WO2014024913A1 - Multilayered paper container - Google Patents

Multilayered paper container Download PDF

Info

Publication number
WO2014024913A1
WO2014024913A1 PCT/JP2013/071344 JP2013071344W WO2014024913A1 WO 2014024913 A1 WO2014024913 A1 WO 2014024913A1 JP 2013071344 W JP2013071344 W JP 2013071344W WO 2014024913 A1 WO2014024913 A1 WO 2014024913A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
ldpe
paper
density polyethylene
low density
Prior art date
Application number
PCT/JP2013/071344
Other languages
French (fr)
Japanese (ja)
Inventor
奥出 秀樹
Original Assignee
日本製紙株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本製紙株式会社 filed Critical 日本製紙株式会社
Priority to CN201380028020.3A priority Critical patent/CN104334459B/en
Priority to JP2014529528A priority patent/JPWO2014024913A1/en
Priority to KR20147032674A priority patent/KR20150042745A/en
Publication of WO2014024913A1 publication Critical patent/WO2014024913A1/en
Priority to HK15104709.7A priority patent/HK1203915A1/en

Links

Images

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/082Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/20Layered products comprising a layer of metal comprising aluminium or copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/28Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D5/00Rigid or semi-rigid containers of polygonal cross-section, e.g. boxes, cartons or trays, formed by folding or erecting one or more blanks made of paper
    • B65D5/02Rigid or semi-rigid containers of polygonal cross-section, e.g. boxes, cartons or trays, formed by folding or erecting one or more blanks made of paper by folding or erecting a single blank to form a tubular body with or without subsequent folding operations, or the addition of separate elements, to close the ends of the body
    • B65D5/06Rigid or semi-rigid containers of polygonal cross-section, e.g. boxes, cartons or trays, formed by folding or erecting one or more blanks made of paper by folding or erecting a single blank to form a tubular body with or without subsequent folding operations, or the addition of separate elements, to close the ends of the body with end-closing or contents-supporting elements formed by folding inwardly a wall extending from, and continuously around, an end of the tubular body
    • B65D5/064Rectangular containers having a body with gusset-flaps folded outwardly or adhered to the side or the top of the container
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D5/00Rigid or semi-rigid containers of polygonal cross-section, e.g. boxes, cartons or trays, formed by folding or erecting one or more blanks made of paper
    • B65D5/42Details of containers or of foldable or erectable container blanks
    • B65D5/56Linings or internal coatings, e.g. pre-formed trays provided with a blow- or thermoformed layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/50Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54Yield strength; Tensile strength
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/50Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558Impact strength, toughness
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/726Permeability to liquids, absorption
    • B32B2307/7265Non-permeable
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00Containers; Receptacles
    • B32B2439/70Food packaging
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D5/00Rigid or semi-rigid containers of polygonal cross-section, e.g. boxes, cartons or trays, formed by folding or erecting one or more blanks made of paper
    • B65D5/40Rigid or semi-rigid containers of polygonal cross-section, e.g. boxes, cartons or trays, formed by folding or erecting one or more blanks made of paper specially constructed to contain liquids

Definitions

  • the present invention relates to a multi-layer paper container with high storage stability.
  • it relates to a container that can be heated and sealed.
  • a metal can, a glass bottle, a plastic container, a paper container, or a film or metal foil is laminated and laminated as a container for filling and packaging food and drink, pharmaceuticals, cosmetics, detergents, chemicals, miscellaneous goods, and various other contents.
  • the container etc. which heat-sealed the laminated body and made it the bag shape are used.
  • the contents are conventionally packed in an airtight container such as a metal can, a glass bottle, a plastic pouch, a laminated pouch of plastic and aluminum foil, high temperature of 120 ° C., 4 minutes or more Sterilization under high pressure (hereinafter referred to as "retort") is performed.
  • heating conditions of food and drink are various depending on types of food and drink and sterilization conditions.
  • the pasteurization condition of milk is defined as "a method of heating at 63 ° C for 30 minutes or having a bactericidal effect equal to or higher than this" under "Ministerial Ordinance on Component Specifications of Milk and Dairy Products". As a method equivalent to heating at 63 ° C.
  • the method is defined as “method of heating at 40 ° C for 40 minutes or method having the same or higher efficacy”, but soymilk is coagulated after filling, and as a method having the same or higher efficacy after coagulation, high temperature treatment with milk (120 ⁇ Similarly to the case of 135 ° C., high temperature treatment is not desirable because the product is exposed to high temperature of 100 ° C. or more, air bubbles are generated inside the tofu, and the quality and flavor are deteriorated.
  • the total amount of energy received by the container (accumulated amount) is higher for sterilization at low temperature for a long time than for high temperature short time sterilization, and it can be said that sterilization for low temperature long time sterilization is more severe than high temperature short time sterilization as heating conditions.
  • the paper container can be expanded and folded, the container is not bulky, light in weight, and easily combustible, so it is excellent in ease of disposal and recyclability. For this reason, paper-based packaging materials are in widespread use.
  • stacked the low density polyethylene resin layer on both sides of the paper base material, and gave water resistance to paper is used.
  • the side edges of the packaging material are stacked and heat sealed to produce various forms of packaging containers.
  • the contents are filled and packaged from the opening of the packaging container to manufacture various packaging products.
  • a packaging container for long-term preservation of contents requiring barriers such as soy sauce, sake, juice, and prepared foods, a laminate obtained by laminating aluminum foil, plastic, etc. as a barrier layer on the middle layer is laminated.
  • the used paper container is widely used.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 5-213337
  • a multi-layered paper container in which the layer forming the inner surface of the container is a polyethylene film having an uneven surface and the layer forming the outer surface is an extrusion laminated polyethylene layer
  • Patent Document 2 Japanese Patent Application Laid-Open No. 7-40975
  • the left and right end portions of a blank plate having a predetermined shape are heat-sealed to form a cylinder having a fusion-bonded portion, and one open end of the cylinder is sealed.
  • the blank plate has a base layer and an outer surface made of a polyolefin resin provided on one side of the base layer.
  • a container comprising a laminated sheet comprising a layer and an inner surface layer made of polyacrylonitrile resin provided on the other surface of the base material layer, which has odor retention and chemical resistance to contents.
  • a container which can stably store even liquid having high permeability such as alcoholic beverages.
  • Patent Document 3 Japanese Patent No. 4936346 includes constituent layers of an outermost thermoplastic material layer, a paper base layer, a barrier layer, and an innermost thermoplastic material layer, and these layers are laminated in the above order.
  • a packaging material for a liquid food paper container wherein the innermost thermoplastic material layer is laminated by an extrusion lamination method, and linear low density polyethylene 55 having a narrow molecular weight distribution obtained by polymerization with a metallocene catalyst Consisting of a blend polymer of ⁇ 75 wt% and 45-25 wt% of low density polyethylene obtained by polymerization with multi-site catalyst, average density of 0.905 ⁇ 0.915, peak melting point of 88 ⁇ 103 ° C., 15
  • a packaging material for a liquid food paper container having a melt flow index of ⁇ 17, a swelling ratio (SR) of 1.4 ⁇ 1.6 and a layer thickness of 20 ⁇ 30 ⁇ m Easy to pack, can be heat-sealed quickly, enables tougher seal strength, and
  • the multilayer paper laminate used for this paper packaging container is produced separately from the inner layer portion on the innermost thermoplastic material layer side from the aluminum foil and the outer layer portion including the paper base and the outermost layer, and then the inner layer portion and the outer layer portion Join and manufacture.
  • the inner layer is a metallocene-polymerized narrow molecular weight linear low density polyethylene (mLLDPE) and high-pressure low density polyethylene blended on one side of a 9 ⁇ m thick aluminum foil to give an average density of 0.910, Melt-extrusion of an adhesive layer with a peak melting point of 97 ° C, a melt flow index of 15, a swelling ratio of 1.5 and a layer thickness of 13 ⁇ m, and a metallocene-polymerized narrow molecular weight distribution linear low density polyethylene (mLLDPE) Of high density and low density polyethylene by high pressure method, the innermost thermoplastic material layer of average density of 0.907, peak melting point of 96 ° C, melt flow index of 14, swell ratio of 1.5 and layer
  • the extrusion coating is applied to laminate the outermost thermoplastic material layer.
  • the low density polyethylene / paper base paper side and the aluminum foil side of the aluminum foil laminate are blended with a metallocene catalyst polymerized linear low density polyethylene (mLLDPE) of narrow molecular weight distribution and low density polyethylene by high pressure method
  • mLLDPE metallocene catalyst polymerized linear low density polyethylene
  • Patent Document 4 Japanese Patent Laid-Open No. 2004-17984 discloses an outermost layer made of a thermoplastic resin, a paper base layer, an intervening resin layer, a barrier layer, a pinhole resistant layer made of a thermoplastic resin, and a thermoplastic resin.
  • a printed layer is provided on the inner surface of the outermost layer or on the surface of the paper substrate layer, there is no delamination, and the appearance and the interlayer strength are excellent.
  • retort paper containers have been proposed which can withstand shock due to transportation.
  • An object of the present invention is to realize a paper container using a multi-layered paper laminated material which can simplify the number of manufacturing processes. Furthermore, the present invention aims to develop a paper container suitable for low temperature and long time sterilization treatment.
  • the present invention is a container suitable for low-temperature long-term sterilization and using a thermoplastic synthetic resin having a common melting temperature to provide a multilayer paper container having a simple structure in which the manufacturing process is simplified.
  • the main configurations of the present invention are as follows.
  • thermoplastic resin layer (A layer), the paper base layer (B layer), the thermoplastic resin layer (E layer), the barrier layer (C layer), the adhesive layer (F layer)
  • a layer is low density polyethylene resin (LDPE)
  • F layer is ethylene / (meth) acrylic acid copolymer resin (E (M) AA)
  • D layer and E layer are linear low density polyethylene resin (L-
  • L- A multilayer paper container characterized in that it is a layer having LDPE as a main component. 2.
  • the low density polyethylene resin (LDPE) used for the layer A has an average density of 0.910 to 0.930 g / cm 3 , a peak melting point of 105 to 125 ° C.
  • the linear low density polyethylene resin (L-LDPE) used for the D layer has an average density of 0.905 to 0.935 g / cm 3 , a peak melting point of 100 to 125 ° C.
  • Low density polyethylene resin (L-LDPE) has an average density of 0.905 to 0.935 g / cm 3 , a peak melting point of 105 to 125 ° C.
  • a resin used for D layer and E layer is 2.0 to It is characterized by having a melt flow rate (MFR) of 16.0 g / 10 min.
  • Multilayer paper container as described. 3.
  • the A layer, the E layer, the F layer, and the D layer are laminated with the B layer and the C layer by the extrusion lamination method. Or 2.
  • Food and drink are characterized by tofu.
  • thermoplastic resin layer A layer
  • the paper base layer B layer
  • the thermoplastic resin layer E layer
  • the barrier layer C layer
  • the adhesive layer F layer
  • a layer (E layer) containing a linear low density polyethylene resin (L-LDPE) as a main component is melted and extruded to a paper base layer (B layer) and a barrier layer (C layer) is formed.
  • L-LDPE linear low density polyethylene resin
  • the layer (A layer) mainly composed of low density polyethylene resin (LDPE) is melt extruded and laminated on the paper base layer (B layer) side of the laminate obtained in the second step.
  • thermoplastic resin layer A layer
  • the paper base layer B layer
  • the thermoplastic resin layer E layer
  • the barrier layer C layer
  • the adhesive layer F layer
  • a multilayer paper container provided with a thermoplastic resin layer A layer and E layer are low density polyethylene resin (LDPE)
  • F layer is ethylene / (meth) acrylic acid copolymer resin (E (M) AA)
  • D layer is linear low density polyethylene resin (L- A multilayer paper container characterized in that it is a layer containing LDPE as a main component.
  • the low density polyethylene resin (LDPE) used in layers A and E has an average density of 0.910 to 0.930 g / cm 3 and a peak melting point of 105 to 125 ° C.
  • the linear low density polyethylene resin (L-LDPE) used for the D layer has an average density of 0.905 to 0.935 g / cm 3 , a peak melting point of 100 to 125 ° C., and the linear chain used for the D layer
  • Low density polyethylene resin (L-LDPE) and low density polyethylene resin (LDPE) used for the E layer are characterized by a melt flow rate (MFR) of 2.0 to 16.0 g / 10 min. Multilayer paper container as described. 10.
  • thermoplastic resin layer (A layer), the paper base layer (B layer), the thermoplastic resin layer (E layer), the barrier layer (C layer), the adhesive layer (F layer) A method for producing a multi-layered paper container base paper provided with a thermoplastic resin layer (D layer), As the first step, the layer (E layer) mainly composed of low density polyethylene resin (LDPE) is melt extruded to the paper base layer (B layer) and the barrier layer (C layer) is supplied to perform lamination.
  • LDPE low density polyethylene resin
  • the layer (A layer) mainly composed of low density polyethylene resin (LDPE) is melt extruded and laminated on the paper base layer (B layer) side of the laminate obtained in the second step.
  • a method of producing a base paper for a multilayer paper container which comprises continuously laminating the above three steps.
  • L-LDPE linear low density polyethylene resin
  • F layer adhesive layer
  • E (M) AA ethylene / (meth) acrylic acid copolymer resin
  • D layer a layer
  • Linear low density polyethylene resin is more flexible than low density polyethylene resin (LDPE), and can maintain pinhole resistance against irritation such as boiling. According to the layer configuration of the present invention, it is possible to provide a container for food and drink that requires low temperature and long time sterilization treatment.
  • the peak temperature of the resin used for layer A and E was set to 105 to 125 ° C, and the peak melting point of the resin used for layer D was set to 100 to 125 ° C, so it is suitable for paper containers heated at around 90 ° C. ing. Since the pinhole resistance is strong, it is suitable for food and drink having various pH, and it is particularly suitable as a container for tofu filling in which the low temperature heating time is long and the accumulated heat amount is large. 3.
  • a resin having common temperature physical properties in particular, melt flow rate (MFR)
  • MFR melt flow rate
  • the linear low density polyethylene resin used for the D layer has an average density of 0.905 to 0.935 g / cm 3 , the peak melting point of 100 to 125 ° C.
  • the resin used for the E layer has a density of 0.905 to Extrusion with an average density of 0.935 g / cm 3 , a peak melting point of 105 to 125 ° C., and a resin used for layer D and layer E having a melt flow rate of 2.0 to 16.0 / 10 minutes It is easy to carry out lamination continuously.
  • the resin used for the D layer and the F layer has a melt flow rate of 2.0 to 16.0 / 10 minutes, the interlayer seal between the D layer and the F layer and the lateral seal between the D layers are firmly adhered. Be done.
  • the figure which shows the example of the paper container of this invention The figure which shows the structural example of the paper laminated body used for the multilayer paper container of a 1st form. The figure which shows the structural example of the paper laminated body used for the multilayer paper container of 2nd form. The figure which shows the pinhole test by an electricity supply system.
  • the entire layer configuration of the multilayer paper container of the first embodiment of the present invention is at least a thermoplastic resin layer (A layer), a paper base layer (B layer), a thermoplastic resin layer E)), a barrier layer (C layer), an adhesive layer (F layer), and a thermoplastic resin layer (D layer), wherein the A layer is a low density polyethylene resin, the F layer is ethylene,
  • the (meth) acrylic acid copolymer resin and the D layer and the E layer each have a linear low density polyethylene resin as a main component.
  • the use of a thermoplastic resin suitable for extrusion lamination in each layer simplifies the manufacturing process.
  • a layer (D layer) mainly composed of a linear low density polyethylene resin through an adhesive layer (F layer) made of ethylene / (meth) acrylic acid copolymer resin from the barrier layer to the inner surface side of the container , Excellent in pinhole resistance.
  • the low density polyethylene resin used in the A layer has an average density of 0.910 to 0.930 g / cm 3 , the peak melting point of 105 to 125 ° C., and the linear low density polyethylene resin used in the D layer is 0.905 to Average density of 0.935 g / cm 3 , peak melting point of 100 to 125 ° C., linear low density polyethylene resin used for E layer, average density of 0.905 to 0.935 g / cm 3 , 105 to 125 ° C.
  • the temperature physical properties were made common, assuming that the peak melting point, and the resin used for the D layer and the E layer had a melt flow rate of 2.0 to 16.0 / 10 minutes.
  • the peak melting point temperatures of the layers A and E were set to 105 to 125 ° C., and the peak melting point temperature of the layer D to 100 to 125 ° C. so as to sufficiently withstand 95 ° C. so as to correspond to the boiling.
  • the entire layer configuration of the multilayer paper container of the second embodiment of the present invention is at least a thermoplastic resin layer (A layer), a paper base layer (B layer), a thermoplastic resin layer (from the outer surface side to the inner surface side) E layer), a barrier layer (C layer), an adhesive layer (F layer), and a thermoplastic resin layer (D layer), wherein the A layer and the E layer are low density polyethylene resin, F layer
  • the ethylene / (meth) acrylic acid copolymer resin and the D layer mainly contain a linear low density polyethylene resin.
  • a layer (D layer) mainly composed of a linear low density polyethylene resin through an adhesive layer (F layer) made of ethylene / (meth) acrylic acid copolymer resin from the barrier layer to the inner surface side of the container , It is a paper container excellent in pinhole resistance.
  • the low density polyethylene resin used for layer A and layer E has an average density of 0.910 to 0.930 g / cm 3 , a peak melting point of 105 to 125 ° C., and the linear low density polyethylene resin used for layer D is 0 With an average density of 905 to 0.935 g / cm 3 , a peak melting point of 100 to 125 ° C., and a resin used for layer D and layer E having a melt flow rate of 2.0 to 16.0 / 10 minutes, The temperature property was made common.
  • the peak melting point temperatures of the layers A and E were set to 105 to 125 ° C., and the peak melting point temperature of the layer D to 100 to 125 ° C. so as to sufficiently withstand 95 ° C. so as to correspond to the boiling.
  • the main component means containing more than 50 wt%.
  • the content is more preferably 70 wt% or more, still more preferably 80 wt% or more, and most preferably 90 wt% or more.
  • the peak melting point of the resin used in each layer is measured by differential scanning calorimetry, and at least 1 when multiple peaks are measured.
  • the peak of the book may be included in the above temperature range.
  • the paper container of the present invention is suitable as a container for aseptically filling food and drink after cooking at high temperature, and as a container for food and drink after boil and readjustment, for example, at 90 ° C. to 95 ° C. after aseptic filling.
  • a container for food and drink after boil and readjustment for example, at 90 ° C. to 95 ° C. after aseptic filling.
  • after tofu is mixed with soy milk and mixed with a coagulant, it is boiled at about 90 ° C. for coagulation. Then, heat treatment at a temperature of 90 ° C. for 40 minutes or a method having the same or higher efficacy is required.
  • it is suitable for food and drink such as jelly, which is liquid at the time of filling but becomes gel after filling, in particular, contents requiring waterproofness, moisture resistance, light shielding property, oxygen barrier property and the like.
  • the paper container of the present invention has barrier properties and heat sealing properties, can be disposed of as paper, and is excellent in volume reduction and weight reduction. When made into a brick-like container, it is excellent also in storability, preservability, and conveyance nature.
  • the brick type paper container 11 shown in FIG. 1 is a container formed by bending a base paper for paper container and heat-sealing (heat sealing) side surfaces and upper and lower openings to form a square brick-like cube.
  • the right and left sides 12, the front surface 13, the back surface 14, the upper surface 15, and the lower surface 16 are constituted by six surfaces.
  • the side portions of the base paper for paper containers are heat-sealed portions 18 which are overlapped and joined. Further, the upper and lower end portions are also overlapped and joined to form a thermally fused portion 19.
  • the folded-ear portion 17 is joined to the side surface 12 by being bent from the upper surface portion to the side surface portion.
  • the heat sealing portion 18 is bent from the back surface to the upper surface or the lower surface in a state of being overlapped at the bending corner portion.
  • the heat-sealing part 19 is bent in a state of being overlapped at the bending corner part from the upper surface to the side surface.
  • the shape itself of the brick-like paper container is similar to that of the conventional one.
  • the structural example of the paper laminated body used for the multilayer paper container of a 1st form is shown in FIG.
  • the layer structure of the paper laminate is at least a thermoplastic resin layer (A layer), a paper base layer (B layer), a thermoplastic resin layer (E layer), a barrier layer (C layer) from the outer surface side to the inner surface side ), An adhesive layer (F layer), and a thermoplastic resin layer (D layer).
  • the printed layer uses a pre-printed paper substrate. It is also possible not to provide this printing layer. Moreover, a printing layer can also be provided on the surface of A layer.
  • An adhesive layer (G layer) made of a thermoplastic resin may be provided between the thermoplastic resin layer (E layer) and the barrier layer (C layer).
  • a layer is low density polyethylene resin (LDPE), F layer is ethylene / (meth) acrylic acid copolymer resin (E (M) AA), D layer and E layer are linear low density polyethylene resin (L- Each of LDPE) is a main component.
  • LDPE low density polyethylene resin
  • F layer is ethylene / (meth) acrylic acid copolymer resin (E (M) AA)
  • D layer and E layer are linear low density polyethylene resin (L-
  • LDPE low density polyethylene resin
  • the low density polyethylene resin (LDPE) used for the layer A has an average density of 0.910 to 0.930 g / cm 3 and a peak melting point of 105 to 125 ° C.
  • the paper base used for the layer B can be appropriately selected according to the desired quality of the paper container, and is not particularly limited.
  • the paper base used for a paper container for liquid packaging can be used .
  • a single layer paper base or a multilayer paper base can be used. It is preferable to be excellent in bending resistance and drop impact absorption, molding water resistance, and the like.
  • a multilayer paper base in which a high density layer is formed on both sides of a low density inner layer is a paper base excellent in the function of the low density layer to absorb bending stress and impact from falling.
  • the paper base contains, as an internal sizing agent, at least 0.15 parts by weight but less than 0.80 parts by weight based on 100 parts by weight of total raw material pulp (absolute dry pulp weight) to improve water resistance. It is also effective to do. Furthermore, the addition of a cationized starch, an amphoteric starch, a starch such as oxidized starch, and / or a sulfuric acid band is preferable because it has the effect of improving the fixing of the alkyl ketene dimer to the pulp and in particular improves the water resistance.
  • the barrier material used for C layer can use barrier materials, such as aluminum foil generally used for a multilayer paper container.
  • barrier materials such as aluminum foil generally used for a multilayer paper container.
  • a common aluminum metal can be used as aluminum which comprises a thin film layer of aluminum foil or aluminum.
  • the linear low density polyethylene resin (L-LDPE) used for the D layer has an average density of 0.905 to 0.935 g / cm 3 and a peak melting point of 100 to 125 ° C.
  • Low density polyethylene resin (L-LDPE) has an average density of 0.905 to 0.935 g / cm 3 and a peak melting point of 105 to 125 ° C., and is a linear low density polyethylene used for D layer and E layer
  • the resin (L-LDPE) is preferably a melt flow rate (MFR) of 2.0 to 16.0 / 10 minutes.
  • the average density of the linear low density polyethylene resin (L-LDPE) used in the D layer is 0.905 to 0.935 g / cm 3
  • the peak melting point is 105 to 125 ° C.
  • the average density of linear low density polyethylene resin (L-LDPE) is 0.910 to 0.925 g / cm 3
  • the peak melting point is 105 to 125 ° C.
  • the melt flow rate (MFR) is 6.
  • the edges of the base paper for paper containers are heat-sealed (heat-sealed) in order to constitute the paper container, but the transverse seal formed by the heat seal required at that time is firmly adhered.
  • the two edge D / D layers are heat sealed to form a transverse seal, but the transverse seal exhibits sufficient resistance even when heated at a low temperature for a long time.
  • the ethylene / (meth) acrylic acid copolymer resin (E (M) AA) used for the F layer is not particularly limited, which is determined according to the required performance, but usually, the average density is 0.910 to 0 .950 g / cm 3 , peak melting point 80 to 110 ° C., melt flow rate (MFR) 2.0 to 16.0 / 10 minutes, D layer and ethylene (meth) acrylic acid copolymer resin
  • the adhesive property with the adhesive layer (F layer) consisting of (E (M) AA) that is, the adhesive strength between the D layer and the F layer is good and also the pinhole resistance against stimuli such as boiling and the side of the paper container It is preferable because the adhesiveness of the sealing portion (the portion of No. 19 in FIG. 1: the bonding portion between the thermoplastic resin layers (D layers) on the inner surface of the container) becomes good.
  • thermoplastic resin used for the G layer is not particularly limited, but the resin used for the F layer is preferably used.
  • the layer structure of the paper laminate is at least a thermoplastic resin layer (A layer), a paper base layer (B layer), a thermoplastic resin layer (E layer), a barrier layer (C layer) from the outer surface side to the inner surface side ), An adhesive layer (F layer), and a thermoplastic resin layer (D layer).
  • the printed layer uses a pre-printed paper substrate. It is also possible not to provide this printing layer. Moreover, a printing layer can also be provided on the surface of A layer.
  • An adhesive layer (G layer) made of a thermoplastic resin may be provided between the thermoplastic resin layer (E layer) and the barrier layer (C layer).
  • a layer and E layer are low density polyethylene resin (LDPE), F layer is ethylene / (meth) acrylic acid copolymer resin (E (M) AA), D layer is linear low density polyethylene resin (L- LDPE) is a layer containing each as a main component.
  • LDPE low density polyethylene resin
  • F layer is ethylene / (meth) acrylic acid copolymer resin (E (M) AA)
  • D layer is linear low density polyethylene resin (L- LDPE) is a layer containing each as a main component.
  • the low density polyethylene resin (LDPE) used for the E layer has an average density of 0.910 to 0.930 g / cm 3 and a peak melting point of 105 to 125 ° C.
  • LDPE low density polyethylene resin
  • a layer, B layer, C layer, D layer, F layer, and G layer those used for the first paper laminate can be used.
  • Linear low density polyethylene resin (L-LDPE) used in layer D and low density polyethylene resin (LDPE) used in layer E have a melt flow rate (MFR) of 2.0 to 16.0 / 10 minutes Is preferred.
  • MFR melt flow rate
  • the average density of the linear low density polyethylene resin (L-LDPE) used in the D layer is 0.905 to 0.935 g / cm 3
  • the peak melting point is 105 to 125 ° C.
  • D The average density of the linear low density polyethylene resin (L-LDPE) used in the layer and the low density polyethylene resin (LDPE) used in the E layer is 0.910 to 0.925 g / cm 3
  • the peak melting point is 105 to 125 ° C, melt flow rate (MFR) 6.0 to 15.0 / 10 min
  • MFR melt flow rate
  • L-LDPE linear low density polyethylene resin
  • LDPE low used in layer D and low used in layer E Density polyethylene resin
  • the average density is 0.910 to 0.925 g / cm 3
  • the peak melting point is 105 to 125 ° C.
  • MFR melt flow rate
  • the edges of the base paper for paper containers are heat-sealed (heat-sealed) in order to constitute the paper container, but the transverse seal formed by the heat seal required at that time is firmly adhered.
  • the two edge D / D layers are heat sealed to form a transverse seal, but the transverse seal exhibits sufficient resistance even when heated at a low temperature for a long time.
  • a base paper 1 for multilayer paper container is produced.
  • the adhesive layer (F layer) is an ethylene / acrylic acid copolymer resin (EAA) (Made by Dow Chemical Company, product name: PRIMACOR 3003) having an average density of 0.935 g / cm 3 , peak melting point 100 ° C. and MFR 7.8.
  • EAA ethylene / acrylic acid copolymer resin
  • Example 8 The same as Example 4 except that L-LDPE was used as the main layer by adding LDPE resin (LC602A) to L-LDPE layer (D layer) to be 15 wt%, 25 wt% and 45 wt%, respectively. Then, base papers 5 to 7 for multilayer paper containers and paper containers were produced.
  • LDPE resin LC602A
  • E layer L-LDPE layer
  • EAA resin PRIMACOR 3003
  • the L-LDPE layer is a layer mainly composed of LDPE consisting of 95 wt% of LDPE resin (LC602A) and 5 wt% of EAA resin (PRIMACOR 3003)
  • the base paper 9 and a paper container were produced.
  • a multilayer was prepared in the same manner as in Examples 4 to 7 except that the L-LDPE layer (E layer) was a layer containing LDPE as a main component consisting of 95 wt% of LDPE resin (LC602A) and 5 wt% of EAA resin (PRIMACOR 3003). Base papers 10 to 13 for paper containers and paper containers were produced.
  • E layer L-LDPE layer
  • LC602A LDPE resin
  • EAA resin PRIMACOR 3003
  • Example 10 is the same as Example 10 except that an adhesive layer (G layer) made of an EAA resin (PRIMACOR 3003) is provided between the layer (E layer) containing LDPE as the main component and the barrier layer (C layer) according to the following steps.
  • G layer an adhesive layer made of an EAA resin (PRIMACOR 3003) is provided between the layer (E layer) containing LDPE as the main component and the barrier layer (C layer) according to the following steps.
  • a multi-layered paper container base paper 14 and a paper container were produced.
  • a base paper 14 for multilayer paper container is produced.
  • the layer (D layer) containing L-LDPE as a main component has an average density of 0.910 g / cm 3 , a peak melting point of 124 ° C., and an MFR of 15 with L-LDPE (Dow Chemical Company, product name: ELITE 5815)
  • L-LDPE Low Chemical Company, product name: ELITE 5815
  • a multilayer paper was prepared in the same manner as in Example 14 except that in the layer (D layer) containing L-LDPE as the main component, L-LDPE having an average density of 0.913 g / cm 3 , peak melting point of 121 ° C. and MFR 6.0 was used.
  • Container base paper 16 and a paper container were produced.
  • E layer the layer containing LDPE as the main component
  • Example 19 Example except that in the layer (A layer) containing LDPE as the main component, LDPE (product name: KC507S, manufactured by Japan Polyethylene Corporation) having an average density of 0.906 g / cm 3 , a peak melting point of 102 ° C., and an MFR of 10.5. The same procedure as No. 14 was carried out to prepare a multilayer paper container base paper 18 and a paper container. [Example 19]
  • the thermoplastic resin (D layer) is L-LDPE having an average density of 0.921 g / cm 3 , a peak melting point of 122 ° C., and an MFR of 12.0, and as the second step, the barrier layer (C of the laminate obtained in the first step) Example 1 except that the EMAA layer (F layer) and the L-LDPE layer (D layer) were melt-extruded on the layer side and the adhesive layer (F layer) and the thermoplastic resin layer (D layer) were laminated, respectively.
  • a base paper 20 for multilayer paper containers and a paper container were produced.
  • thermoplastic resin (D layer) is L-LDPE having an average density of 0.930 g / cm 3 , a peak melting point of 123 ° C., and an MFR of 11.0, and as a second step, the barrier layer (C of the laminate obtained in the first step) Example 1 except that the EMAA layer (F layer) and the L-LDPE layer (D layer) were melt-extruded on the layer side and the adhesive layer (F layer) and the thermoplastic resin layer (D layer) were laminated, respectively.
  • a base paper 21 for multilayer paper containers and a paper container were produced.
  • thermoplastic resin (D layer) is L-LDPE having an average density of 0.937 g / cm 3 , a peak melting point of 123 ° C., and an MFR of 11.0, and as a second step, the barrier layer (C of the laminate obtained in the first step) Example 1 except that the EMAA layer (F layer) and the L-LDPE layer (D layer) were melt-extruded on the layer side and the adhesive layer (F layer) and the thermoplastic resin layer (D layer) were laminated, respectively.
  • a base paper 22 for multilayer paper containers and a paper container were produced.
  • thermoplastic resin (D layer) is L-LDPE having an average density of 0.901 g / cm 3 , a peak melting point of 112 ° C., and an MFR of 8.0, and as a second step, a barrier layer of the laminate obtained in the first step (C Example 1 except that the EMAA layer (F layer) and the L-LDPE layer (D layer) were melt-extruded on the layer side and the adhesive layer (F layer) and the thermoplastic resin layer (D layer) were laminated, respectively.
  • a base paper 23 for multilayer paper containers and a paper container were produced.
  • the adhesive layer (F layer) and the thermoplastic resin (D layer) were made L-LDPE having an average density of 0.930 g / cm 3 , a peak melting point of 123 ° C., and an MFR of 11.0, and were obtained in the first step as the second step.
  • the L-LDPE layer (F layer) and the L-LDPE layer (D layer) are respectively melt-extruded on the barrier layer (C layer) side of the laminate to form an adhesive layer (F layer) and a thermoplastic resin layer (D layer)
  • a multilayer paper container base paper 24 and a paper container were produced in the same manner as in Example 1 except that the above were laminated.
  • Thermoplastic resin (D layer) was used as LDPE with an average density of 0.928 g / cm 3 , peak melting point of 114 ° C., and MFR 3.0 (product name: LC561 manufactured by Japan Polyethylene Corporation), obtained as the second step in the first step
  • LDPE low density polyethylene
  • MFR 3.0 product name: LC561 manufactured by Japan Polyethylene Corporation
  • Thermoplastic resin (D layer) was made into LDPE (Made in Japan, product name: M201P) with an average density of 0.917 g / cm 3 , peak melting point of 106 ° C. and MFR 8.0, obtained as the second step in the first step
  • LDPE Mel in Japan, product name: M201P
  • a multilayer paper base paper 27 and a paper container were produced in the same manner as in Example 3 except that 55 wt% of LDPE resin (LC602A) was added to the L-LDPE layer (E layer).
  • LDPE resin LC602A
  • a base paper 28 for a multilayer paper container and a paper container were produced in the same manner as in Example 3 except that 75 wt% of LDPE resin (LC602A) was added to the L-LDPE layer (E layer).
  • LDPE resin LC602A
  • ⁇ Pinhole resistance test> (A: container inner surface) A paper container heated (boiled) in hot water at 90 ° C. for 40 minutes with filling material (water) cut into two in the lateral direction at the center of the body, and the inside of the container is filled with water. This is immersed in water, and it is energized at 1 kV between the inner surface and the outer surface of the container using an energizing checker (Pinhole checker HV-M, manufactured by Shinko Electric Instruments Co., Ltd.), and the presence or absence of an electrification reaction is confirmed.
  • FIG. A schematic diagram of a pinhole test according to the energization method is shown in FIG. As shown in FIG.
  • the outer surface of the container is further dipped in a red penetrant (water to which a red dye is added) to confirm the presence or absence of staining of the paper substrate (B layer).
  • a red penetrant water to which a red dye is added
  • the red penetrant is permeated from the pinhole and the paper substrate (layer B) is dyed.
  • Evaluation 2 Although it does not peel off at the transverse seal portion (the interface between the D layer and the D layer), the adhesive layer (F (Layer) and the thermoplastic resin layer (layer D) peel off.
  • Evaluation 1 Peeling off at the transverse seal portion (the interface between the D layer and the D layer).
  • Table 3 shows the evaluation results of the paper containers prepared in the example and the comparative example.
  • pinholes occur on both the inside and outside of the container, the outside air intrudes into the inside of the container and leads to deterioration and decay of the food and drink that are the contents, or the contents exude to the outside of the container and cause staining and odor Lead to
  • the aluminum foil of the barrier layer (C layer) and the contents come into contact, and depending on the type of contents, the aluminum foil is corroded. May lead to the deterioration of the entire container.
  • pinhole resistance is an element related to the intrinsic physical properties of the container, it was an important evaluation element. Since the adhesion test of the transverse seal portion is a heating test in water at 90 ° C.
  • the multilayer paper container of the present invention has a heat sealability sufficiently resistant to sterilization at low temperatures for a long time ing.
  • the multilayer paper container of the present invention is a combination of the adhesive layer (F layer) with E (M) AA and the thermoplastic resin layer (D layer) with L-LDPE as a main component. It has been confirmed that sufficient adhesive strength is exhibited between the layers on the inner surface side of the container rather than the aluminum foil of the layer). By this test, a paper container configuration that can be sterilized at low temperature for a long time can be developed, and it is confirmed that extrusion lamination can be continuously performed by combination of thermoplastic resins constituting each layer to manufacture base paper for multilayer paper containers. did it.

Abstract

The purpose of the present invention is to produce a paper container using a multilayered paper laminate material, wherein it is possible to reduce the number of production steps. A multilayered paper container at least provided with a thermoplastic resin layer (layer A), a paper base material layer (layer B), a thermoplastic resin layer (layer E), a barrier layer (layer C), an adhesive layer (layer F), and a thermoplastic resin layer (layer D) from the outer surface side towards the inner surface side, wherein the main component of layer A is a low-density polyethylene resin (LDPE), the main component of layer F is an ethylene-(meth)acrylic acid copolymer resin (E(M)AA), the main component of layer D is a linear low-density polyethylene resin (L-LDPE), and the main component of layer E is a linear low-density polyethylene resin (L-LDPE) or a low-density polyethylene resin (LDPE).

Description

多層紙容器Multi-layered paper container
 本発明は、保存性の高い多層紙容器に関する。特に、加熱、密閉して保存可能な容器に関する。 The present invention relates to a multi-layer paper container with high storage stability. In particular, it relates to a container that can be heated and sealed.
 飲食品、医薬品、化粧品、洗剤、化学品、雑貨品、その他の種々の内容物を充填包装する容器として、金属缶、ガラス瓶、プラスチック容器、紙容器、あるいはフィルム、金属箔をラミネートして積層した積層体をヒートシールして袋状にした容器等が使用されている。
 また、内容物を常温にて長期保存するため、従来、金属缶、ガラス瓶、プラスチックパウチ、プラスチックとアルミニウム箔のラミネートパウチ等の気密性容器に内容物を詰め、120℃、4分以上の高温、高圧下(以下「レトルト」という。)で殺菌することが行われている。レトルト処理用容器は、通常、物理的にも化学的にも過酷な条件におかれることから、レトルト処理用容器を構成する包装材料には、厳しい包装適性が要求され、外観、変形防止強度、耐ピンホ-ル性、耐熱性、密封性、品質保全性、作業性、衛生性、その他の種々の条件が要求されるものである。
 一方、飲食品の加熱条件は、飲食品の種類および殺菌条件により種々ある。例えば、日本国では、「乳及び乳製品の成分規格等に関する省令」において牛乳の殺菌条件は、「63℃で30分間加熱するか、又はこれと同等以上の殺菌効果を有する方法」と定められており、63℃で30分間加熱と同等の方法としては、72~78℃で15秒間、120~135℃で1~3秒間が挙げられる。また、日本国では、「食品、添加物等の規格基準」において包装豆腐(豆乳に凝固剤を添加して容器包装に充てんした後加熱凝固させたものをいう。)の殺菌条件は、「90℃で40分間加熱する方法又はこれと同等以上の効力を有する方法」と定められているが、豆乳を充填後に凝固させ、凝固後に同等以上の効力を有する方法として牛乳での高温処理(120~135℃)と同様に100℃以上の高温に曝すと、豆腐内部に気泡が生じるなどして品質、風味が劣化するので、高温処理は望ましくない。しかも、容器が受ける総エネルギー量(積算量)は高温短時間殺菌より低温長時間殺菌の方が多くなり、加熱条件としては高温短時間殺菌より低温長時間殺菌の方が厳しいともいえる。
 また、環境問題から、使用済容器の廃棄性や、リサイクル適性が求められ、包装の簡素化、軽容化、軽量化、包装材料の易燃焼性が進められている。紙容器は、容器を展開して折り畳むことが可能なため、嵩張らず、また、軽量で、易燃焼性であるため、易廃棄性や、リサイクル適性に優れている。このため、紙系の包装材料が普及している。
 牛乳等の液状の内容物を保存する紙容器としては、紙製基材の両側に低密度のポリエチレン樹脂層を積層して紙に耐水性を付与した包装材料を用いている。この包装材料の側縁部同士を重ねてヒートシールして、種々の形態の包装用容器を製造する。しかして、該包装用容器の開口部から、内容物を充填包装して、各種の包装製品を製造している。
 醤油、清酒、ジュースや調理済みの食品などバリアを必要とする内容物を長期保存する包装用容器としては、中間層にバリア層として、アルミニウム箔、プラスチック等をラミネートして貼り合せた積層体を用いた紙容器が広く使用されている。
A metal can, a glass bottle, a plastic container, a paper container, or a film or metal foil is laminated and laminated as a container for filling and packaging food and drink, pharmaceuticals, cosmetics, detergents, chemicals, miscellaneous goods, and various other contents. The container etc. which heat-sealed the laminated body and made it the bag shape are used.
In addition, in order to store the contents for a long time at room temperature, the contents are conventionally packed in an airtight container such as a metal can, a glass bottle, a plastic pouch, a laminated pouch of plastic and aluminum foil, high temperature of 120 ° C., 4 minutes or more Sterilization under high pressure (hereinafter referred to as "retort") is performed. Since retort containers are usually subjected to harsh conditions physically and chemically, the packaging materials constituting the retort containers are required to have severe packaging suitability, and their appearance, deformation resistance, Pinhole resistance, heat resistance, sealability, quality maintenance, workability, hygiene, and various other conditions are required.
On the other hand, heating conditions of food and drink are various depending on types of food and drink and sterilization conditions. For example, in Japan, the pasteurization condition of milk is defined as "a method of heating at 63 ° C for 30 minutes or having a bactericidal effect equal to or higher than this" under "Ministerial Ordinance on Component Specifications of Milk and Dairy Products". As a method equivalent to heating at 63 ° C. for 30 minutes, mention may be made of 72 to 78 ° C. for 15 seconds and 120 to 135 ° C. for 1 to 3 seconds. Furthermore, in Japan, the sterilization conditions for “packing tofu (in which soy milk is added with a coagulant and filled in containers and packaging and then heated and solidified) according to“ standards for food, additives, etc. ”are“ 90 The method is defined as “method of heating at 40 ° C for 40 minutes or method having the same or higher efficacy”, but soymilk is coagulated after filling, and as a method having the same or higher efficacy after coagulation, high temperature treatment with milk (120 ~ Similarly to the case of 135 ° C., high temperature treatment is not desirable because the product is exposed to high temperature of 100 ° C. or more, air bubbles are generated inside the tofu, and the quality and flavor are deteriorated. Moreover, the total amount of energy received by the container (accumulated amount) is higher for sterilization at low temperature for a long time than for high temperature short time sterilization, and it can be said that sterilization for low temperature long time sterilization is more severe than high temperature short time sterilization as heating conditions.
In addition, due to environmental problems, disposal of used containers and recyclability are required, and packaging simplification, weight reduction, weight reduction, and flammable properties of packaging materials are being promoted. Since the paper container can be expanded and folded, the container is not bulky, light in weight, and easily combustible, so it is excellent in ease of disposal and recyclability. For this reason, paper-based packaging materials are in widespread use.
As a paper container which preserve | saves liquid content, such as milk, the packaging material which laminated | stacked the low density polyethylene resin layer on both sides of the paper base material, and gave water resistance to paper is used. The side edges of the packaging material are stacked and heat sealed to produce various forms of packaging containers. Then, the contents are filled and packaged from the opening of the packaging container to manufacture various packaging products.
As a packaging container for long-term preservation of contents requiring barriers such as soy sauce, sake, juice, and prepared foods, a laminate obtained by laminating aluminum foil, plastic, etc. as a barrier layer on the middle layer is laminated. The used paper container is widely used.
 特許文献1(特開平5-213337号公報)には、容器の内表面をなす層が、表面が凹凸状のポリエチレンフィルムからなり、外表面をなす層が押出しラミネートしたポリエチレン層からなる多層紙容器であって、臭気の問題が生ぜず、ヒートシール性も良好であるとともに、表面の滑り性が良く、もって成形時やハンドリング時における機械適性が優れた多層紙容器が開示されている。
 特許文献2(特開平7-40975号公報)には、所定形状のブランク板の左右両端部を熱融着して融着部を有する筒体とし、該筒体の一方の開口端を密封して底部とし、前記筒体の他方の開口端を密封して口部を形成した容器において、前記ブランク板は基材層と、該基材層の一方の面に設けられたポリオレフィン樹脂からなる外面層と、前記基材層の他方の面に設けられたポリアクリロニトリル系樹脂からなる内面層とを備える積層シートで構成された容器であって、内容物に対する保香性および耐薬品性を有し、かつ酒類のように浸透性の高い液体でも安定して保存可能な容器が開示されている。
In Patent Document 1 (Japanese Patent Application Laid-Open No. 5-213337), a multi-layered paper container in which the layer forming the inner surface of the container is a polyethylene film having an uneven surface and the layer forming the outer surface is an extrusion laminated polyethylene layer There is disclosed a multilayer paper container which is free from the problem of odor, has good heat sealability, has good surface slipperiness, and has excellent mechanical suitability at the time of molding and handling.
In Patent Document 2 (Japanese Patent Application Laid-Open No. 7-40975), the left and right end portions of a blank plate having a predetermined shape are heat-sealed to form a cylinder having a fusion-bonded portion, and one open end of the cylinder is sealed. In the case where the bottom portion is formed and the other open end of the cylindrical body is sealed to form the mouth portion, the blank plate has a base layer and an outer surface made of a polyolefin resin provided on one side of the base layer. A container comprising a laminated sheet comprising a layer and an inner surface layer made of polyacrylonitrile resin provided on the other surface of the base material layer, which has odor retention and chemical resistance to contents There is also disclosed a container which can stably store even liquid having high permeability such as alcoholic beverages.
 特許文献3(特許第4936346号公報)には、最外熱可塑性材料層、紙基材層、バリア層、最内熱可塑性材料層の各構成層を含み、これらの各層が上記の順序で積層されてからなる液体食品用紙容器用包材であって、該最内熱可塑性材料層が、押出しラミネーション法により積層され、メタロセン触媒で重合して得られた狭い分子量分布を有する線形低密度ポリエチレン55~75重量%とマルチサイト触媒で重合して得られた低密度ポリエチレン45~25重量%とのブレンドポリマーからなり、0.905~0.915の平均密度、88~103℃のピーク融点、15~17のメルトフローインデックス、1.4~1.6のスウェリング率(SR)及び20~30μmの層厚を有する液体食品用紙容器用包材であって、紙容器への充填包装が容易であり、迅速にヒートシールすることができ、より強靱なシール強度を可能にし、かつ、充填内容物の温度に影響を受けず良好なシールが得られ、保香性若しくは品質保持性を有する紙包装容器が開示されている。
 この紙包装容器に用いる多層紙積層材は、アルミ箔から最内熱可塑性材料層側の内層部と紙基材と最外層を含む外層部とを別々に製造した後、内層部と外層部を接合して製造する。
 内層部は、厚さ9μmのアルミニウム箔の一面に、メタロセン触媒で重合した狭い分子量分布の線形低密度ポリエチレン(mLLDPE)と高圧法による低密度ポリエチレンとをブレンドして、0.910の平均密度、97℃のピーク融点、15のメルトフローインデックス、1.5のスウェリング率及び13μmの層厚の接着剤層を溶融押出しして、メタロセン触媒で重合した狭い分子量分布の線形低密度ポリエチレン(mLLDPE)と高圧法による低密度ポリエチレンとをブレンドして0.907の平均密度、96℃のピーク融点、14のメルトフローインデックス、1.5のスウェリング率及び25μmの層厚の最内熱可塑性材料層を積層してアルミニウム箔/接着剤層/最内熱可塑性材料ブレンド層からなる積層フィルムを作成する。
 外層部は、高圧法による低密度ポリエチレン(密度=0.920g/cm3、MI=5.1)を厚さ20μmで紙基材(坪量=320g/m2)上に押出温度330℃にて押出コーティングして最外熱可塑性材料層を積層する。
 次いで、低密度ポリエチレン/紙基材の紙側とアルミニウム箔積層体のアルミニウム箔側とを、メタロセン触媒で重合した狭い分子量分布の線形低密度ポリエチレン(mLLDPE)と高圧法による低密度ポリエチレンとをブレンドして0.920の平均密度、99℃のピーク融点、17のメルトフローインデックス、1.5のスウェリング率及び12μmの層厚で接着性熱可塑性材料層を溶融押出しして、積層して積層構成の連続した長尺の積層包材を得る。
 この包材を用いて、充填機にてブリック形状の液体食品充填包装体を得る。
Patent Document 3 (Japanese Patent No. 4936346) includes constituent layers of an outermost thermoplastic material layer, a paper base layer, a barrier layer, and an innermost thermoplastic material layer, and these layers are laminated in the above order. A packaging material for a liquid food paper container, wherein the innermost thermoplastic material layer is laminated by an extrusion lamination method, and linear low density polyethylene 55 having a narrow molecular weight distribution obtained by polymerization with a metallocene catalyst Consisting of a blend polymer of ̃75 wt% and 45-25 wt% of low density polyethylene obtained by polymerization with multi-site catalyst, average density of 0.905 ̃0.915, peak melting point of 88 ̃103 ° C., 15 A packaging material for a liquid food paper container, having a melt flow index of ̃17, a swelling ratio (SR) of 1.4 ̃1.6 and a layer thickness of 20 ̃30 μm Easy to pack, can be heat-sealed quickly, enables tougher seal strength, and can achieve good seal without being affected by the temperature of the filling contents, odor retention or quality retention A paper packaging container is disclosed.
The multilayer paper laminate used for this paper packaging container is produced separately from the inner layer portion on the innermost thermoplastic material layer side from the aluminum foil and the outer layer portion including the paper base and the outermost layer, and then the inner layer portion and the outer layer portion Join and manufacture.
The inner layer is a metallocene-polymerized narrow molecular weight linear low density polyethylene (mLLDPE) and high-pressure low density polyethylene blended on one side of a 9 μm thick aluminum foil to give an average density of 0.910, Melt-extrusion of an adhesive layer with a peak melting point of 97 ° C, a melt flow index of 15, a swelling ratio of 1.5 and a layer thickness of 13 μm, and a metallocene-polymerized narrow molecular weight distribution linear low density polyethylene (mLLDPE) Of high density and low density polyethylene by high pressure method, the innermost thermoplastic material layer of average density of 0.907, peak melting point of 96 ° C, melt flow index of 14, swell ratio of 1.5 and layer thickness of 25μm To form a laminated film consisting of an aluminum foil / adhesive layer / innermost thermoplastic material blend layer
The outer layer part is an extrusion temperature of 330 ° C. on a paper substrate (basis weight = 320 g / m 2 ) with a thickness of 20 μm and low density polyethylene (density = 0.920 g / cm 3 , MI = 5.1) by high pressure method. The extrusion coating is applied to laminate the outermost thermoplastic material layer.
Then, the low density polyethylene / paper base paper side and the aluminum foil side of the aluminum foil laminate are blended with a metallocene catalyst polymerized linear low density polyethylene (mLLDPE) of narrow molecular weight distribution and low density polyethylene by high pressure method Then melt extrude the adhesive thermoplastic material layer with an average density of 0.920, a peak melting point of 99 ° C., a melt flow index of 17, a swelling ratio of 1.5 and a layer thickness of 12 μm, laminate and laminate A continuous long laminated packaging material is obtained.
Using this packaging material, a brick-shaped liquid food filled package is obtained in a filling machine.
 特許文献4(特開2004-17984号公報)には、熱可塑性樹脂からなる最外層、紙基材層、介在樹脂層、バリア層、熱可塑性樹脂からなる耐ピンホール性層、熱可塑性樹脂からなる最内層を順次積層した積層体を用いた紙容器であって、印刷層が最外層の内面または紙基材層の表面に設けられており、層間剥離がなく、外観、層間強度に優れ、かつ、輸送による衝撃にも耐えることができるレトルト処理用紙容器が提案されている。 Patent Document 4 (Japanese Patent Laid-Open No. 2004-17984) discloses an outermost layer made of a thermoplastic resin, a paper base layer, an intervening resin layer, a barrier layer, a pinhole resistant layer made of a thermoplastic resin, and a thermoplastic resin. A printed layer is provided on the inner surface of the outermost layer or on the surface of the paper substrate layer, there is no delamination, and the appearance and the interlayer strength are excellent. In addition, retort paper containers have been proposed which can withstand shock due to transportation.
特開平5-213337号公報JP-A-5-213337 特開平7-40975号公報Japanese Patent Laid-Open No. 7-40975 特許第4936346号公報Patent 4936346 gazette 特開2004-17984号公報JP 2004-17984 A
 アルミ箔などのバリア層を備えた多層紙積層材を用いた容器では、外層、内層及び接着層として使用される熱可塑性合成樹脂は、複数の種類が用いられており、押し出しラミネーションを複数回行う必要があり、工程数が多くなり、煩雑であった。
 本発明は、製造工程数を簡素化できる多層紙積層材を利用した紙容器を実現することを目的とする。さらに、本発明は、低温長時間殺菌処理に適した紙容器を開発することを目的とする。
In containers using a multilayer paper laminate having a barrier layer such as aluminum foil, a plurality of types of thermoplastic synthetic resins are used as the outer layer, the inner layer, and the adhesive layer, and extrusion lamination is performed multiple times It was necessary, and the number of processes increased and it was complicated.
An object of the present invention is to realize a paper container using a multi-layered paper laminated material which can simplify the number of manufacturing processes. Furthermore, the present invention aims to develop a paper container suitable for low temperature and long time sterilization treatment.
 本発明は、低温長時間殺菌に適した容器であるとともに、共通する溶融温度を有する熱可塑性合成樹脂を使用することにより、製造工程を簡略した簡素な構造の多層紙容器を提供する。本発明の主な構成は次のとおりである。 The present invention is a container suitable for low-temperature long-term sterilization and using a thermoplastic synthetic resin having a common melting temperature to provide a multilayer paper container having a simple structure in which the manufacturing process is simplified. The main configurations of the present invention are as follows.
1.外表面側から内表面側にかけて、少なくとも熱可塑性樹脂層(A層)、紙基材層(B層)、熱可塑性樹脂層(E層)、バリア層(C層)、接着層(F層)、熱可塑性樹脂層(D層)を備えた多層紙容器であって、
 A層が低密度ポリエチレン樹脂(LDPE)を、F層がエチレン・(メタ)アクリル酸共重合樹脂(E(M)AA)を、D層及びE層が直鎖状低密度ポリエチレン樹脂(L-LDPE)を、それぞれを主成分とする層であることを特徴とする多層紙容器。
2.A層に用いられる低密度ポリエチレン樹脂(LDPE)が、0.910~0.930g/cm3の平均密度、105~125℃のピーク融点であり、
 D層に用いられる直鎖状低密度ポリエチレン樹脂(L-LDPE)が、0.905~0.935g/cm3の平均密度、100~125℃のピーク融点であり、E層に用いられる直鎖状低密度ポリエチレン樹脂(L-LDPE)が、0.905~0.935g/cm3の平均密度、105~125℃のピーク融点であり、D層及びE層に用いられる樹脂が2.0~16.0g/10分のメルトフローレート(MFR)であることを特徴とする1.記載の多層紙容器。
3.A層、E層、F層、D層は、押出しラミネーション法によりB層、C層と積層形成されていることを特徴とする1.又は2.記載の多層紙容器。
4.レンガ状容器であることを特徴とする1.~3.のいずれかに記載の多層紙容器。
5.飲食料を容器に充填した後、90~95℃の低温で長時間の加熱処理されることを特徴とする1.~4.のいずれかに記載の多層紙容器。
6.飲食料が豆腐であることを特徴とする5.記載の多層紙容器。
7.外表面側から内表面側にかけて、少なくとも熱可塑性樹脂層(A層)、紙基材層(B層)、熱可塑性樹脂層(E層)、バリア層(C層)、接着層(F層)、熱可塑性樹脂層(D層)を備えた多層紙容器用原紙を製造する方法であって、
第1工程として、紙基材層(B層)に対して直鎖状低密度ポリエチレン樹脂(L-LDPE)を主成分とする層(E層)を溶融押し出しすると共にバリア層(C層)を供給してラミネーションし、
第2工程として、第1工程で得られた積層体のバリア層(C層)側にエチレン・(メタ)アクリル酸共重合樹脂(E(M)AA)を主成分とする層(F層)と直鎖状低密度ポリエチレン樹脂(L-LDPE)を主成分とする層(D層)とを溶融押し出しして接着層(F層)と熱可塑性樹脂層(D層)をラミネーションし、
第3工程として、第2工程で得られた積層体の紙基材層(B層)側に低密度ポリエチレン樹脂(LDPE)を主成分とする層(A層)を溶融押し出しラミネーションする、
上記3つの工程を連続してラミネーションすることを特徴とする多層紙容器用原紙を製造する方法。
8.外表面側から内表面側にかけて、少なくとも熱可塑性樹脂層(A層)、紙基材層(B層)、熱可塑性樹脂層(E層)、バリア層(C層)、接着層(F層)、熱可塑性樹脂層(D層)を備えた多層紙容器であって、
 A層及びE層が低密度ポリエチレン樹脂(LDPE)を、F層がエチレン・(メタ)アクリル酸共重合樹脂(E(M)AA)を、D層が直鎖状低密度ポリエチレン樹脂(L-LDPE)を、それぞれ主成分とする層であることを特徴とする多層紙容器。
9.A層及びE層に用いられる低密度ポリエチレン樹脂(LDPE)が、0.910~0.930g/cm3の平均密度、105~125℃のピーク融点であり、
 D層に用いられる直鎖状低密度ポリエチレン樹脂(L-LDPE)が、0.905~0.935g/cm3の平均密度、100~125℃のピーク融点であり、D層に用いられる直鎖状低密度ポリエチレン樹脂(L-LDPE)及びE層に用いられる低密度ポリエチレン樹脂(LDPE)が2.0~16.0g/10分のメルトフローレート(MFR)であることを特徴とする8.記載の多層紙容器。
10.外表面側から内表面側にかけて、少なくとも熱可塑性樹脂層(A層)、紙基材層(B層)、熱可塑性樹脂層(E層)、バリア層(C層)、接着層(F層)、熱可塑性樹脂層(D層)を備えた多層紙容器用原紙を製造する方法であって、
第1工程として、紙基材層(B層)に対して低密度ポリエチレン樹脂(LDPE)を主成分とする層(E層)を溶融押し出しすると共にバリア層(C層)を供給してラミネーションし、
第2工程として、第1工程で得られた積層体のバリア層(C層)側にエチレン・(メタ)アクリル酸共重合樹脂(E(M)AA)を主成分とする層(F層)と直鎖状低密度ポリエチレン樹脂(L-LDPE)を主成分とする層(D層)とを溶融押し出しして接着層(F層)と熱可塑性樹脂層(D層)をラミネーションし、
第3工程として、第2工程で得られた積層体の紙基材層(B層)側に低密度ポリエチレン樹脂(LDPE)を主成分とする層(A層)を溶融押し出しラミネーションする、
上記3つの工程を連続してラミネーションすることを特徴とする多層紙容器用原紙を製造する方法。
1. From the outer surface side to the inner surface side, at least the thermoplastic resin layer (A layer), the paper base layer (B layer), the thermoplastic resin layer (E layer), the barrier layer (C layer), the adhesive layer (F layer) A multilayer paper container provided with a thermoplastic resin layer (D layer),
A layer is low density polyethylene resin (LDPE), F layer is ethylene / (meth) acrylic acid copolymer resin (E (M) AA), D layer and E layer are linear low density polyethylene resin (L- A multilayer paper container characterized in that it is a layer having LDPE as a main component.
2. The low density polyethylene resin (LDPE) used for the layer A has an average density of 0.910 to 0.930 g / cm 3 , a peak melting point of 105 to 125 ° C.,
The linear low density polyethylene resin (L-LDPE) used for the D layer has an average density of 0.905 to 0.935 g / cm 3 , a peak melting point of 100 to 125 ° C., and a linear chain used for the E layer Low density polyethylene resin (L-LDPE) has an average density of 0.905 to 0.935 g / cm 3 , a peak melting point of 105 to 125 ° C., and a resin used for D layer and E layer is 2.0 to It is characterized by having a melt flow rate (MFR) of 16.0 g / 10 min. Multilayer paper container as described.
3. The A layer, the E layer, the F layer, and the D layer are laminated with the B layer and the C layer by the extrusion lamination method. Or 2. Multilayer paper container as described.
4. It is a brick-like container 1. To 3. A multilayer paper container according to any of the above.
5. After filling the food and drink in a container, it is characterized in that it is heat-treated at a low temperature of 90 to 95 ° C. for a long time. To 4. A multilayer paper container according to any of the above.
6. Food and drink are characterized by tofu. Multilayer paper container as described.
7. From the outer surface side to the inner surface side, at least the thermoplastic resin layer (A layer), the paper base layer (B layer), the thermoplastic resin layer (E layer), the barrier layer (C layer), the adhesive layer (F layer) A method for producing a multi-layered paper container base paper provided with a thermoplastic resin layer (D layer),
As a first step, a layer (E layer) containing a linear low density polyethylene resin (L-LDPE) as a main component is melted and extruded to a paper base layer (B layer) and a barrier layer (C layer) is formed. Supply and laminate,
As a second step, a layer (F layer) containing ethylene / (meth) acrylic acid copolymer resin (E (M) AA) as a main component on the barrier layer (C layer) side of the laminate obtained in the first step And melt extruding a layer (D layer) mainly composed of a linear low density polyethylene resin (L-LDPE) and laminating an adhesive layer (F layer) and a thermoplastic resin layer (D layer),
As the third step, the layer (A layer) mainly composed of low density polyethylene resin (LDPE) is melt extruded and laminated on the paper base layer (B layer) side of the laminate obtained in the second step.
A method of producing a base paper for a multilayer paper container, which comprises continuously laminating the above three steps.
8. From the outer surface side to the inner surface side, at least the thermoplastic resin layer (A layer), the paper base layer (B layer), the thermoplastic resin layer (E layer), the barrier layer (C layer), the adhesive layer (F layer) A multilayer paper container provided with a thermoplastic resin layer (D layer),
A layer and E layer are low density polyethylene resin (LDPE), F layer is ethylene / (meth) acrylic acid copolymer resin (E (M) AA), D layer is linear low density polyethylene resin (L- A multilayer paper container characterized in that it is a layer containing LDPE as a main component.
9. The low density polyethylene resin (LDPE) used in layers A and E has an average density of 0.910 to 0.930 g / cm 3 and a peak melting point of 105 to 125 ° C.
The linear low density polyethylene resin (L-LDPE) used for the D layer has an average density of 0.905 to 0.935 g / cm 3 , a peak melting point of 100 to 125 ° C., and the linear chain used for the D layer Low density polyethylene resin (L-LDPE) and low density polyethylene resin (LDPE) used for the E layer are characterized by a melt flow rate (MFR) of 2.0 to 16.0 g / 10 min. Multilayer paper container as described.
10. From the outer surface side to the inner surface side, at least the thermoplastic resin layer (A layer), the paper base layer (B layer), the thermoplastic resin layer (E layer), the barrier layer (C layer), the adhesive layer (F layer) A method for producing a multi-layered paper container base paper provided with a thermoplastic resin layer (D layer),
As the first step, the layer (E layer) mainly composed of low density polyethylene resin (LDPE) is melt extruded to the paper base layer (B layer) and the barrier layer (C layer) is supplied to perform lamination. ,
As a second step, a layer (F layer) containing ethylene / (meth) acrylic acid copolymer resin (E (M) AA) as a main component on the barrier layer (C layer) side of the laminate obtained in the first step And melt extruding a layer (D layer) mainly composed of a linear low density polyethylene resin (L-LDPE) and laminating an adhesive layer (F layer) and a thermoplastic resin layer (D layer),
As the third step, the layer (A layer) mainly composed of low density polyethylene resin (LDPE) is melt extruded and laminated on the paper base layer (B layer) side of the laminate obtained in the second step.
A method of producing a base paper for a multilayer paper container, which comprises continuously laminating the above three steps.
1.バリア層から容器内表面側にエチレン・(メタ)アクリル酸共重合樹脂(E(M)AA)からなる接着層(F層)を介して直鎖状低密度ポリエチレン樹脂(L-LDPE)を主成分とする層(D層)を形成することにより、簡単な構成であっても、強い接着強度とピンホール耐性を維持できる容器を実現した。直鎖状低密度ポリエチレン樹脂は、低密度ポリエチレン樹脂(LDPE)よりも柔軟性があり、ボイルなどの刺激に対してもピンホール耐性を保つことができる。本発明の層構成によって、低温長時間殺菌処理が必要な飲食品用の容器を提供することができる。
2.A層及びE層に用いられる樹脂のピーク温度を105~125℃、D層に用いられる樹脂のピーク融点を100~125℃と設定したので、90℃前後でボイル加熱処理される紙容器に適している。
 ピンホール耐性が強いので、様々なpHである飲食料に適しており、低温加熱時間が長く積算熱量が多くなる豆腐充填用の容器として特に適している。
3.少なくとも紙基材(B層)から容器内側の樹脂層(D層)に使用される熱可塑性樹脂層に、共通の温度物性(特に、メルトフローレート(MFR)。)を備えている樹脂を用いることにより、押し出しラミネーションを連続して行うことができる。なお、表面のA層は断熱性の高いB層を挟んでいるので、他の熱可塑性樹脂層ほどシビアな共通性は求められない。
4.レンガ状容器に適しており、無菌充填タイプの紙容器に適している。
 D層に用いられる直鎖状低密度ポリエチレン樹脂が、0.905~0.935g/cm3の平均密度、100~125℃のピーク融点であり、E層に用いられる樹脂が、0.905~0.935g/cm3の平均密度、105~125℃のピーク融点であり、D層及びE層に用いられる樹脂が2.0~16.0/10分のメルトフローレートであることにより、押し出しラミネーションを連続して行うことが容易である。また、D層及びF層に用いられる樹脂が2.0~16.0/10分のメルトフローレートであることにより、D層とF層の層間、及びD層同士の横シールが強固に接着される。
1. Mainly a linear low density polyethylene resin (L-LDPE) through the adhesive layer (F layer) consisting of ethylene / (meth) acrylic acid copolymer resin (E (M) AA) from the barrier layer to the inner surface side of the container By forming a layer (D layer) as a component, a container capable of maintaining strong adhesive strength and pinhole resistance even with a simple configuration is realized. Linear low density polyethylene resin is more flexible than low density polyethylene resin (LDPE), and can maintain pinhole resistance against irritation such as boiling. According to the layer configuration of the present invention, it is possible to provide a container for food and drink that requires low temperature and long time sterilization treatment.
2. The peak temperature of the resin used for layer A and E was set to 105 to 125 ° C, and the peak melting point of the resin used for layer D was set to 100 to 125 ° C, so it is suitable for paper containers heated at around 90 ° C. ing.
Since the pinhole resistance is strong, it is suitable for food and drink having various pH, and it is particularly suitable as a container for tofu filling in which the low temperature heating time is long and the accumulated heat amount is large.
3. A resin having common temperature physical properties (in particular, melt flow rate (MFR)) is used for the thermoplastic resin layer used for at least the paper base (B layer) to the resin layer (D layer) inside the container. Thus, extrusion lamination can be performed continuously. In addition, since the A layer on the surface sandwiches the B layer having high heat insulating property, the commonality is not as severe as other thermoplastic resin layers.
4. Suitable for brick-like containers, suitable for aseptic filling type paper containers.
The linear low density polyethylene resin used for the D layer has an average density of 0.905 to 0.935 g / cm 3 , the peak melting point of 100 to 125 ° C., and the resin used for the E layer has a density of 0.905 to Extrusion with an average density of 0.935 g / cm 3 , a peak melting point of 105 to 125 ° C., and a resin used for layer D and layer E having a melt flow rate of 2.0 to 16.0 / 10 minutes It is easy to carry out lamination continuously. In addition, when the resin used for the D layer and the F layer has a melt flow rate of 2.0 to 16.0 / 10 minutes, the interlayer seal between the D layer and the F layer and the lateral seal between the D layers are firmly adhered. Be done.
本発明の紙容器の例を示す図。The figure which shows the example of the paper container of this invention. 第一の形態の多層紙容器に用いられる紙積層体の構造例を示す図。The figure which shows the structural example of the paper laminated body used for the multilayer paper container of a 1st form. 第二の形態の多層紙容器に用いられる紙積層体の構造例を示す図。The figure which shows the structural example of the paper laminated body used for the multilayer paper container of 2nd form. 通電方式によるピンホール試験を示す図。The figure which shows the pinhole test by an electricity supply system.
11:ブリックタイプ容器
12:側面
13:正面
14:背面
15:上面
16:下面
17:折り耳部
18、19:熱融着部
11: brick type container 12: side surface 13: front surface 14: rear surface 15: upper surface 16: lower surface 17: folding edge portion 18, 19: heat sealing portion
 本発明の第一の形態の多層紙容器の全体層構成は、外表面側から内表面側にかけて、少なくとも熱可塑性樹脂層(A層)、紙基材層(B層)、熱可塑性樹脂層(E層)、バリア層(C層)、接着層(F層)、熱可塑性樹脂層(D層)を備えた多層紙容器であって、A層が低密度ポリエチレン樹脂を、F層がエチレン・(メタ)アクリル酸共重合樹脂を、D層及びE層が直鎖状低密度ポリエチレン樹脂を、それぞれ主成分とする。各層に押し出しラミネーションに適した熱可塑性樹脂を使用することによって、製造工程を簡素化している。バリア層から容器内表面側にエチレン・(メタ)アクリル酸共重合樹脂からなる接着層(F層)を介して直鎖状低密度ポリエチレン樹脂を主成分とする層(D層)とすることにより、ピンホール耐性に優れている。
 A層に用いられる低密度ポリエチレン樹脂を0.910~0.930g/cm3の平均密度、105~125℃のピーク融点とし、D層に用いられる直鎖状低密度ポリエチレン樹脂を0.905~0.935g/cm3の平均密度、100~125℃のピーク融点、E層に用いられる直鎖状低密度ポリエチレン樹脂を0.905~0.935g/cm3の平均密度、105~125℃のピーク融点、D層及びE層に用いられる樹脂が2.0~16.0/10分のメルトフローレートであることとして、温度物性を共通化した。
 ボイルに対応するように、95℃には十分に耐え得るために、A層、E層のピーク融点温度を105~125℃、D層のピーク融点温度を100~125℃に設定した。
From the outer surface side to the inner surface side, the entire layer configuration of the multilayer paper container of the first embodiment of the present invention is at least a thermoplastic resin layer (A layer), a paper base layer (B layer), a thermoplastic resin layer E)), a barrier layer (C layer), an adhesive layer (F layer), and a thermoplastic resin layer (D layer), wherein the A layer is a low density polyethylene resin, the F layer is ethylene, The (meth) acrylic acid copolymer resin and the D layer and the E layer each have a linear low density polyethylene resin as a main component. The use of a thermoplastic resin suitable for extrusion lamination in each layer simplifies the manufacturing process. By forming a layer (D layer) mainly composed of a linear low density polyethylene resin through an adhesive layer (F layer) made of ethylene / (meth) acrylic acid copolymer resin from the barrier layer to the inner surface side of the container , Excellent in pinhole resistance.
The low density polyethylene resin used in the A layer has an average density of 0.910 to 0.930 g / cm 3 , the peak melting point of 105 to 125 ° C., and the linear low density polyethylene resin used in the D layer is 0.905 to Average density of 0.935 g / cm 3 , peak melting point of 100 to 125 ° C., linear low density polyethylene resin used for E layer, average density of 0.905 to 0.935 g / cm 3 , 105 to 125 ° C. The temperature physical properties were made common, assuming that the peak melting point, and the resin used for the D layer and the E layer had a melt flow rate of 2.0 to 16.0 / 10 minutes.
The peak melting point temperatures of the layers A and E were set to 105 to 125 ° C., and the peak melting point temperature of the layer D to 100 to 125 ° C. so as to sufficiently withstand 95 ° C. so as to correspond to the boiling.
 本発明の第二の形態の多層紙容器の全体層構成は、外表面側から内表面側にかけて、少なくとも熱可塑性樹脂層(A層)、紙基材層(B層)、熱可塑性樹脂層(E層)、バリア層(C層)、接着層(F層)、熱可塑性樹脂層(D層)を備えた多層紙容器であって、A層及びE層が低密度ポリエチレン樹脂を、F層がエチレン・(メタ)アクリル酸共重合樹脂を、D層が直鎖状低密度ポリエチレン樹脂を、それぞれ主成分とする。各層に押し出しラミネーションに適した熱可塑性樹脂を使用することによって、製造工程を簡素化している。バリア層から容器内表面側にエチレン・(メタ)アクリル酸共重合樹脂からなる接着層(F層)を介して直鎖状低密度ポリエチレン樹脂を主成分とする層(D層)とすることにより、ピンホール耐性に優れた紙容器である。
 A層及びE層に用いられる低密度ポリエチレン樹脂を0.910~0.930g/cm3の平均密度、105~125℃のピーク融点とし、D層に用いられる直鎖状低密度ポリエチレン樹脂を0.905~0.935g/cm3の平均密度、100~125℃のピーク融点、D層及びE層に用いられる樹脂が2.0~16.0/10分のメルトフローレートであることとして、温度物性を共通化した。
 ボイルに対応するように、95℃には十分に耐え得るために、A層、E層のピーク融点温度を105~125℃、D層のピーク融点温度を100~125℃に設定した。
The entire layer configuration of the multilayer paper container of the second embodiment of the present invention is at least a thermoplastic resin layer (A layer), a paper base layer (B layer), a thermoplastic resin layer (from the outer surface side to the inner surface side) E layer), a barrier layer (C layer), an adhesive layer (F layer), and a thermoplastic resin layer (D layer), wherein the A layer and the E layer are low density polyethylene resin, F layer The ethylene / (meth) acrylic acid copolymer resin and the D layer mainly contain a linear low density polyethylene resin. The use of a thermoplastic resin suitable for extrusion lamination in each layer simplifies the manufacturing process. By forming a layer (D layer) mainly composed of a linear low density polyethylene resin through an adhesive layer (F layer) made of ethylene / (meth) acrylic acid copolymer resin from the barrier layer to the inner surface side of the container , It is a paper container excellent in pinhole resistance.
The low density polyethylene resin used for layer A and layer E has an average density of 0.910 to 0.930 g / cm 3 , a peak melting point of 105 to 125 ° C., and the linear low density polyethylene resin used for layer D is 0 With an average density of 905 to 0.935 g / cm 3 , a peak melting point of 100 to 125 ° C., and a resin used for layer D and layer E having a melt flow rate of 2.0 to 16.0 / 10 minutes, The temperature property was made common.
The peak melting point temperatures of the layers A and E were set to 105 to 125 ° C., and the peak melting point temperature of the layer D to 100 to 125 ° C. so as to sufficiently withstand 95 ° C. so as to correspond to the boiling.
 本発明の第一の形態及び第二の形態において、主成分とするとは、50wt%より多く含有することを意味する。より好ましくは70wt%以上含有し、更に好ましくは80wt%以上含有し、最も好ましくは90wt%以上含有する。
 本発明の第一の形態及び第二の形態において、各層に用いられる樹脂のピーク融点とは、示差走査熱量測定法により測定されるものであり、複数本のピークが測定される場合は少なくとも1本のピークが、上記温度範囲に含まれていればよい。
In the first and second embodiments of the present invention, as the main component means containing more than 50 wt%. The content is more preferably 70 wt% or more, still more preferably 80 wt% or more, and most preferably 90 wt% or more.
In the first form and the second form of the present invention, the peak melting point of the resin used in each layer is measured by differential scanning calorimetry, and at least 1 when multiple peaks are measured. The peak of the book may be included in the above temperature range.
 本発明の紙容器は、高温で調理した後の飲食品を無菌充填する容器や、無菌充填したのちに例えば90℃~95℃でボイルして再調整する飲食品用容器に適している。例えば、豆腐は、豆乳に凝固剤を混合して充填した後に、凝固のために90℃前後でボイル加熱処理される。そして、90℃で40分間加熱するかそれと同等以上の効力を有する方法での加熱処理が求められる。その他、ゼリーのように、充填時に液体であるが充填後にゲル状となる飲食品、特に防水性、防湿性、遮光性、酸素バリア性等を必要とする内容物に適する。充填後100℃以上の高温で処理する飲食品には適さない。
 本発明の紙容器は、バリア性、ヒートシール性を備え、紙として廃棄処理することができ、減容化、軽量化にすぐれる。レンガ状容器とした場合は、収納性、保存性、搬送性にも優れている。
The paper container of the present invention is suitable as a container for aseptically filling food and drink after cooking at high temperature, and as a container for food and drink after boil and readjustment, for example, at 90 ° C. to 95 ° C. after aseptic filling. For example, after tofu is mixed with soy milk and mixed with a coagulant, it is boiled at about 90 ° C. for coagulation. Then, heat treatment at a temperature of 90 ° C. for 40 minutes or a method having the same or higher efficacy is required. In addition, it is suitable for food and drink such as jelly, which is liquid at the time of filling but becomes gel after filling, in particular, contents requiring waterproofness, moisture resistance, light shielding property, oxygen barrier property and the like. It is not suitable for food and drink processed at high temperature of 100 ° C or more after filling.
The paper container of the present invention has barrier properties and heat sealing properties, can be disposed of as paper, and is excellent in volume reduction and weight reduction. When made into a brick-like container, it is excellent also in storability, preservability, and conveyance nature.
 以下、本発明の実施例について図面を参照しながら説明する。
 本発明の容器の一例として、いわゆるレンガ状(ブリックタイプ)の紙容器を例にとって説明する。
 図1に示すブリックタイプ紙容器11は、紙容器用原紙を折り曲げて、側面と上下の開口を熱融着(ヒートシール)して四角のレンガ状の立方体に成形した容器である。左右の側面12、正面13、背面14、上面15、下面16の六面から構成されている。紙容器用原紙の側辺部は重ね合わされて接合された熱融着部18となっている。また、上下の端辺部も重ね合わされて接合されて熱融着部19となっている。上面部から側面部に折り曲げられて折り耳部17が、側面12に接合されている。熱融着部18は、背面から上面あるいは下面へ屈曲角部で重ねられた状態で折り曲げられる。また、熱融着部19は、上面から側面へ屈曲角部で重ねられた状態で折り曲げられる。
 レンガ状の紙容器の形状自体は従来のものと同様である。
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
As an example of the container of the present invention, a so-called brick-type paper container will be described as an example.
The brick type paper container 11 shown in FIG. 1 is a container formed by bending a base paper for paper container and heat-sealing (heat sealing) side surfaces and upper and lower openings to form a square brick-like cube. The right and left sides 12, the front surface 13, the back surface 14, the upper surface 15, and the lower surface 16 are constituted by six surfaces. The side portions of the base paper for paper containers are heat-sealed portions 18 which are overlapped and joined. Further, the upper and lower end portions are also overlapped and joined to form a thermally fused portion 19. The folded-ear portion 17 is joined to the side surface 12 by being bent from the upper surface portion to the side surface portion. The heat sealing portion 18 is bent from the back surface to the upper surface or the lower surface in a state of being overlapped at the bending corner portion. Further, the heat-sealing part 19 is bent in a state of being overlapped at the bending corner part from the upper surface to the side surface.
The shape itself of the brick-like paper container is similar to that of the conventional one.
 第一の形態の多層紙容器に用いられる紙積層体の構造例を図2に示す。
 紙積層体の層構成は、外表面側から内表面側にかけて、少なくとも熱可塑性樹脂層(A層)、紙基材層(B層)、熱可塑性樹脂層(E層)、バリア層(C層)、接着層(F層)、熱可塑性樹脂層(D層)を備える。
 印刷層は、予め印刷した紙基材を用いている。この印刷層を設けないことも可能である。また、A層の表面に印刷層を設けることもできる。熱可塑性樹脂層(E層)とバリア層(C層)との間に、熱可塑性樹脂からなる接着層(G層)を設けても良い。
 A層が低密度ポリエチレン樹脂(LDPE)を、F層がエチレン・(メタ)アクリル酸共重合樹脂(E(M)AA)を、D層及びE層が直鎖状低密度ポリエチレン樹脂(L-LDPE)を、それぞれ主成分とする。
The structural example of the paper laminated body used for the multilayer paper container of a 1st form is shown in FIG.
The layer structure of the paper laminate is at least a thermoplastic resin layer (A layer), a paper base layer (B layer), a thermoplastic resin layer (E layer), a barrier layer (C layer) from the outer surface side to the inner surface side ), An adhesive layer (F layer), and a thermoplastic resin layer (D layer).
The printed layer uses a pre-printed paper substrate. It is also possible not to provide this printing layer. Moreover, a printing layer can also be provided on the surface of A layer. An adhesive layer (G layer) made of a thermoplastic resin may be provided between the thermoplastic resin layer (E layer) and the barrier layer (C layer).
A layer is low density polyethylene resin (LDPE), F layer is ethylene / (meth) acrylic acid copolymer resin (E (M) AA), D layer and E layer are linear low density polyethylene resin (L- Each of LDPE) is a main component.
 A層に用いられる低密度ポリエチレン樹脂(LDPE)は、平均密度が0.910~0.930g/cm3、ピーク融点が105~125℃である。 The low density polyethylene resin (LDPE) used for the layer A has an average density of 0.910 to 0.930 g / cm 3 and a peak melting point of 105 to 125 ° C.
 B層に用いられる紙基材は、所望する紙容器品質に合わせて適宜選択可能であり、特に限定されないが、一例として液体包装用の紙容器に用いられている紙基材を用いることができる。1層構成の紙基材あるいは多層構造の紙基材が使用できる。成形に伴う屈曲耐性や落下衝撃吸収性、端面の耐水性などに優れていることが好ましい。
 例えば、低密度の内層の両側に高密度層を形成した多層紙基材は、低密度層が曲げ応力や落下の衝撃を吸収する機能に優れた紙基材である。
 紙基材は、耐水性を向上させるために、内添サイズ剤としてアルキルケテンダイマー等を全原料パルプ100重量部(絶乾パルプ重量)に対し0.15重量部以上0.80重量部未満含有することも有効である。さらに、カチオン化澱粉、両性澱粉、酸化澱粉などの澱粉、及び/または硫酸バンドを添加すると、アルキルケテンダイマーのパルプへの定着を向上させる効果があり、特に耐水性が向上するため好ましい。
The paper base used for the layer B can be appropriately selected according to the desired quality of the paper container, and is not particularly limited. For example, the paper base used for a paper container for liquid packaging can be used . A single layer paper base or a multilayer paper base can be used. It is preferable to be excellent in bending resistance and drop impact absorption, molding water resistance, and the like.
For example, a multilayer paper base in which a high density layer is formed on both sides of a low density inner layer is a paper base excellent in the function of the low density layer to absorb bending stress and impact from falling.
The paper base contains, as an internal sizing agent, at least 0.15 parts by weight but less than 0.80 parts by weight based on 100 parts by weight of total raw material pulp (absolute dry pulp weight) to improve water resistance. It is also effective to do. Furthermore, the addition of a cationized starch, an amphoteric starch, a starch such as oxidized starch, and / or a sulfuric acid band is preferable because it has the effect of improving the fixing of the alkyl ketene dimer to the pulp and in particular improves the water resistance.
 C層に用いられるバリア材は、一般的に多層紙容器に使用されているアルミ箔等のバリア材を使用することができる。
 アルミ箔若しくはアルミニウムの薄膜層を構成するアルミニウムとしては、通常のアルミニウム金属を使用することができる。
The barrier material used for C layer can use barrier materials, such as aluminum foil generally used for a multilayer paper container.
A common aluminum metal can be used as aluminum which comprises a thin film layer of aluminum foil or aluminum.
 D層に用いられる直鎖状低密度ポリエチレン樹脂(L-LDPE)は、平均密度が0.905~0.935g/cm3、ピーク融点が100~125℃であり、E層に用いられる直鎖状低密度ポリエチレン樹脂(L-LDPE)は、平均密度が0.905~0.935g/cm3、ピーク融点が105~125℃であり、D層及びE層に用いられる直鎖状低密度ポリエチレン樹脂(L-LDPE)は2.0~16.0/10分のメルトフローレート(MFR)であることが好ましい。平均密度、ピーク融点、メルトフローレート(MFR)を上記範囲とすることで、押し出しラミネーションを連続して行うことが容易であるため好ましい。より好ましくはD層に用いられる直鎖状低密度ポリエチレン樹脂(L-LDPE)の平均密度が0.905~0.935g/cm3、ピーク融点が105~125℃であり、さらに好ましくはD層及びE層に用いられる直鎖状低密度ポリエチレン樹脂(L-LDPE)の平均密度が0.910~0.925g/cm3、ピーク融点が105~125℃、メルトフローレート(MFR)が6.0~15.0/10分であり、最も好ましくは、D層及びE層に用いられる直鎖状低密度ポリエチレン樹脂(L-LDPE)の平均密度が0.910~0.925g/cm3、ピーク融点が105~125℃、メルトフローレート(MFR)が8.0~12.0/10分である。
 本発明では、紙容器を構成するために紙容器用原紙の縁部を熱融着(ヒートシール)するが、その際に必要なヒートシールによって形成される横シールがしっかり密着する。本多層紙容器では、2つの縁部のD層/D層がヒートシールされて横シールを形成するが、この横シールは低温長時間加熱されても、十分な耐性が発揮されている。
The linear low density polyethylene resin (L-LDPE) used for the D layer has an average density of 0.905 to 0.935 g / cm 3 and a peak melting point of 100 to 125 ° C. Low density polyethylene resin (L-LDPE) has an average density of 0.905 to 0.935 g / cm 3 and a peak melting point of 105 to 125 ° C., and is a linear low density polyethylene used for D layer and E layer The resin (L-LDPE) is preferably a melt flow rate (MFR) of 2.0 to 16.0 / 10 minutes. By setting the average density, the peak melting point, and the melt flow rate (MFR) in the above-mentioned ranges, it is preferable to perform extrusion lamination continuously, which is preferable. More preferably, the average density of the linear low density polyethylene resin (L-LDPE) used in the D layer is 0.905 to 0.935 g / cm 3 , the peak melting point is 105 to 125 ° C., and more preferably the D layer And E layers, the average density of linear low density polyethylene resin (L-LDPE) is 0.910 to 0.925 g / cm 3 , the peak melting point is 105 to 125 ° C., and the melt flow rate (MFR) is 6. 0 to 15.0 / 10 minutes, and most preferably, the average density of linear low density polyethylene resin (L-LDPE) used in layer D and layer E is 0.910 to 0.925 g / cm 3 , The peak melting point is 105 to 125 ° C., and the melt flow rate (MFR) is 8.0 to 12.0 / 10 minutes.
In the present invention, the edges of the base paper for paper containers are heat-sealed (heat-sealed) in order to constitute the paper container, but the transverse seal formed by the heat seal required at that time is firmly adhered. In this multilayer paper container, the two edge D / D layers are heat sealed to form a transverse seal, but the transverse seal exhibits sufficient resistance even when heated at a low temperature for a long time.
 F層に用いられるエチレン・(メタ)アクリル酸共重合樹脂(E(M)AA)は、要求される性能に従って決定され特に限定されるものではないが、通常、平均密度が0.910~0.950g/cm3、ピーク融点が80~110℃であり、メルトフローレート(MFR)が2.0~16.0/10分であると、D層とエチレン・(メタ)アクリル酸共重合樹脂(E(M)AA)からなる接着層(F層)との接着性、すなわち、D層/F層間の接着強度が良好であると共に、ボイルなどの刺激に対するピンホール耐性や、紙容器の横シール部(図1のNo.19の箇所:容器内面の熱可塑性樹脂層(D層)同士の接着部)の接着性が良好となるため好ましい。 The ethylene / (meth) acrylic acid copolymer resin (E (M) AA) used for the F layer is not particularly limited, which is determined according to the required performance, but usually, the average density is 0.910 to 0 .950 g / cm 3 , peak melting point 80 to 110 ° C., melt flow rate (MFR) 2.0 to 16.0 / 10 minutes, D layer and ethylene (meth) acrylic acid copolymer resin The adhesive property with the adhesive layer (F layer) consisting of (E (M) AA), that is, the adhesive strength between the D layer and the F layer is good and also the pinhole resistance against stimuli such as boiling and the side of the paper container It is preferable because the adhesiveness of the sealing portion (the portion of No. 19 in FIG. 1: the bonding portion between the thermoplastic resin layers (D layers) on the inner surface of the container) becomes good.
 G層に用いられる熱可塑性樹脂は特に限定されるものではないが、上記F層に用いられる樹脂が好適に用いられる。 The thermoplastic resin used for the G layer is not particularly limited, but the resin used for the F layer is preferably used.
 第二の形態の多層紙容器に用いられる紙積層体の構造例を図3に示す。
 紙積層体の層構成は、外表面側から内表面側にかけて、少なくとも熱可塑性樹脂層(A層)、紙基材層(B層)、熱可塑性樹脂層(E層)、バリア層(C層)、接着層(F層)、熱可塑性樹脂層(D層)を備える。
 印刷層は、予め印刷した紙基材を用いている。この印刷層を設けないことも可能である。また、A層の表面に印刷層を設けることもできる。熱可塑性樹脂層(E層)とバリア層(C層)との間に、熱可塑性樹脂からなる接着層(G層)を設けても良い。
 A層及びE層が低密度ポリエチレン樹脂(LDPE)を、F層がエチレン・(メタ)アクリル酸共重合樹脂(E(M)AA)を、D層が直鎖状低密度ポリエチレン樹脂(L-LDPE)を、それぞれ主成分とする層である。
The structural example of the paper laminated body used for the multilayer paper container of 2nd form is shown in FIG.
The layer structure of the paper laminate is at least a thermoplastic resin layer (A layer), a paper base layer (B layer), a thermoplastic resin layer (E layer), a barrier layer (C layer) from the outer surface side to the inner surface side ), An adhesive layer (F layer), and a thermoplastic resin layer (D layer).
The printed layer uses a pre-printed paper substrate. It is also possible not to provide this printing layer. Moreover, a printing layer can also be provided on the surface of A layer. An adhesive layer (G layer) made of a thermoplastic resin may be provided between the thermoplastic resin layer (E layer) and the barrier layer (C layer).
A layer and E layer are low density polyethylene resin (LDPE), F layer is ethylene / (meth) acrylic acid copolymer resin (E (M) AA), D layer is linear low density polyethylene resin (L- LDPE) is a layer containing each as a main component.
 E層に用いられる低密度ポリエチレン樹脂(LDPE)は、平均密度が0.910~0.930g/cm3、ピーク融点が105~125℃である。
 A層、B層、C層、D層、F層、G層は、それぞれ、上記第一の紙積層体に用いたものを使用することができる。
The low density polyethylene resin (LDPE) used for the E layer has an average density of 0.910 to 0.930 g / cm 3 and a peak melting point of 105 to 125 ° C.
As the A layer, B layer, C layer, D layer, F layer, and G layer, those used for the first paper laminate can be used.
 D層に用いられる直鎖状低密度ポリエチレン樹脂(L-LDPE)及びE層に用いられる低密度ポリエチレン樹脂(LDPE)は2.0~16.0/10分のメルトフローレート(MFR)であることが好ましい。平均密度、ピーク融点、メルトフローレート(MFR)を上記範囲とすることで、押し出しラミネーションを連続して行うことが容易であるため好ましい。より好ましくは、D層に用いられる直鎖状低密度ポリエチレン樹脂(L-LDPE)の平均密度が0.905~0.935g/cm3、ピーク融点が105~125℃であり、 さらに好ましくはD層に用いられる直鎖状低密度ポリエチレン樹脂(L-LDPE)及びE層に用いられる低密度ポリエチレン樹脂(LDPE)の平均密度が0.910~0.925g/cm3、ピーク融点が105~125℃、メルトフローレート(MFR)が6.0~15.0/10分であり、最も好ましくは、D層に用いられる直鎖状低密度ポリエチレン樹脂(L-LDPE)及びE層に用いられる低密度ポリエチレン樹脂(LDPE)の平均密度が0.910~0.925g/cm3、ピーク融点が105~125℃、メルトフローレート(MFR)が8.0~12.0/10分である。 Linear low density polyethylene resin (L-LDPE) used in layer D and low density polyethylene resin (LDPE) used in layer E have a melt flow rate (MFR) of 2.0 to 16.0 / 10 minutes Is preferred. By setting the average density, the peak melting point, and the melt flow rate (MFR) in the above-mentioned ranges, it is preferable to perform extrusion lamination continuously, which is preferable. More preferably, the average density of the linear low density polyethylene resin (L-LDPE) used in the D layer is 0.905 to 0.935 g / cm 3 , the peak melting point is 105 to 125 ° C., and more preferably D The average density of the linear low density polyethylene resin (L-LDPE) used in the layer and the low density polyethylene resin (LDPE) used in the E layer is 0.910 to 0.925 g / cm 3 , and the peak melting point is 105 to 125 ° C, melt flow rate (MFR) 6.0 to 15.0 / 10 min, most preferably linear low density polyethylene resin (L-LDPE) used in layer D and low used in layer E Density polyethylene resin (LDPE), the average density is 0.910 to 0.925 g / cm 3 , the peak melting point is 105 to 125 ° C., and the melt flow rate (MFR) is 8. It is 0 to 12.0 / 10 minutes.
 本発明では、紙容器を構成するために紙容器用原紙の縁部を熱融着(ヒートシール)するが、その際に必要なヒートシールによって形成される横シールがしっかり密着する。本多層紙容器では、2つの縁部のD層/D層がヒートシールされて横シールを形成するが、この横シールは低温長時間加熱されても、十分な耐性が発揮されている。
[実施例1]
In the present invention, the edges of the base paper for paper containers are heat-sealed (heat-sealed) in order to constitute the paper container, but the transverse seal formed by the heat seal required at that time is firmly adhered. In this multilayer paper container, the two edge D / D layers are heat sealed to form a transverse seal, but the transverse seal exhibits sufficient resistance even when heated at a low temperature for a long time.
Example 1
<層構成>
・熱可塑性樹脂(A層):
 LDPE(日本ポリエチレン社製、製品名:LC602A、
 平均密度0.919g/cm3、ピーク融点107℃、MFR8.2)
・紙基材層(B層):坪量200g/m2の液体包装用原紙(1層構成)
・熱可塑性樹脂(E層):
 L-LDPE(日本ポリエチレン社製、製品名:NH745N、
 平均密度0.913g/cm3、ピーク融点121℃、MFR8.0)
・バリア層(C層):アルミ箔(住友軽金属社製、厚さ7μm)
・接着層(F層):
 EMAA(三井デュポン社製、製品名:NC0908C、
 平均密度0.930g/cm3、ピーク融点99℃、MFR8.0)
・熱可塑性樹脂(D層):
 L-LDPE(日本ポリエチレン社製、製品名:NH745N、
 平均密度0.913g/cm3、ピーク融点121℃、MFR8.0)
<Layer composition>
Thermoplastic resin (layer A):
LDPE (manufactured by Japan Polyethylene Corporation, product name: LC602A,
Average density 0.919 g / cm 3 , peak melting point 107 ° C., MFR 8.2)
Paper base layer (B layer): base paper for liquid packaging having a basis weight of 200 g / m 2 (one-layer structure)
Thermoplastic resin (E layer):
L-LDPE (manufactured by Japan Polyethylene Corporation, product name: NH745N,
Average density 0.913 g / cm 3 , peak melting point 121 ° C., MFR 8.0)
-Barrier layer (C layer): Aluminum foil (Sumitomo Light Metal Co., Ltd., 7 μm thick)
Adhesive layer (F layer):
EMAA (made by Mitsui DuPont, product name: NC0908C,
Average density 0.930 g / cm 3 , peak melting point 99 ° C., MFR 8.0)
Thermoplastic resin (D layer):
L-LDPE (manufactured by Japan Polyethylene Corporation, product name: NH745N,
Average density 0.913 g / cm 3 , peak melting point 121 ° C., MFR 8.0)
<工程>
 次の3つの工程を連続してラミネーションすることにより、多層紙容器用原紙1を作製する。
第1工程:
  紙基材層(B層)に対してL-LDPE層(E層)を溶融押し出しすると共にバリア層(C層)を供給してラミネーションし、
第2工程:
  第1工程で得られた積層体のバリア層(C層)側にEMAA層(F層)と、L-LDPE層(D層)とを溶融押し出しして接着層(F層)と熱可塑性樹脂層(D層)をラミネーションし、
第3工程:
  第2工程で得られた積層体の紙基材層(B層)側にLDPE層(A層)を溶融押し出しラミネーションする。
<Process>
By sequentially laminating the following three steps, a base paper 1 for multilayer paper container is produced.
First step:
The L-LDPE layer (E layer) is melt-extruded to the paper base layer (B layer) and the barrier layer (C layer) is supplied for lamination,
Second step:
Adhesive layer (F layer) and thermoplastic resin by melt-extrusion of the EMAA layer (F layer) and L-LDPE layer (D layer) on the barrier layer (C layer) side of the laminate obtained in the first step Layer (D layer),
Third step:
The LDPE layer (A layer) is melt extruded and laminated on the paper base layer (B layer) side of the laminate obtained in the second step.
<紙容器の作製>
 得られた多層紙容器用原紙について、充填機(機名・型番:UP-FUJI MA60、四国化工機社製、SLIM200ml設定)を使用して、図1に示すブリックタイプ紙容器(充填物:水)を連続的に5000個作製した。
[実施例2]
<Preparation of paper container>
About the obtained base paper for multilayer paper containers, using a filling machine (machine name / model number: UP-FUJI MA60, manufactured by Shikoku Kako Co., Ltd., SLIM 200 ml setting), a brick type paper container (filling material: water shown in FIG. 1) ) Were continuously produced.
Example 2
 接着層(F層)を平均密度0.935g/cm3、ピーク融点100℃、MFR7.8のエチレン・アクリル酸共重合樹脂(EAA)(Dow Chemical Company社製、製品名:PRIMACOR3003)とした以外は、実施例1と同様にして多層紙容器用原紙2及び紙容器を作製した。
[実施例3]
The adhesive layer (F layer) is an ethylene / acrylic acid copolymer resin (EAA) (Made by Dow Chemical Company, product name: PRIMACOR 3003) having an average density of 0.935 g / cm 3 , peak melting point 100 ° C. and MFR 7.8. In the same manner as in Example 1, a multi-layer paper container base paper 2 and a paper container were produced.
[Example 3]
 LDPE層(A層)中にEAA樹脂(PRIMACOR3003)が5wt%となるように加えてLDPEを主成分とする層とした以外は、実施例2と同様にして多層紙容器用原紙3及び紙容器を作製した。
[実施例4]
Base paper 3 for a multilayer paper container and a paper container in the same manner as in Example 2 except that the LDPE layer (layer A) was added with an EAA resin (PRIMACOR 3003) to be 5 wt% and made a layer containing LDPE as a main component. Was produced.
Example 4
 L-LDPE層(D層)中にLDPE樹脂(LC602A)が10wt%となるように加えてL-LDPEを主成分とする層とした以外は、実施例3と同様にして多層紙容器用原紙4及び紙容器を作製した。
[実施例5~7]
Base paper for multi-layered paper containers in the same manner as in Example 3 except that L-LDPE was added to L-LDPE layer (D layer) so that 10 wt% of LDPE resin (LC602A) was added to make L-LDPE-based layer. 4 and a paper container were made.
[Examples 5 to 7]
 L-LDPE層(D層)中にLDPE樹脂(LC602A)がそれぞれ15wt%、25wt%、45wt%となるように加えてL-LDPEを主成分とする層とした以外は、実施例4と同様にして多層紙容器用原紙5~7及び紙容器を作製した。
[実施例8]
The same as Example 4 except that L-LDPE was used as the main layer by adding LDPE resin (LC602A) to L-LDPE layer (D layer) to be 15 wt%, 25 wt% and 45 wt%, respectively. Then, base papers 5 to 7 for multilayer paper containers and paper containers were produced.
[Example 8]
 L-LDPE層(E層)中にEAA樹脂(PRIMACOR3003)が5wt%となるように加えてL-LDPEを主成分とする層とした以外は実施例4と同様にして多層紙容器用原紙8及び紙容器を作成した。
[実施例9]
A base paper for a multilayer paper container 8 in the same manner as in Example 4 except that the L-LDPE layer (E layer) was added with an EAA resin (PRIMACOR 3003) in an amount of 5 wt% to make the layer mainly composed of L-LDPE. And made a paper container.
[Example 9]
 L-LDPE層(E層)を、LDPE樹脂(LC602A)95wt%、EAA樹脂(PRIMACOR3003)5wt%からなるLDPEを主成分とする層とした以外は、実施例3と同様にして多層紙容器用原紙9及び紙容器を作製した。
[実施例10~13]
For a multilayer paper container in the same manner as in Example 3 except that the L-LDPE layer (E layer) is a layer mainly composed of LDPE consisting of 95 wt% of LDPE resin (LC602A) and 5 wt% of EAA resin (PRIMACOR 3003) The base paper 9 and a paper container were produced.
[Examples 10 to 13]
 L-LDPE層(E層)を、LDPE樹脂(LC602A)95wt%、EAA樹脂(PRIMACOR3003)5wt%からなるLDPEを主成分とする層とした以外は、それぞれ実施例4~7と同様にして多層紙容器用原紙10~13及び紙容器を作製した。
[実施例14]
A multilayer was prepared in the same manner as in Examples 4 to 7 except that the L-LDPE layer (E layer) was a layer containing LDPE as a main component consisting of 95 wt% of LDPE resin (LC602A) and 5 wt% of EAA resin (PRIMACOR 3003). Base papers 10 to 13 for paper containers and paper containers were produced.
Example 14
 LDPEを主成分とする層(E層)とバリア層(C層)との間に、下記工程に従いEAA樹脂(PRIMACOR3003)からなる接着層(G層)を設けた以外は、実施例10と同様にして多層紙容器用原紙14及び紙容器を作製した。 Example 10 is the same as Example 10 except that an adhesive layer (G layer) made of an EAA resin (PRIMACOR 3003) is provided between the layer (E layer) containing LDPE as the main component and the barrier layer (C layer) according to the following steps. A multi-layered paper container base paper 14 and a paper container were produced.
<工程>
 次の3つの工程を連続してラミネーションすることにより、多層紙容器用原紙14を作製する。
第1工程:
  紙基材層(B層)に対してLDPEを主成分とする(E層)及び接着層(G層)を溶融押し出しすると共にバリア層(C層)を供給してラミネーションし、
第2工程:
  第1工程で得られた積層体のバリア層(C層)側にEAA層(F層)と、L-LDPEを主成分とする層(D層)とを溶融押し出しして接着層(F層)と熱可塑性樹脂層(D層)をラミネーションし、
第3工程:
  第2工程で得られた積層体の紙基材層(B層)側にLDPEを主成分とする層(A層)を溶融押し出しラミネーションする。
[実施例15]
<Process>
By sequentially laminating the following three steps, a base paper 14 for multilayer paper container is produced.
First step:
(E layer) and adhesive layer (G layer) mainly composed of LDPE are melt extruded to a paper base layer (B layer) and a barrier layer (C layer) is supplied for lamination,
Second step:
Adhesive layer (F layer) by melt-extruding the EAA layer (F layer) and the layer containing L-LDPE as the main component (D layer) on the barrier layer (C layer) side of the laminate obtained in the first step ) And thermoplastic resin layer (D layer),
Third step:
A layer (layer A) containing LDPE as a main component is melt extruded and laminated on the paper base layer (layer B) side of the laminate obtained in the second step.
[Example 15]
 L-LDPEを主成分とする層(D層)において、平均密度0.910g/cm3、ピーク融点124℃、MFR15のL-LDPE(Dow Chemical Company社製、製品名:ELITE5815)とした以外は、実施例14と同様にして多層紙容器用原紙15及び紙容器を作製した。
[実施例16]
The layer (D layer) containing L-LDPE as a main component has an average density of 0.910 g / cm 3 , a peak melting point of 124 ° C., and an MFR of 15 with L-LDPE (Dow Chemical Company, product name: ELITE 5815) In the same manner as in Example 14, a base paper 15 for multilayer paper containers and a paper container were produced.
[Example 16]
 L-LDPEを主成分とする層(D層)において、平均密度0.913g/cm3、ピーク融点121℃、MFR6.0のL-LDPEとした以外は、実施例14と同様にして多層紙容器用原紙16及び紙容器を作製した。
[実施例17]
A multilayer paper was prepared in the same manner as in Example 14 except that in the layer (D layer) containing L-LDPE as the main component, L-LDPE having an average density of 0.913 g / cm 3 , peak melting point of 121 ° C. and MFR 6.0 was used. Container base paper 16 and a paper container were produced.
[Example 17]
 LDPEを主成分とする層(E層)を、LDPE(LC602A)60wt%、L-LDPE(NH745N)40wt%からなる層とした以外は、実施例13と同様にして多層紙容器用原紙17及び紙容器を作製した。
[実施例18]
Base paper 17 for multilayer paper containers and multilayer paper container in the same manner as in Example 13 except that the layer containing LDPE as the main component (E layer) is a layer consisting of 60 wt% of LDPE (LC602A) and 40 wt% of L-LDPE (NH745N). A paper container was made.
[Example 18]
 LDPEを主成分とする層(A層)において、平均密度0.906g/cm3、ピーク融点102℃、MFR10.5のLDPE(日本ポリエチレン社製、製品名:KC507S)とした以外は、実施例14と同様にして多層紙容器用原紙18及び紙容器を作製した。
[実施例19]
Example except that in the layer (A layer) containing LDPE as the main component, LDPE (product name: KC507S, manufactured by Japan Polyethylene Corporation) having an average density of 0.906 g / cm 3 , a peak melting point of 102 ° C., and an MFR of 10.5. The same procedure as No. 14 was carried out to prepare a multilayer paper container base paper 18 and a paper container.
[Example 19]
 LDPEを主成分とする層(E層)において、平均密度0.906g/cm3、ピーク融点102℃、MFR10.5のLDPE(日本ポリエチレン社製、製品名:KC507S)とした以外は、実施例14と同様にして多層紙容器用原紙19及び紙容器を作製した。
[実施例20]
An example except that in the layer (E layer) containing LDPE as a main component, the average density is 0.906 g / cm 3 , peak melting point is 102 ° C., and MFR is 10.5 LDPE (product name: KC507S, manufactured by Japan Polyethylene Corporation). In the same manner as in 14, a base paper 19 for multilayer paper containers and a paper container were produced.
[Example 20]
 熱可塑性樹脂(D層)を平均密度0.921g/cm3、ピーク融点122℃、MFR12.0のL-LDPEとし、第2工程として、第1工程で得られた積層体のバリア層(C層)側にEMAA層(F層)、L-LDPE層(D層)を、それぞれ溶融押し出しして接着層(F層)と熱可塑性樹脂層(D層)をラミネーションした以外は、実施例1と同様にして多層紙容器用原紙20及び紙容器を作製した。
[実施例21]
The thermoplastic resin (D layer) is L-LDPE having an average density of 0.921 g / cm 3 , a peak melting point of 122 ° C., and an MFR of 12.0, and as the second step, the barrier layer (C of the laminate obtained in the first step) Example 1 except that the EMAA layer (F layer) and the L-LDPE layer (D layer) were melt-extruded on the layer side and the adhesive layer (F layer) and the thermoplastic resin layer (D layer) were laminated, respectively. In the same manner as in the above, a base paper 20 for multilayer paper containers and a paper container were produced.
[Example 21]
 熱可塑性樹脂(D層)を平均密度0.930g/cm3、ピーク融点123℃、MFR11.0のL-LDPEとし、第2工程として、第1工程で得られた積層体のバリア層(C層)側にEMAA層(F層)、L-LDPE層(D層)を、それぞれ溶融押し出しして接着層(F層)と熱可塑性樹脂層(D層)をラミネーションした以外は、実施例1と同様にして多層紙容器用原紙21及び紙容器を作製した。
[実施例22]
A thermoplastic resin (D layer) is L-LDPE having an average density of 0.930 g / cm 3 , a peak melting point of 123 ° C., and an MFR of 11.0, and as a second step, the barrier layer (C of the laminate obtained in the first step) Example 1 except that the EMAA layer (F layer) and the L-LDPE layer (D layer) were melt-extruded on the layer side and the adhesive layer (F layer) and the thermoplastic resin layer (D layer) were laminated, respectively. In the same manner as in the above, a base paper 21 for multilayer paper containers and a paper container were produced.
Example 22
 熱可塑性樹脂(D層)を平均密度0.937g/cm3、ピーク融点123℃、MFR11.0のL-LDPEとし、第2工程として、第1工程で得られた積層体のバリア層(C層)側にEMAA層(F層)、L-LDPE層(D層)を、それぞれ溶融押し出しして接着層(F層)と熱可塑性樹脂層(D層)をラミネーションした以外は、実施例1と同様にして多層紙容器用原紙22及び紙容器を作製した。
[実施例23]
A thermoplastic resin (D layer) is L-LDPE having an average density of 0.937 g / cm 3 , a peak melting point of 123 ° C., and an MFR of 11.0, and as a second step, the barrier layer (C of the laminate obtained in the first step) Example 1 except that the EMAA layer (F layer) and the L-LDPE layer (D layer) were melt-extruded on the layer side and the adhesive layer (F layer) and the thermoplastic resin layer (D layer) were laminated, respectively. In the same manner as in the above, a base paper 22 for multilayer paper containers and a paper container were produced.
[Example 23]
 熱可塑性樹脂(D層)を平均密度0.901g/cm3、ピーク融点112℃、MFR8.0のL-LDPEとし、第2工程として、第1工程で得られた積層体のバリア層(C層)側にEMAA層(F層)、L-LDPE層(D層)を、それぞれ溶融押し出しして接着層(F層)と熱可塑性樹脂層(D層)をラミネーションした以外は、実施例1と同様にして多層紙容器用原紙23及び紙容器を作製した。 A thermoplastic resin (D layer) is L-LDPE having an average density of 0.901 g / cm 3 , a peak melting point of 112 ° C., and an MFR of 8.0, and as a second step, a barrier layer of the laminate obtained in the first step (C Example 1 except that the EMAA layer (F layer) and the L-LDPE layer (D layer) were melt-extruded on the layer side and the adhesive layer (F layer) and the thermoplastic resin layer (D layer) were laminated, respectively. In the same manner as in the above, a base paper 23 for multilayer paper containers and a paper container were produced.
比較例1Comparative Example 1
 接着層(F層)及び熱可塑性樹脂(D層)を平均密度0.930g/cm3、ピーク融点123℃、MFR11.0のL-LDPEとし、第2工程として、第1工程で得られた積層体のバリア層(C層)側にL-LDPE層(F層)及びL-LDPE層(D層)を、それぞれ溶融押し出しして接着層(F層)と熱可塑性樹脂層(D層)をラミネーションした以外は、実施例1と同様にして多層紙容器用原紙24及び紙容器を作製した。 The adhesive layer (F layer) and the thermoplastic resin (D layer) were made L-LDPE having an average density of 0.930 g / cm 3 , a peak melting point of 123 ° C., and an MFR of 11.0, and were obtained in the first step as the second step. The L-LDPE layer (F layer) and the L-LDPE layer (D layer) are respectively melt-extruded on the barrier layer (C layer) side of the laminate to form an adhesive layer (F layer) and a thermoplastic resin layer (D layer) A multilayer paper container base paper 24 and a paper container were produced in the same manner as in Example 1 except that the above were laminated.
比較例2Comparative example 2
 熱可塑性樹脂(D層)を平均密度0.928g/cm3、ピーク融点114℃、MFR3.0のLDPE(日本ポリエチレン社製、製品名:LC561)とし、第2工程として、第1工程で得られた積層体のバリア層(C層)側にEMAA層(F層)、LDPE層(D層)を、それぞれ溶融押し出しして接着層(F層)と熱可塑性樹脂層(D層)をラミネーションした以外は、実施例1と同様にして多層紙容器用原紙25及び紙容器を作製した。 Thermoplastic resin (D layer) was used as LDPE with an average density of 0.928 g / cm 3 , peak melting point of 114 ° C., and MFR 3.0 (product name: LC561 manufactured by Japan Polyethylene Corporation), obtained as the second step in the first step Each of the EMAA layer (F layer) and the LDPE layer (D layer) is melt-extruded on the barrier layer (C layer) side of the laminated body, and the adhesive layer (F layer) and the thermoplastic resin layer (D layer) are laminated. In the same manner as in Example 1 except for the above, a base paper 25 for multilayer paper containers and a paper container were produced.
比較例3Comparative example 3
 熱可塑性樹脂(D層)を平均密度0.917g/cm3、ピーク融点106℃、MFR8.0のLDPE(日本ポリエチレン社製、製品名:M201P)とし、第2工程として、第1工程で得られた積層体のバリア層(C層)側にEMAA層(F層)、LDPE層(D層)を、それぞれ溶融押し出しして接着層(F層)と熱可塑性樹脂層(D層)をラミネーションした以外は、実施例1と同様にして多層紙容器用原紙26及び紙容器を作製した。 Thermoplastic resin (D layer) was made into LDPE (Made in Japan, product name: M201P) with an average density of 0.917 g / cm 3 , peak melting point of 106 ° C. and MFR 8.0, obtained as the second step in the first step Each of the EMAA layer (F layer) and the LDPE layer (D layer) is melt-extruded on the barrier layer (C layer) side of the laminated body, and the adhesive layer (F layer) and the thermoplastic resin layer (D layer) are laminated. A multilayer paper base paper 26 and a paper container were produced in the same manner as in Example 1 except for the above.
比較例4Comparative example 4
 L-LDPE層(E層)中に、LDPE樹脂(LC602A)が55wt%となるように加えた以外は、実施例3と同様にして多層紙容器用原紙27及び紙容器を作製した。 A multilayer paper base paper 27 and a paper container were produced in the same manner as in Example 3 except that 55 wt% of LDPE resin (LC602A) was added to the L-LDPE layer (E layer).
比較例5Comparative example 5
 L-LDPE層(E層)中に、LDPE樹脂(LC602A)が75wt%となるように加えた以外は、実施例3と同様にして多層紙容器用原紙28及び紙容器を作製した。 A base paper 28 for a multilayer paper container and a paper container were produced in the same manner as in Example 3 except that 75 wt% of LDPE resin (LC602A) was added to the L-LDPE layer (E layer).
 実施例及び比較例で作成した多層紙容器用原紙の各層の樹脂、及びD層の物性を表1、2に示す。 The physical properties of the resin and the layer D of each layer of the base paper for multilayer paper containers prepared in Examples and Comparative Examples are shown in Tables 1 and 2.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
 実施例及び比較例で作成した紙容器を使用して、ピンホール耐性試験、C層/F層間の接着性試験、横シール部(D層/D層間)の接着性試験を行って、容器の評価を行った。 Using the paper containers prepared in Examples and Comparative Examples, pinhole resistance test, adhesion test between C / F layers, adhesion test of transverse seal portion (D / D layers) were carried out, and I made an evaluation.
<ピンホール耐性試験>
(A:容器内面)
 充填物(水)を入れたまま、90℃の湯中で40分間加熱(ボイル)した紙容器を胴部中央で横方向に2つに切り割り、容器の内部に水を満たす。これを水中に浸し、通電チェッカー(信光電気計装株式会社製:ピンホールチェッカー HV-M)を使用して容器の内面と外面の間に1kVで通電させ、通電反応の有無を確認する。
 通電方式によるピンホール試験の概略図を図4に示す。図4(a)に示すように、容器内面の接着層(F層)及び熱可塑性樹脂層(D層)にピンホールが発生していない場合は、通電層であるバリア層(C層)のアルミ箔は電気的には絶縁状態であるので通電しない。一方、ピンホールが発生している場合は、図4(b)に示すように、ピンホールを経由して、内側の液体(水)→ピンホール→アルミ箔→アルミ箔の端面→外側の液体(水)の順に電気が流れ、通電が検知される。
<Pinhole resistance test>
(A: container inner surface)
A paper container heated (boiled) in hot water at 90 ° C. for 40 minutes with filling material (water) cut into two in the lateral direction at the center of the body, and the inside of the container is filled with water. This is immersed in water, and it is energized at 1 kV between the inner surface and the outer surface of the container using an energizing checker (Pinhole checker HV-M, manufactured by Shinko Electric Instruments Co., Ltd.), and the presence or absence of an electrification reaction is confirmed.
A schematic diagram of a pinhole test according to the energization method is shown in FIG. As shown in FIG. 4 (a), when no pinholes are generated in the adhesive layer (F layer) and the thermoplastic resin layer (D layer) on the inner surface of the container, the barrier layer (C layer) which is a conductive layer Since the aluminum foil is electrically insulated, it is not energized. On the other hand, when a pinhole is generated, as shown in FIG. 4 (b), the inner liquid (water) → pinhole → aluminum foil → end face of aluminum foil → outside liquid via the pinhole Electricity flows in the order of (water), and energization is detected.
(B:容器外面)
 通電反応があった場合は、更に容器の外面をレッド浸透液(赤染料を添加した水)に浸して、紙基材(B層)の染色の有無を確認する。容器外面の熱可塑性樹脂層(A層)にピンホールが発生していると、ピンホールからレッド浸透液が浸透し、紙基材(B層)が染色される。
(B: container outer surface)
If there is an electrification reaction, the outer surface of the container is further dipped in a red penetrant (water to which a red dye is added) to confirm the presence or absence of staining of the paper substrate (B layer). When a pinhole is generated in the thermoplastic resin layer (layer A) on the outer surface of the container, the red penetrant is permeated from the pinhole and the paper substrate (layer B) is dyed.
 評価基準は次のとおりとする。
 評価5:紙容器500個(測定サンプル1000個)において、容器内面
     、外面共にピンホールが発生していない(容器内面にピンホール
     がある=通電反応のある紙容器が0個)。
 評価4:紙容器500個(測定サンプル1000個)において、極少量の
     容器内面にはピンホールが発生しているが、容器外面にはピンホ
     ールが発生していない(容器内面にピンホールがある紙容器が1
     000個中1個以上5個未満、容器外面にピンホールがある=紙
     基材(B層)が染色された紙容器が0個)。
 評価3:紙容器500個(測定サンプル1000個)において、少量の容
     器内面にはピンホールが発生しているが、容器外面にはピンホー
     ルが発生していない(容器内面にピンホールがある紙容器が10
     00個中5個以上10個未満、容器外面にピンホールがある=紙
     基材(B層)が染色された紙容器が0個)。
 評価2:紙容器500個(測定サンプル1000個)において、容器内面
     にはピンホールが発生しているが、容器外面にはピンホールが発
     生していない(容器内面にピンホールがある紙容器が1000個
     中10個以上、容器外面にピンホールがある=紙基材(B層)が
     染色された紙容器が0個)。
 評価1:紙容器500個(測定サンプル1000個)において、容器外面
     にもピンホールが発生している(容器外面にピンホールがある=
     紙基材(B層)が染色された紙容器が1個以上)。
Evaluation criteria are as follows.
Evaluation 5: In 500 paper containers (1000 measurement samples), no pinhole is generated on both the inner surface and the outer surface of the container (a pinhole is present on the inner surface of the container = no paper container having an electric reaction).
Evaluation 4: In 500 paper containers (1000 measurement samples), although pinholes are generated on the inner surface of a very small amount of container, pinholes are not generated on the outer surface of the container (pin holes are formed on the inner surface of the container) One paper container is 1
1 or more and less than 5 out of 000, and there are pinholes on the outer surface of the container = 0 paper containers on which a paper base (layer B) is dyed).
Evaluation 3: In 500 paper containers (1000 measurement samples), although a pinhole is generated on the inner surface of a small amount of containers, no pinhole is generated on the outer surface of the container (a pinhole is formed on the inner surface of the container) 10 paper containers
There are 5 or more and less than 10 in 00, and there are pinholes on the outer surface of the container = 0 paper containers on which the paper base (layer B) is dyed).
Evaluation 2: In 500 paper containers (1000 measurement samples), although a pinhole is generated on the inner surface of the container, no pinhole is generated on the outer surface of the container (a paper container having a pinhole on the inner surface of the container) There are 10 or more out of 1000, and there are pinholes on the outer surface of the container = 0 paper containers (layer B) are dyed).
Evaluation 1: In 500 paper containers (1000 measurement samples), pinholes are also generated on the outer surface of the container (there is pinhole on the outer surface of the container =
One or more paper containers on which a paper substrate (layer B) is dyed).
<C層/F層間の接着性試験>
 バリア層(C層)と接着層(F層)の界面にカミソリで切れ目を入れ、そこに手を掛け引き剥がし、C層とF層の間の接着性を評価した。
 評価基準は次のとおりとする。
 OK:C層とF層の界面で剥がれない。
 NG:C層とF層の界面で剥がれる。
<Adhesion test between C layer and F layer>
The interface between the barrier layer (C layer) and the adhesive layer (F layer) was nicked with a razor, hand-hooked there and peeled off, and the adhesion between the C layer and the F layer was evaluated.
Evaluation criteria are as follows.
OK: It does not peel off at the interface of C layer and F layer.
NG: Peeling off at the interface between the C layer and the F layer.
<横シール部(D層/D層間)の接着性試験>
 充填物(水)を入れたまま、90℃の湯中で40分間加熱(ボイル)した紙容器の横シール部(図1のNo.19の箇所:容器内面の熱可塑性樹脂層(D層)同士の接着部)の界面にカミソリで切れ目を入れ、そこに手を掛け引き剥がし、横シール部の接着性を評価した。
 横シールは紙容器を形成するために必須の要素であるため、横シールが剥がれないことを確認する必要がある。
 評価基準は次のとおりとする。
 評価3:横シール部(D層とD層の界面)で剥がれない。
 評価2:横シール部(D層とD層の界面)では剥がれないが、接着層(F
     層)と熱可塑性樹脂層(D層)の界面で剥がれる。
 評価1:横シール部(D層とD層の界面)で剥がれる。
<Adhesiveness test of horizontal seal part (D layer / D layer)>
Horizontal seal of a paper container heated (boiled) in hot water at 90 ° C for 40 minutes with the filler (water) in place (location No. 19 in Fig. 1: thermoplastic resin layer (D layer) on the inner surface of the container) A razor cut was made in the interface between the bonding parts), and the hand was pulled off and peeled off to evaluate the adhesion of the lateral sealing part.
Since the transverse seal is an essential element for forming a paper container, it is necessary to confirm that the transverse seal does not peel off.
Evaluation criteria are as follows.
Evaluation 3: It does not peel off at the horizontal seal portion (the interface between the D layer and the D layer).
Evaluation 2: Although it does not peel off at the transverse seal portion (the interface between the D layer and the D layer), the adhesive layer (F
(Layer) and the thermoplastic resin layer (layer D) peel off.
Evaluation 1: Peeling off at the transverse seal portion (the interface between the D layer and the D layer).
 実施例及び比較例で作成した紙容器の評価結果を表3に示す。

Table 3 shows the evaluation results of the paper containers prepared in the example and the comparative example.

Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
 表3の試験結果において、評価1、もしくはNGがあるものは、本発明の多層紙容器として適していないと判断される。
 評価2以上、かつOK以上を使用可能な多層紙容器と判断して実施例とし、実施例の中でピンホール耐性を優先して全体評価をした結果、実施例1~5、8~11、14~19、20、21、22が特に優れた多層紙容器である。さらに実施例1~4、8~10、14、17、20の条件は、ピンホール耐性、バリア層(C層)のアルミ箔よりも容器内面側の層間の接着性、容器の横シール部の接着性(ヒートシール性)のいずれにも優れた結果となっている。
 容器内面と外面の両方にピンホールが発生すると、外気が容器内部に侵入して内容物である飲食品の変質、腐敗などにつながる、あるいは、内容物が容器外部に染み出して汚損や悪臭などにつながる。また、容器内面のみにピンホールが発生した場合でも、バリア層(C層)のアルミ箔と内容物が接触することとなり、特に酸性、アルカリ性が強いなど、内容物の種類によってはアルミ箔が腐食され、容器全体の劣化につながる可能性がある。このように、ピンホール耐性は容器としての本来的な物性に関わる要素であるため、重要な評価要素とした。
 横シール部の接着性試験は、90℃40分間の湯中加熱試験であるので、本発明の多層紙容器は、低温長時間殺菌に十分に耐え得るヒートシール性を有していることを示している。
 本発明の多層紙容器は、接着層(F層)をE(M)AA、熱可塑性樹脂層(D層)をL-LDPEを主成分とする層の組み合わせとすることにより、バリア層(C層)のアルミ箔よりも容器内面側の層間において十分な接着強度を発揮することが確認できた。
 本試験によって、低温長時間殺菌可能な紙容器構成を開発することができ、各層を構成する熱可塑性樹脂の組み合わせによって、連続して押し出しラミネーションを行い、多層紙容器用の原紙を製造できることが確認できた。
In the test results in Table 3, those with Evaluation 1 or NG are judged not to be suitable as the multilayer paper container of the present invention.
Evaluations of 2 or more, and OK or more are judged as usable multilayer paper containers, and are taken as examples. In the examples, the pinhole resistance is given priority and overall evaluation results show Examples 1 to 5, 8 to 11, 14-19, 20, 21, 22 are particularly good multilayer paper containers. Furthermore, the conditions of Examples 1 to 4, 8 to 10, 14, 17 and 20 are pinhole resistance, adhesion between the inner layer side of the barrier layer (C layer) and the inner surface of the container than the aluminum foil, and lateral seal of the container. The results are excellent for both adhesion (heat sealability).
If pinholes occur on both the inside and outside of the container, the outside air intrudes into the inside of the container and leads to deterioration and decay of the food and drink that are the contents, or the contents exude to the outside of the container and cause staining and odor Lead to In addition, even if pinholes occur only on the inner surface of the container, the aluminum foil of the barrier layer (C layer) and the contents come into contact, and depending on the type of contents, the aluminum foil is corroded. May lead to the deterioration of the entire container. Thus, since pinhole resistance is an element related to the intrinsic physical properties of the container, it was an important evaluation element.
Since the adhesion test of the transverse seal portion is a heating test in water at 90 ° C. for 40 minutes, it is shown that the multilayer paper container of the present invention has a heat sealability sufficiently resistant to sterilization at low temperatures for a long time ing.
The multilayer paper container of the present invention is a combination of the adhesive layer (F layer) with E (M) AA and the thermoplastic resin layer (D layer) with L-LDPE as a main component. It has been confirmed that sufficient adhesive strength is exhibited between the layers on the inner surface side of the container rather than the aluminum foil of the layer).
By this test, a paper container configuration that can be sterilized at low temperature for a long time can be developed, and it is confirmed that extrusion lamination can be continuously performed by combination of thermoplastic resins constituting each layer to manufacture base paper for multilayer paper containers. did it.

Claims (10)

  1.  外表面側から内表面側にかけて、少なくとも熱可塑性樹脂層(A層)、紙基材層(B層)、熱可塑性樹脂層(E層)、バリア層(C層)、接着層(F層)、熱可塑性樹脂層(D層)を備えた多層紙容器であって、
     A層が低密度ポリエチレン樹脂(LDPE)を、F層がエチレン・(メタ)アクリル酸共重合樹脂(E(M)AA)を、D層及びE層が直鎖状低密度ポリエチレン樹脂(L-LDPE)を、それぞれ主成分とすることを特徴とする多層紙容器。
    From the outer surface side to the inner surface side, at least the thermoplastic resin layer (A layer), the paper base layer (B layer), the thermoplastic resin layer (E layer), the barrier layer (C layer), the adhesive layer (F layer) A multilayer paper container provided with a thermoplastic resin layer (D layer),
    A layer is low density polyethylene resin (LDPE), F layer is ethylene / (meth) acrylic acid copolymer resin (E (M) AA), D layer and E layer are linear low density polyethylene resin (L- A multilayer paper container characterized in that each of LDPE) is a main component.
  2.  A層に用いられる低密度ポリエチレン樹脂(LDPE)が、0.910~0.930g/cm3の平均密度、105~125℃のピーク融点であり、
     D層に用いられる直鎖状低密度ポリエチレン樹脂(L-LDPE)が、0.905~0.935g/cm3の平均密度、100~125℃のピーク融点であり、E層に用いられる直鎖状低密度ポリエチレン樹脂(L-LDPE)が、0.905~0.935g/cm3の平均密度、105~125℃のピーク融点であり、D層及びE層に用いられる直鎖状低密度ポリエチレン樹脂(L-LDPE)が2.0~16.0g/10分のメルトフローレート(MFR)であることを特徴とする請求項1記載の多層紙容器。
    The low density polyethylene resin (LDPE) used for the layer A has an average density of 0.910 to 0.930 g / cm 3 , a peak melting point of 105 to 125 ° C.,
    The linear low density polyethylene resin (L-LDPE) used for the D layer has an average density of 0.905 to 0.935 g / cm 3 , a peak melting point of 100 to 125 ° C., and a linear chain used for the E layer Low density polyethylene resin (L-LDPE) has an average density of 0.905 to 0.935 g / cm 3 , peak melting point of 105 to 125 ° C., and linear low density polyethylene used for D layer and E layer The multilayer paper container according to claim 1, wherein the resin (L-LDPE) is a melt flow rate (MFR) of 2.0 to 16.0 g / 10 min.
  3.  A層、E層、F層、D層は、押出しラミネーション法により形成されていることを特徴とする請求項1又は2記載の多層紙容器。 The multilayer paper container according to claim 1 or 2, wherein the layer A, the layer E, the layer F, and the layer D are formed by an extrusion lamination method.
  4.  レンガ状容器であることを特徴とする請求項1~3のいずれかに記載の多層紙容器。 The multilayer paper container according to any one of claims 1 to 3, which is a brick-like container.
  5.  飲食料を容器に充填した後、90~95℃に加熱処理されることを特徴とする請求項1~4のいずれかに記載の多層紙容器。 The multi-layered paper container according to any one of claims 1 to 4, which is heat-treated to 90 to 95 属 C after filling the container with the food and drink.
  6.  飲食料が豆腐であることを特徴とする請求項5記載の多層紙容器。 The multi-layered paper container according to claim 5, wherein the food and drink is tofu.
  7.  外表面側から内表面側にかけて、少なくとも熱可塑性樹脂層(A層)、紙基材層(B層)、熱可塑性樹脂層(E層)、バリア層(C層)、接着層(F層)、熱可塑性樹脂層(D層)を備えた多層紙容器用原紙を製造する方法であって、
    第1工程として、紙基材層(B層)に対して直鎖状低密度ポリエチレン樹脂(L-LDPE)を主成分とする層(E層)を溶融押し出しすると共にバリア層(C層)を供給してラミネーションし、
    第2工程として、第1工程で得られた積層体のバリア層(C層)側にエチレン・(メタ)アクリル酸共重合樹脂(E(M)AA)を主成分とする層(F層)と直鎖状低密度ポリエチレン樹脂(L-LDPE)を主成分とする層(D層)とを溶融押し出しして接着層(F層)と熱可塑性樹脂層(D層)をラミネーションし、
    第3工程として、第2工程で得られた積層体の紙基材層(B層)側に低密度ポリエチレン樹脂(LDPE)を主成分とする層(A層)を溶融押し出しラミネーションする、
    上記3つの工程を連続してラミネーションすることを特徴とする多層紙容器用原紙を製造する方法。
    From the outer surface side to the inner surface side, at least the thermoplastic resin layer (A layer), the paper base layer (B layer), the thermoplastic resin layer (E layer), the barrier layer (C layer), the adhesive layer (F layer) A method for producing a multi-layered paper container base paper provided with a thermoplastic resin layer (D layer),
    As a first step, a layer (E layer) containing a linear low density polyethylene resin (L-LDPE) as a main component is melted and extruded to a paper base layer (B layer) and a barrier layer (C layer) is formed. Supply and laminate,
    As a second step, a layer (F layer) containing ethylene / (meth) acrylic acid copolymer resin (E (M) AA) as a main component on the barrier layer (C layer) side of the laminate obtained in the first step And melt extruding a layer (D layer) mainly composed of a linear low density polyethylene resin (L-LDPE) and laminating an adhesive layer (F layer) and a thermoplastic resin layer (D layer),
    As the third step, the layer (A layer) mainly composed of low density polyethylene resin (LDPE) is melt extruded and laminated on the paper base layer (B layer) side of the laminate obtained in the second step.
    A method of producing a base paper for a multilayer paper container, which comprises continuously laminating the above three steps.
  8.  外表面側から内表面側にかけて、少なくとも熱可塑性樹脂層(A層)、紙基材層(B層)、熱可塑性樹脂層(E層)、バリア層(C層)、接着層(F層)、熱可塑性樹脂層(D層)を備えた多層紙容器であって、
     A層及びE層が低密度ポリエチレン樹脂(LDPE)を、F層がエチレン・(メタ)アクリル酸共重合樹脂(E(M)AA)を、D層が直鎖状低密度ポリエチレン樹脂(L-LDPE)を、それぞれ主成分とすることを特徴とする多層紙容器。
    From the outer surface side to the inner surface side, at least the thermoplastic resin layer (A layer), the paper base layer (B layer), the thermoplastic resin layer (E layer), the barrier layer (C layer), the adhesive layer (F layer) A multilayer paper container provided with a thermoplastic resin layer (D layer),
    A layer and E layer are low density polyethylene resin (LDPE), F layer is ethylene / (meth) acrylic acid copolymer resin (E (M) AA), D layer is linear low density polyethylene resin (L- A multilayer paper container characterized in that each of LDPE) is a main component.
  9.  A層及びE層に用いられる低密度ポリエチレン樹脂(LDPE)が、0.910~0.930g/cm3の平均密度、105~125℃のピーク融点であり、
     D層に用いられる直鎖状低密度ポリエチレン樹脂(L-LDPE)が、0.905~0.935g/cm3の平均密度、100~125℃のピーク融点であり、D層に用いられる直鎖状低密度ポリエチレン樹脂(L-LDPE)及びE層に用いられる低密度ポリエチレン樹脂(LDPE)が2.0~16.0g/10分のメルトフローレート(MFR)であることを特徴とする請求項8記載の多層紙容器。
    The low density polyethylene resin (LDPE) used in layers A and E has an average density of 0.910 to 0.930 g / cm 3 and a peak melting point of 105 to 125 ° C.
    The linear low density polyethylene resin (L-LDPE) used for the D layer has an average density of 0.905 to 0.935 g / cm 3 , a peak melting point of 100 to 125 ° C., and the linear chain used for the D layer Low density polyethylene resin (L-LDPE) and low density polyethylene resin (LDPE) used for the E layer have a melt flow rate (MFR) of 2.0 to 16.0 g / 10 min. The multi-layered paper container according to 8.
  10.  外表面側から内表面側にかけて、少なくとも熱可塑性樹脂層(A層)、紙基材層(B層)、熱可塑性樹脂層(E層)、バリア層(C層)、接着層(F層)、熱可塑性樹脂層(D層)を備えた多層紙容器用原紙を製造する方法であって、
    第1工程として、紙基材層(B層)に対して低密度ポリエチレン樹脂(LDPE)を主成分とする層(E層)を溶融押し出しすると共にバリア層(C層)を供給してラミネーションし、
    第2工程として、第1工程で得られた積層体のバリア層(C層)側にエチレン・(メタ)アクリル酸共重合樹脂(E(M)AA)を主成分とする層(F層)と直鎖状低密度ポリエチレン樹脂(L-LDPE)を主成分とする層(D層)とを溶融押し出しして接着層(F層)と熱可塑性樹脂層(D層)をラミネーションし、
    第3工程として、第2工程で得られた積層体の紙基材層(B層)側に低密度ポリエチレン樹脂(LDPE)を主成分とする層(A層)を溶融押し出しラミネーションする、
    上記3つの工程を連続してラミネーションすることを特徴とする多層紙容器用原紙を製造する方法。
    From the outer surface side to the inner surface side, at least the thermoplastic resin layer (A layer), the paper base layer (B layer), the thermoplastic resin layer (E layer), the barrier layer (C layer), the adhesive layer (F layer) A method for producing a multi-layered paper container base paper provided with a thermoplastic resin layer (D layer),
    As the first step, the layer (E layer) mainly composed of low density polyethylene resin (LDPE) is melt extruded to the paper base layer (B layer) and the barrier layer (C layer) is supplied to perform lamination. ,
    As a second step, a layer (F layer) containing ethylene / (meth) acrylic acid copolymer resin (E (M) AA) as a main component on the barrier layer (C layer) side of the laminate obtained in the first step And melt extruding a layer (D layer) mainly composed of a linear low density polyethylene resin (L-LDPE) and laminating an adhesive layer (F layer) and a thermoplastic resin layer (D layer),
    As the third step, the layer (A layer) mainly composed of low density polyethylene resin (LDPE) is melt extruded and laminated on the paper base layer (B layer) side of the laminate obtained in the second step.
    A method of producing a base paper for a multilayer paper container, which comprises continuously laminating the above three steps.
PCT/JP2013/071344 2012-08-10 2013-08-07 Multilayered paper container WO2014024913A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201380028020.3A CN104334459B (en) 2012-08-10 2013-08-07 Multi-ply paper container
JP2014529528A JPWO2014024913A1 (en) 2012-08-10 2013-08-07 Multi-layer paper container
KR20147032674A KR20150042745A (en) 2012-08-10 2013-08-07 Multilayered paper container
HK15104709.7A HK1203915A1 (en) 2012-08-10 2015-05-18 Multilayered paper container

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012-178274 2012-08-10
JP2012178274 2012-08-10

Publications (1)

Publication Number Publication Date
WO2014024913A1 true WO2014024913A1 (en) 2014-02-13

Family

ID=50068136

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/071344 WO2014024913A1 (en) 2012-08-10 2013-08-07 Multilayered paper container

Country Status (5)

Country Link
JP (1) JPWO2014024913A1 (en)
KR (1) KR20150042745A (en)
CN (1) CN104334459B (en)
HK (1) HK1203915A1 (en)
WO (1) WO2014024913A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016023993A1 (en) * 2014-08-14 2016-02-18 Tetra Laval Holdings & Finance S.A. Packaging laminate, method for producing same, and packaging container produced from the packaging laminate
JP2017024762A (en) * 2015-07-24 2017-02-02 日本製紙株式会社 Paper container for packed food
JP2020521656A (en) * 2017-05-31 2020-07-27 テトラ ラバル ホールディングス アンド ファイナンス エス エイ Laminated packaging materials, packaging containers made therefrom, and methods for making laminated materials
WO2021166919A1 (en) * 2020-02-17 2021-08-26 日本製紙株式会社 Paper container for packed food
JP2022500640A (en) * 2018-09-12 2022-01-04 クロマティック テクノロジーズ インコーポレイテッドChromatic Technologies, Inc. High pressure processing pressure sensor

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6264359B2 (en) * 2015-11-24 2018-01-24 ダイニック株式会社 Lid material
CN109130333A (en) * 2017-06-16 2019-01-04 深圳市云罐科技有限公司 A kind of paper can production method
CN109130353A (en) * 2017-06-18 2019-01-04 深圳市云罐科技有限公司 A kind of composite can made of paper and iron sheet processing method
KR102091344B1 (en) 2019-01-21 2020-03-19 류길수 Multilayer sheet for radiation shielding and adhesive special paper comprising the same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002205363A (en) * 2000-11-09 2002-07-23 Nihon Tetra Pak Kk Laminate for packaging material
JP2002264936A (en) * 1999-01-29 2002-09-18 Nihon Tetra Pak Kk Paper packaging container
JP2005524585A (en) * 2002-05-07 2005-08-18 テトラ ラバル ホールデイングス エ フイナンス ソシエテ アノニム Packaging laminate, method for producing the same, and packaging container produced from the packaging laminate
JP2007253993A (en) * 2006-03-23 2007-10-04 Japan Polypropylene Corp Easily peelable heat-sealed article, and its manufacturing method

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU584276B2 (en) * 1986-02-27 1989-05-18 Dow Chemical Company, The Blends of vinylidene chloride copolymers and olefin copolymers and films produced therefrom
JP3037622B2 (en) * 1995-11-27 2000-04-24 日本製紙株式会社 Easily openable paper container
JP4727782B2 (en) * 1999-12-13 2011-07-20 大日本印刷株式会社 Liquid paper container
US20050037162A1 (en) * 2003-08-11 2005-02-17 Adams John Peter Paperboard laminate for food packaging applications
US20070264468A1 (en) * 2004-11-29 2007-11-15 Avery Dennison Corporation Coextruded Multilayer Colored Films
FI123071B (en) * 2006-07-28 2012-10-31 Stora Enso Oyj Use of ethylene methyl acrylate copolymer to reduce the absorption of D-limonene from citrus juice
US20080163978A1 (en) * 2007-01-09 2008-07-10 Botros Maged G Process for producing multi-layer structures having improved metal adhesion
JP4790762B2 (en) * 2008-06-18 2011-10-12 大王製紙株式会社 Food packaging material using sheets
JP5563557B2 (en) * 2009-03-31 2014-07-30 日本製紙株式会社 Base paper for paper container and laminated sheet for paper container using the same
CN102686489B (en) * 2009-07-24 2015-11-25 陶氏环球技术有限责任公司 Case, its preparation method of coating

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002264936A (en) * 1999-01-29 2002-09-18 Nihon Tetra Pak Kk Paper packaging container
JP2002205363A (en) * 2000-11-09 2002-07-23 Nihon Tetra Pak Kk Laminate for packaging material
JP2005524585A (en) * 2002-05-07 2005-08-18 テトラ ラバル ホールデイングス エ フイナンス ソシエテ アノニム Packaging laminate, method for producing the same, and packaging container produced from the packaging laminate
JP2007253993A (en) * 2006-03-23 2007-10-04 Japan Polypropylene Corp Easily peelable heat-sealed article, and its manufacturing method

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016023993A1 (en) * 2014-08-14 2016-02-18 Tetra Laval Holdings & Finance S.A. Packaging laminate, method for producing same, and packaging container produced from the packaging laminate
CN106660315A (en) * 2014-08-14 2017-05-10 利乐拉瓦尔集团及财务有限公司 Packaging laminate, method for producing same, and packaging container produced from the packaging laminate
JP2017524620A (en) * 2014-08-14 2017-08-31 テトラ ラバル ホールディングス アンド ファイナンス エス エイ Laminate for packaging, method for producing it, and packaging container produced from the laminate for packaging
RU2693757C2 (en) * 2014-08-14 2019-07-04 Тетра Лаваль Холдингз Энд Файнэнс С.А. Packaging laminated material, method for production thereof and packaging container produced from laminated packaging material
JP2017024762A (en) * 2015-07-24 2017-02-02 日本製紙株式会社 Paper container for packed food
WO2017018026A1 (en) * 2015-07-24 2017-02-02 日本製紙株式会社 Paper container for packaged foods
JP2020521656A (en) * 2017-05-31 2020-07-27 テトラ ラバル ホールディングス アンド ファイナンス エス エイ Laminated packaging materials, packaging containers made therefrom, and methods for making laminated materials
JP7109481B2 (en) 2017-05-31 2022-07-29 テトラ ラバル ホールディングス アンド ファイナンス エス エイ Laminated packaging material, packaging container made therefrom, and method for producing laminated material
JP2022500640A (en) * 2018-09-12 2022-01-04 クロマティック テクノロジーズ インコーポレイテッドChromatic Technologies, Inc. High pressure processing pressure sensor
JP7260633B2 (en) 2018-09-12 2023-04-18 クロマティック テクノロジーズ インコーポレイテッド High pressure processing pressure sensor
WO2021166919A1 (en) * 2020-02-17 2021-08-26 日本製紙株式会社 Paper container for packed food
JP2021127172A (en) * 2020-02-17 2021-09-02 日本製紙株式会社 Paper container for packed food
JP7075424B2 (en) 2020-02-17 2022-05-25 日本製紙株式会社 Filled food paper container

Also Published As

Publication number Publication date
CN104334459B (en) 2018-02-02
CN104334459A (en) 2015-02-04
KR20150042745A (en) 2015-04-21
HK1203915A1 (en) 2015-11-06
JPWO2014024913A1 (en) 2016-07-25

Similar Documents

Publication Publication Date Title
WO2014024913A1 (en) Multilayered paper container
JP4424716B2 (en) Manufacturing method of laminate for packaging material and laminate for packaging material
JP5615366B2 (en) Thermo-mechanically stable and heat-sealable barrier coat thin film, packaging laminate comprising the thin film, packaging container formed from the packaging laminate, and method for producing the thin film
US4977004A (en) Barrier structure for food packages
US4981739A (en) Oxygen impermeable leak free container
US4921733A (en) Oxygen impermeable leak free container
US4894267A (en) Blow-molded plastic bottle with barrier structure for food packages
US11167534B2 (en) Polymer barrier liminate tube for container
JP6620438B2 (en) Low adsorptive coextrusion multilayer sealant film
WO2002074537A1 (en) Coextruded retortable multilayer film
AU2002248623A1 (en) Coextruded retortable multilayer film
JP6737772B2 (en) Packaging laminate, method for producing the same, and packaging container produced from the packaging laminate
US20190077132A1 (en) Laminated packaging material comprising a barrier film and packaging containers manufactured therefrom
EP1620259B1 (en) Nylon barrier board structure
JP2004509030A (en) Packaging laminates and packaging containers made therefrom
JP6146086B2 (en) Paper base sheet for half clear pack and half clear pack
KR20050088082A (en) Laminate and, paper container and package using the same
TW200305508A (en) Non-foil barrier laminates
JP2005528236A (en) Composite materials for heat-sealable packages that are impermeable to light, gases and liquids
JP6318737B2 (en) Food packaging film for boil processing, bottom material for deep-drawn package, and deep-drawn package
JP5751031B2 (en) Packaging material and paper container comprising the same
EP0352127B1 (en) Oxygen impermeable leak free container
WO2001072515A1 (en) Laminated packaging material and process for producing laminated packaging material
TWI569962B (en) Laminated film
JP2015128907A (en) Packaging material and paper container formed of the same

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13827500

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2014529528

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20147032674

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13827500

Country of ref document: EP

Kind code of ref document: A1