in Example 3, the layer structure of the film is a three-layer structure of (C-1) / (D) / (C-2), and the thickness of each layer is 10 μm / 10 μm / 10 μm (total 30 μm). A coextruded multilayer film (I-6) was obtained. The surface of the resin layer (C-1) was subjected to corona treatment, and the surface tension with a wetting reagent was 40 mN / m. The following was performed in the same manner as in Example 1 to obtain a laminate.

Example 7
As the resin for the resin layers (C-1) and (C-2), a resin mixture of 70 parts by mass of COC (1), 20 parts by mass of HDPE, and 10 parts by mass of petroleum resin was used. In addition, MRCP was used as the resin for the resin layer (D). In the same manner as in Example 3, the layer structure of the film is a three-layer structure of (C-1) / (D) / (C-2), and the thickness of each layer is 10 μm / 10 μm / 10 μm (total 30 μm). A coextruded multilayer film (I-7) was obtained. The surface of the resin layer (C-1) was subjected to corona treatment, and the surface tension with a wetting reagent was 40 mN / m. The following was performed in the same manner as in Example 1 to obtain a laminate.

Example 8
As a resin for the resin layer (C-1), a resin mixture of 70 parts by mass of COC (1) and 30 parts by mass of HDPE was used. As resin for the resin layer (C-2), 40 parts by mass of COC (1) and a ring-opening polymer of norbornene-based monomer [“Apel APL6013T” manufactured by Mitsui Chemicals, Inc., MFR: 15 g / 10 min (260 ° C., 21 18N), glass transition temperature: 125 ° C .; hereinafter referred to as “COC (2)”. A resin mixture of 30 parts by mass and 30 parts by mass of HDPE was used. Moreover, LMDPE was used as resin for resin layers (D). These resins are respectively supplied to the resin layer (C-1) and (C-2) extruder (caliber 40 mm) and the resin layer (D) extruder (caliber 50 mm) and melted at 200 to 230 ° C. The melted resin is supplied to a T-die / chill roll co-extrusion multilayer film production apparatus having a feed block (feed block and T-die temperature: 250 ° C.), and co-melt extrusion is performed. A coextruded multilayer film (I-8) having a three-layer structure of (C-1) / (D) / (C-2) and having a thickness of 10 μm / 10 μm / 10 μm (total 30 μm) was obtained. The surface of the resin layer (C-1) was subjected to corona treatment, and the surface tension with a wetting reagent was 40 mN / m. The treated surface side of the film (I-8) and the cup base paper (A) were laminated in the same manner as in Example 1 to produce a laminate.

Comparative Example 1
COC (1) is supplied to an extruder (40 mm in diameter) and melted at 200 to 230 ° C., and the molten resin is supplied to a T die / chill roll film production apparatus (T die temperature: 250 ° C.) to be melted. Extrusion was performed to obtain a film having a thickness of 20 μm. The obtained film was subjected to corona treatment, and the surface tension with a wetting reagent was 40 mN / m. The obtained film and cup base paper (A) were laminated in the same manner as in Example 1 to produce a laminate.

Comparative Example 2
LMDPE is supplied to an extruder (40 mm in diameter) and melted at 200 to 230 ° C., and the melted resin is supplied to a T die / chill roll film production apparatus (T die temperature: 250 ° C.) for melt extrusion. Thus, a film having a thickness of 20 μm was obtained. The obtained film was subjected to corona treatment, and the surface tension with a wetting reagent was 40 mN / m. The obtained film and cup base paper (A) were laminated in the same manner as in Example 1 to produce a laminate.

Comparative Example 3
Biaxially stretched polyester film (O-PET) A two-component reactive polyester resin is applied as an anchor coating agent to a 12 μm film, and the coated surface side and cup base paper (A) are laminated in the same manner as in Example 1, A laminate was produced.

Using the obtained laminate, it was evaluated by the following method.
Moisture proof Aluminum foil 30 μm with an epoxy-type two-part adhesive applied to a container with a 100 mmφ opening shape, a 65 mmφ round bottom shape, and a 100 mm depth container obtained by a paper cup molding machine. After the upper part was sealed, a constant temperature and humidity chamber with a humidity of 40 ° C. and 90% was placed, and the moisture permeation amount (g / 24 hr · 1 piece) was measured from the change in the weight of the container to evaluate the moisture resistance.

Perfume retention The paper cup container obtained above is filled with 15g of bathing agent, preservative (P-dichlorobenzene) and soap, and the upper part is sealed with aluminum foil 30μm coated with epoxy two-component adhesive, and then placed in an aluminum bag. And the sensory evaluation of the odor in the aluminum bag was carried out.
○: No odor ×: Odor

  The results obtained above are shown in Tables 1-2.

Claims (11)

  A film (I) having a resin layer (C) containing a paper substrate (A), an adhesive resin (B), an amorphous cyclic polyolefin resin (c1) and a polyolefin resin (c2), A laminate having a multilayer structure in which (A) / (B) / (I) are laminated in order, and the polyolefin resin (c2) is high-density polyethylene.   The resin layer (C) further contains one or more resins (c3) selected from the group consisting of petroleum resins, coumarone-indene resins, terpene resins, rosin resins, and hydrogenated products thereof. 1. The laminate according to 1.   The laminate according to claim 2, wherein the use ratio of the resin (c3) is in the range of 3 to 50 mass% with respect to the total mass of the resin forming the resin layer (C).   The laminate according to any one of claims 1 to 3, wherein the amorphous cyclic polyolefin resin (c1) is a norbornene polymer.   The laminate according to any one of claims 1 to 4, wherein the adhesive resin (B) is a polyolefin resin.   The said film (I) is a multilayer film formed by laminating | stacking the said resin layer (C) and the resin layer (D) which has polyolefin resin (d) as a main component. Laminated body.   The laminate according to any one of claims 1 to 6, wherein the film (I) has a thickness in the range of 15 to 100 µm.   The laminate according to any one of claims 1 to 7, which is used for molding.   A package formed by molding the laminate according to any one of claims 1 to 8.   A paper base (A), an adhesive resin (B), an amorphous cyclic polyolefin resin (c1) and a resin layer (C2) containing a polyolefin resin (c2), the polyolefin resin (C2) Film (I) whose density is high-density polyethylene is laminated in the order of paper base (A) / adhesive resin (B) / film (I) by extrusion lamination. Method.   The film (I) is a multilayer film formed by laminating the resin layer (C) and a resin layer (D) containing a polyolefin resin as a main component, and the multilayer film is produced by a coextrusion lamination method. The method for manufacturing a laminate according to claim 10.