WO2021048795A1 - 多層構造体、その製造方法および包装容器 - Google Patents
多層構造体、その製造方法および包装容器 Download PDFInfo
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- WO2021048795A1 WO2021048795A1 PCT/IB2020/058441 IB2020058441W WO2021048795A1 WO 2021048795 A1 WO2021048795 A1 WO 2021048795A1 IB 2020058441 W IB2020058441 W IB 2020058441W WO 2021048795 A1 WO2021048795 A1 WO 2021048795A1
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- WIPO (PCT)
- Prior art keywords
- layer
- starch
- adhesive layer
- multilayer structure
- snake
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0013—Extrusion moulding in several steps, i.e. components merging outside the die
- B29C48/0014—Extrusion moulding in several steps, i.e. components merging outside the die producing flat articles having components brought in contact outside the extrusion die
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/23—Articles comprising two or more components, e.g. co-extruded layers the components being layers with means for avoiding adhesion of the layers, e.g. for forming peelable layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
- B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered 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
- B32B7/02—Physical, chemical or physicochemical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered 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
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/02—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising animal or vegetable substances, e.g. cork, bamboo, starch
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
- C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C09J201/06—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
- C09J201/08—Carboxyl groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
- B29C43/04—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles using movable moulds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2003/00—Use of starch or derivatives as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0097—Glues or adhesives, e.g. hot melts or thermofusible adhesives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0081—Tear strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/712—Containers; Packaging elements or accessories, Packages
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B2250/02—2 layers
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- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
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- B32B2264/10—Inorganic particles
- B32B2264/102—Oxide or hydroxide
- B32B2264/1027—Clay
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- B32B2307/00—Properties of the layers or laminate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Definitions
- the present invention relates to a multi-layer structure, a method for producing the multi-layer structure, and a packaging container including the multi-layer structure. Background technique
- a resin layer containing starch as a main component is widely used in containers for packaging foods because it is biodegradable and has excellent gas barrier properties.
- the resin layer containing starch as a main component is highly hydrophilic and tends to significantly impair the barrier property due to the influence of humidity. Therefore, when the barrier property is particularly required, it is necessary to use a water-resistant material for multiple layers (Patent Documents). 1 and 2).
- Patent Documents As a method for forming multiple layers, an extrusion coating method using an outer layer material is often used from the viewpoint of productivity.
- the outer layer material Yincho, Min, Nylon, polyvinyl chloride, polyvinylidene chloride, etc. are used.
- Patent Document 1 Special Table 2 0 1 5 --5 0 8 3 4 No. 1
- Patent Document 2 Special Table 2 0 1 5 --5 3 3 7 3 3 No. Outline of Invention The invention is about to be solved. Task
- an object of the present invention is to maintain peel strength even when stored under low humidity.
- ⁇ 0 2021/048795 ⁇ (: 17132020/058441)
- the present invention includes the following preferred embodiments.
- the material that makes up the adhesive layer (snake) has a density of 0.92 0.
- the substrate layer ( ⁇ 3), which contains 3 or less thermoplastic resin, has a tensile modulus of 10 0.
- the material constituting the starch layer () has a starch content of 20% by mass or more and an amylose content in the starch of 50% by mass or more, according to [1].
- the material constituting the base material layer ( ⁇ ) contains at least one selected from the group consisting of polyethylene terephthalate, polylactic acid, polyethylene, polypropylene, cellophane, aromatic polyester and polyptylene succinate. , The multilayer structure according to any one of [1] to [6]. ⁇ 020 21/048795 ⁇ (: 17132020/058441
- the multilayer structure of the present invention can provide a multilayer structure having a starch resin layer, which maintains peel strength even when stored under low humidity.
- FIG. 1 Shows a schematic diagram of the twin-screw extruder used to make the starch layer () in the examples.
- the multilayer structure of the present invention includes a starch layer (8), an adhesive layer (Snake), and a base material layer ( ⁇ ) in this order.
- the materials that make up the starch layer (8) contain starch and water, and the materials that make up the adhesive layer (Snake) have a density of 0.920.
- the acid value of the material that contains 3 or less thermoplastic resin and constitutes the adhesive layer (Snake) is 0.3.
- the materials constituting the starch layer (8) include starch (8 1) and water. It is preferable that the starch layer (8) has a starch (81) content of 20% by mass or more and an amylose content in the starch (81) of 50% by mass or more. In addition, the demp in the material that makes up the starch layer (8) ⁇ 0 2021/048795 ⁇ (: 17132020/058441
- the content of 4 (81) is preferably 50 to 98% by mass, more preferably 70 to 98% by mass. When the content of starch (81) is within the above range, good gas barrier properties tend to be easily obtained.
- Starch (8 1) includes, for example, arrowroot, corn, potato, sweet potato, sago, tapioca, morokoshi, beans, warabi, hass, hisashi, wheat, rice, and sardine. Examples include starch derived from arrowroot, potato and the like.
- Starch (81) may be modified, modified starch.
- the starch used as a raw material for the modified starch is preferably starch derived from corn or corn, and more preferably starch derived from corn.
- Modified starches include, for example, etherified starch, esterified starch, cationized starch and crosslinked starch.
- the material constituting the starch layer (8) may contain one or more of these modified starches.
- etherified starch examples include alkyl etherified starch such as methyl etherified starch; carboxyalkyl etherified starch such as carboxymethyl etherified starch; for example, hydroxyalkyl having 2 to 6 carbon atoms. Hydroxyalkyl etherified starches such as etherified starches having a group; In addition, allyl etherified starch and the like can also be used.
- esterified starch examples include esterified starch having a structural unit derived from a carboxylic acid such as esterified starch having a structural unit derived from acetic acid; and esterified starch having a structural unit derived from maleic acid anhydride, for example.
- esterified starch having structural units derived from xoic acid such as dempun, phosphoric acid esterified starch, and urea phosphate esterified starch.
- Examples of 5 include xanthate esterified starch and acetoacetic esterified starch.
- Examples of the cationized starch include a reaction product of starch and 2-diethylaminoethyl chloride, and a reaction product of starch and 2, 3-—epoxypropyltrimethylammonium chloride.
- crosslinked starch examples include formaldehyde crosslinked starch, epichlorohydrin crosslinked starch, phosphoric acid crosslinked starch, achlorine crosslinked starch and the like.
- esterified starch having a hydroxyalkyl group having 2 to 6 carbon atoms and dicarboxylic acid anhydride from the viewpoint of easily suppressing a decrease in peel strength under low humidity.
- Esterified denpun having the structural unit of, or a combination thereof is preferable, and esterified den with a structural unit derived from hydroxyethyl etherified starch, hydroxypropyl etherified starch, hydroxybutyl esterified starch, and maleic anhydride.
- Esterified starch having a structural unit derived from phthalic anhydride, esterified starch having a structural unit derived from octenyl succinic anhydride, or a combination thereof is more preferable.
- the etherified starch having a hydroxyalkyl group having 2 to 6 carbon atoms may be obtained by reacting an alkylene oxide with starch.
- alkylene oxide include ethylene oxide, propylene oxide, and petitrene oxide.
- the average number of hydroxy groups used for denaturation is preferably 0.05-2 per glucose unit in starch.
- the modified starch may be produced by modifying starch having a predetermined amylose content by a method known in the art, or commercially available starch may be used.
- typical commercially available modified starches include, for example, I available hydroxypropyl etherified starch. (Registered trademark) and 3 1: 1 ⁇ n 3 I 7 (Registered trademark) ⁇ 020 21/048795 ⁇ (: 17132020/058441
- the starch (A 1) contained in the starch layer (A) has an amylose content of preferably 50% by mass or more, more preferably 55% by mass or more, still more preferably 60% by mass in the starch (A 1). % Or more.
- amylose content preferably 50% by mass or more, more preferably 55% by mass or more, still more preferably 60% by mass in the starch (A 1). % Or more.
- starch (A 1) usually has an amylose content of 90% by mass or less in starch (A 1).
- the content of amylose in starch (A 1) can be measured, for example, by the iodine coloration method described in "S t a r c h 50 No. 4 1 58-1 63 (1 998)".
- the amylose content of starch (A 1) is a weighted average value considering the composition ratio of two or more types of starch, average. Means amylose content.
- Starch (A 1) has a water content of preferably 2 to 15% by mass.
- the water content can be determined, for example, by a / erogen moisture meter.
- the material constituting the starch layer (A) contains water.
- the water content in the starch layer (A) is preferably 5 to 25% by mass, more preferably 10 to 15% by mass. When the water content is within the above range, the thermoformability tends to be excellent.
- the material constituting the starch layer (A) may contain at least one water-soluble polymer.
- the content of the water-soluble polymer in the material constituting the starch layer (A) is preferably 2 to 50% by mass, more preferably 2 to 35% by mass. When the content of the water-soluble polymer is in the above range, the strength at a low temperature tends to be easily obtained.
- polyvinyl alcohol (A2) As a water-soluble polymer, polyvinyl alcohol (A2)
- polyvinyl alcohol (A2) is preferable from the viewpoint of mechanical properties.
- Polyvinyl alcohol (A2) has a preferably saponification degree of 80 to 99.8 mol%. If the degree of saponification of polyvinyl alcohol (A2) is within the above range, it is sufficiently strong. ⁇ 0 2021/048795 ⁇ (: 17132020/058441
- the degree of saponification is more preferably 85 mol% or more, still more preferably 88 mol% or more.
- the degree of saponification refers to the mole fraction of the hydroxyl group with respect to the sum of the hydroxyl group and the ester group in polyvinyl alcohol (82).
- the degree of saponification can be determined, for example, by quantifying the residual acetic acid groups in the sample with sodium hydroxide.
- the polyvinyl alcohol (82) may further contain other monomer units other than the vinyl alcohol unit.
- other monomer units include monomer units derived from ethylenically unsaturated monomers.
- Ethylene unsaturated monomers include ethylene, propylene, —butene, isoptylene, 1 —hexene and other ⁇ -olefins; acrylic acid and salts thereof; unsaturated monomers having an acrylate group of acrylic acid; methacryl Acids and salts thereof; unsaturated monomers with ester methacrylate groups; acrylic acid, 1 ⁇ 1 — methyl acrylic acid,
- Vinyl Sacrifice Vinyl Acetate, Vinyl Propionate, Vinyl Butyrate, Vinyl Isobutyrate, Vinyl Vivalate, Vinyl Versatic, Vinyl Caproate, Vinyl Carliate, Vinyl Laurate, Vinyl Palmitate, Vinyl Stearate, Olein Vinyl ester monomers such as vinyl acetate and vinyl benzoate are exemplified.
- the content of the other monomer unit is preferably 10 mol% or less, preferably
- the monomer unit in polyvinyl alcohol can be measured by using, for example, 1 3 ⁇ _ 1 ⁇ /
- the method for producing the polyvinyl alcohol (82) is not particularly limited.
- a method of copolymerizing a vinyl alcohol monomer with another monomer and saponifying the obtained copolymer to convert it into vinyl alcohol units can be mentioned.
- the polymerization method for copolymerization include batch polymerization, semi-batch polymerization, continuous polymerization, and semi-continuous polymerization.
- the polymerization method include known methods such as a massive polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method.
- a known method can be applied. For example, it can be carried out in a state where the copolymer is dissolved in alcohol or hydrous alcohol.
- the alcohol that can be used at this time is preferably a lower alcohol such as methanol or ethanol.
- the polyvinyl alcohol (8 2) is based on " ⁇ 3 1 8 8 0 3". As described above, it is more preferably 2 0 1 3 3 or more, further preferably 3 1 3 3 or more, preferably 4 5 01 3 3 or less, and more preferably 3 5 01 3 3 or less. When the viscosity of polyvinyl alcohol (82) is at least the above lower limit value and at least the above upper limit value, sufficient strength and oxygen barrier property can be easily obtained.
- the material constituting the starch layer (8) may contain at least one type of clay.
- Clays include synthetic or natural layered silicate clays, such as montmorillonite, bentonite, biderite, mica, hexrite, support, nontronite, soconite, vermiculaite, and ready kai. To, Magadite, Kenya Aito, Steven Site, Vorco ⁇ 0 2021/048795 ⁇ (: 17132020/058441
- the clay may be modified to be hydrophobic or hydrophilic.
- the layered silicate clay may be modified to be hydrophobic or hydrophilic.
- the "hydrophobic clay” or “hydrophobically modified layered silicate clay” is preferably a clay modified by exchange with a surfactant containing a long-chain alkyl group.
- Long chain alkyl groups may contain more than 4 or more than 5 or more than 6 carbon atoms per chain.
- Preferred surfactants include long-chain alkylammonium ions, such as mono or G ⁇ 1 2 — ⁇ 2 2 alkylammonium ions.
- the long chain alkyl group is free of polar substituents, for example, free of hydroxyl groups and free of carboxyl groups.
- I.40 of clay modified to suitable hydrophobicity also ⁇ 1_ ⁇ I 3 I Chomi (registered trademark) 2 0 8 or (3 1_ ⁇ I 3 I Chomi (registered trademark) 2 5 8 from the company.
- the content of clay in the material constituting the starch layer () is preferably 0.1 to 5% by mass, more preferably 0.1 to 3% by mass, and further preferably 0.5 to 2% by mass. is there.
- clay is included in the above range, transparency, flexibility, tensile strength, impact resistance and / or tensile properties tend to be improved.
- the material constituting the starch layer () may include a plasticizer, a moisturizer, a lubricant, and other additives.
- Plasticizers include, for example, polyols, polyethylene glycol, epoxidized linseed oil, epoxidized soybean oil, tributyl citrate, 2, 2, 4 — trimethyl-1,3-pentanediol diisoptylate, and acetyl citrate. Tilt reethyl can be mentioned.
- the content of the plasticizer is preferably 20% by mass or less. ⁇ 020 21/048795 ⁇ (: 17132020/058441
- Moisturizers include, for example, carrageenan, xanthan gum, gum arabic, guar gum, gelatin, and glycerin triacetate. Moisturizers may also function as water knots or gelling agents.
- the content of the moisturizer is preferably 20% by mass or less.
- the lubricant include fatty acids and fatty acid salts. 2 ⁇
- the content of the lubricant is preferably 1.5% by mass or less.
- the density is preferably 0. 9 1 82 Below, more preferably 0.9
- the density is preferable. Or more, more preferably is ⁇ . 85 9 / Rei_rei_1 3 or more
- the material that makes up the adhesive layer (Snake) has a density of ⁇ . 920
- a thermoplastic resin of 3 or less When a thermoplastic resin of 3 or less is contained, the reaction generated by dehydration shrinkage of the starch layer during low-humidity storage can be alleviated, so that the decrease in peel strength tends to be suppressed under low humidity.
- the density of at least one type of thermoplastic resin needs to be ⁇ . 920 9 / ⁇ ⁇ ! 3 or less.
- the weighted average value considering the composition ratio of two or more types of thermoplastic resins is ⁇ . 920 It is preferably 3 or less.
- the density can be measured, for example, by the method described in Examples below.
- the acid value of the materials that make up the adhesive layer (Snake) is ⁇ .3. 9 [ ⁇ 1 ⁇ 1/9 or more. The acid value is ⁇ . 3 9 If less than, it adheres to the starch layer () ⁇ 0 2021/048795 ⁇ (: 17132020/058441
- the acid value of the materials that make up the adhesive layer (Snake) is preferably 0.4. As mentioned above, I like it even more. Even more preferably 1.5 mg K ⁇ H /
- the acid value is preferably Below, more preferably 3 9 It is as follows.
- the acid value of the material constituting the adhesive layer (Snake) is equal to or higher than the lower limit, the adhesive strength between the starch layer (8) and the adhesive layer (Snake) becomes sufficient and is equal to or lower than the upper limit. As a result, the reaction during thermoforming proceeds moderately, so molding defects are unlikely to occur.
- the acid value can be measured, for example, by the method described in Examples described later.
- the acid value of the material refers to the acid value of the material as a mixture measured as described in Examples described later.
- the acid value correlates with the amount of acid in the adhesive layer (Snake).
- the acid in the adhesive layer (Mi) obtains adhesiveness by reacting with the hydroxyl groups on the surface of the starch layer (8), and is thought to contribute to the initial adhesive strength and the peel strength under low humidity. ..
- the initial adhesive strength and the peel strength under low humidity are the effects associated with the reaction between the acid in the adhesive layer (Mino) and the hydroxy group in the starch layer (8), and the starch layer (8) and the adhesive layer (8). It is considered that two effects due to compatibility with starch) are involved. Therefore, in order to achieve good adhesion, as the material constituting the adhesive layer of the multilayer structure of the present invention (Snake) are ⁇ .
- the above acid value is required, ⁇ .
- the above is considered to be more preferable.
- the acid value of the material constituting the adhering layer (snake) can be adjusted above the above lower limit value by appropriately adjusting, for example, the type and composition ratio of the constituent units constituting the thermoplastic resin described later.
- the material constituting the adhesive layer includes a thermoplastic resin.
- the thermoplastic resin include polyolefin-based polymers, polyester-based polymers, and polyamide-based polymers, but it is preferable that the thermoplastic resin contains a polyolefin-based polymer. ⁇ 0 2021/048795 ⁇ (: 17132020/058441
- Modified polyolefin-based polymers include carbons such as ethylene, propylene, 1-butene, 3-methyl-1 —butene, 1—penten, 4—methyl-1—pentene, 1—hexane, 1—octene, 1—decene, etc.
- a resin obtained by modifying about 2 to 20 polyolefins a copolymer of vinyl compounds such as vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid, ester acrylate, ester methacrylate, and polystyrene, and olefin;
- Typical examples are chillene-propylene copolymers, ethylene-propylene copolymers, ethylene _ 1 — butene copolymers, propylene _ 1 — resins modified from polyolefin-based copolymers such as butene copolymers. It can be mentioned as anything.
- As a method of denaturation denaturation under graft reaction conditions can be mentioned.
- Examples of those used for the graft reaction include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, isochronic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and tetrafidrophthalic acid.
- unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, isochronic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and tetrafidrophthalic acid.
- Derivatives such as acid halide, amido, imidazole, anhydride, and ester can be mentioned.
- Specific examples thereof include malenyl chloride, maleamide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, and glycidyl maleate.
- the content of the urethane resin of the material constituting the adhesive layer (mi) is preferably 50% by mass or less, preferably 10% by mass or less. It is preferable, and ⁇ % by mass is most preferable.
- the modified polyolefin-based polymer unsaturated dicarboxylic acid or an anhydride thereof, particularly maleic acid or a resin modified with the anhydride thereof is preferable from the viewpoint of reactivity and hygiene as a food packaging material.
- the resin to be modified an ethylene-based resin, a propylene-based resin, an ethylene-propylene copolymer or an ethylene _1-butene copolymer is suitable. Therefore, in a preferred embodiment of the present invention, a polyolefin-based polymer modified with maleic anhydride, that is, a polyolefin-based polymer having a structural unit derived from maleic anhydride. ⁇ 0 2021/048795 ⁇ (: 17132020/058441
- the base material layer ( ⁇ 3) has a tensile elastic modulus of 10 These are the above layers.
- the tensile elasticity is 100 IV! 3 or more, preferably Above, more preferably 30 or more, even more preferably 500 1 ⁇ / 1? 3 or more, even more preferably 100 0 IV! 3 or more, particularly preferably 2 0 0 IV! 3 or more, and even more particularly. Preferably 3 0 0 0 That is all.
- the elastic modulus can be measured, for example, by the method described in Examples described later. Usually, the elastic modulus is 800 IV! 3 or less.
- the tensile elastic modulus of the base material layer ( ⁇ ) In order to make the tensile elastic modulus of the base material layer ( ⁇ ) equal to or higher than the lower limit value, adjust it to the lower limit value or higher by adjusting the type and composition ratio of the materials constituting the base material layer ( ⁇ 3). be able to. If the elastic modulus is less than 100 IV! 3 , the strength of the base material layer is insufficient and the base material is liable to break.
- the materials that make up the base material layer ( ⁇ 3) are polyethylene terephthalate (Micho) and polylactic acid (! _8).
- the base material layer (the content of the material in ⁇ is preferably 100 to 100% by mass, more preferably 20 to 90% by mass.
- the material constituting the base material layer ( ⁇ ). May further include other materials such as polyolefin, nylon, vinyl chloride, vinylidene chloride, etc. If the substrate layer ( ⁇ ) contains other materials, the substrate layer (of the other material in ⁇ ) The content may be preferably 5 to 50% by mass (the total of all the materials in the base material layer ( ⁇ ) is 100% by mass).
- the base material layer (the resin material contained in ⁇ may be a biodegradable resin.
- the biodegradable resin polyputilene adibe single petitrene terephthalate copolymer (Mihaccho), polyhydroxybuty Examples include rate, polycaprolactone, polyhydroxyalkanoate, polyglycolic acid, modified polyvinyl alcohol, denpun, cellulose, etc.
- the base material layer (the material constituting ⁇ may contain one type of biodegradable resin, and may contain one type of biodegradable resin. Two or more types may be included, and the arrangement when two or more types are included ⁇ 020 21/048795 ⁇ (: 17132020/058441
- the total ratio is not particularly limited.
- the thickness of the multi-layer structure of the present invention is preferably 30 to 1,000,000.
- the thickness of the denpun layer (8) is preferably 20 to 500, and the thickness of the base material layer ( ⁇ ) is preferably 10 to 500.
- the thickness of the starch layer (8) is within the above range, it tends to have a good gas barrier property. Further, when the thickness of the base material layer ( ⁇ is within the above range, the base material is less likely to break.
- the thickness of the adhesive layer is preferably 5 to 50, more preferably 10 to 30. When it is 5 or more, it is easy to obtain sufficient adhesive strength between layers, and when it is 50 or less, it is preferable because appearance defects called whiskers are unlikely to occur during the punching process of the container performed after thermoforming. ..
- the layer structure of the multilayer structure layer is not particularly limited as long as it includes three layers of a starch layer (8), an adhesive layer (Snake), and a base material layer ( ⁇ ) in this order.
- the starch layer (8) is eight
- the adhesive layer (Snake) is a snake
- the base material layer ( ⁇ is ⁇ , for example, a three-layer structure of eight / ⁇ / ⁇ , / ⁇ / ⁇ / /, / ⁇ /
- the five-layer structure of / ⁇ , ⁇ / ⁇ / / ⁇ / ⁇ can be mentioned.
- the layer (mouth) other than the starch layer (8), the adhesive layer ( ⁇ ), and the base material layer ( ⁇ ) is included. If the layer (mouth) is used as the mouth, 0/8 / ⁇ / ⁇ , ⁇ / ⁇ / ⁇ / ⁇ , / ⁇ / ⁇ / ⁇ , / ⁇ / ⁇ / ⁇ , 8 / ⁇ / ⁇ / ⁇ / ⁇ , / ⁇ / ⁇ / / ⁇ , / ⁇ / ⁇ / ⁇ , ⁇ / / ⁇ / ⁇ , ⁇ / / ⁇ / / ⁇ , ⁇ / ⁇ / / / / ⁇ , ⁇ / ⁇ / / / / / ⁇ etc.
- the composition is preferable.
- the layer (0) is not particularly limited, but for example, paper.
- Paper is not particularly limited, but for example, starch paper, kraft paper, fine paper, medium quality paper, embossed paper, and coat. Paper, starch — Bonn paper, paperboard, etc.
- the multilayer structure of the present invention has a temperature of 23 ° 0, After that, the peel strength (1) between the starch layer (8) and the adhesive layer (Snake) is 1.01 ⁇ 9 chi / 15 The above is preferable.
- the temperature of the multilayer structure of the present invention is 4 ⁇ 0 2021/048795 ⁇ (: 17132020/058441
- the peel strength (2) between the starch layer (8) and the adhesive layer (Snake) after being left for 48 hours under 3 ⁇ 4 1 to 1 is ⁇ . 5 1 ⁇ 9 dry / 15 or more is preferable.
- the rate of decrease in peel strength represented by the following equation is usually less than 60%, preferably less than 50%, and more preferably less than 30%.
- the peel strength can be measured, for example, by the method described in Examples described later. Rate of decrease in peel strength
- the manufacturing method of the multilayer structure of the present invention is not particularly limited.
- a method including a step of co-extruding the adhesive layer (Mino) and the base material layer ( ⁇ ) and then coating the adhesive layer (Mino) side with the starch layer (8) can be mentioned.
- Other methods include, for example, a step of extruding the adhesive layer (Snake) and then coating the adhesive layer (Snake) between the starch layer (8) and the substrate layer (0).
- the cylinder temperature can be 250 to 2700 ° ⁇
- the adapter temperature can be 270 ° ⁇
- the die temperature can be 275 ° ⁇ .
- the cylinder temperature is 175 to 270 ° ⁇
- the adapter temperature is 270 ° ⁇
- the die temperature is 2 It can be 75 ° ⁇ .
- the absolute value is preferably 1 0 ° ⁇ within the difference between the die temperature of the die temperature and the extruder of the extruder (1) (2), and more preferably 0 ° ⁇ .
- the optimum die temperature differs between the resin used for the extruder (1) and the resin used for the extruder (2), the one with the higher optimum die temperature can be used to adjust the die temperature. preferable. ⁇ 0 2021/048795 ⁇ (: 17132020/058441
- the adhesive layer (Mi) side of the co-extruded laminate is taken over the starch layer (8).
- a method of coating and pasting with a nip roll can be adopted.
- the pick-up speed is preferably 1 to 10 / min.
- the packaging container of the present invention comprises the multilayer structure of the present invention.
- the packaging container may be composed of only the multilayer structure of the present invention, or may be a composite of other materials.
- the multilayer structure of the present invention can be thermoformed into a packaging container.
- the thermoforming method is not particularly limited, but is generally vacuum forming, compressed air forming, a plug assist method in which a plug is brought into contact with one side of a multi-layer structure for molding, and a multi-layer structure. Examples include a so-called multi-mold molding method in which a pair of male and female molds are brought into contact with each other on both sides of the body for molding.
- non-contact heating or direct heating can be mentioned, and as non-contact heating, radiant heating by infrared heating or the like can be mentioned.
- direct heating a known heating method such as hot plate heating in which the hot plate is in direct contact with the hot plate can be applied.
- the packaging container made of the multilayer structure of the present invention is excellent as a packaging container because the peeling strength is maintained even when it is stored under low humidity. In a more preferred embodiment, it is excellent in acid barrier property and biodegradability, so that it can be particularly suitably used as a packaging container for foods.
- the value of the peel strength was determined by the same method as>.
- the required peel strength of the packaging material under low humidity and normal humidity differs depending on the product shape. For example, in the tray-shaped packaging material obtained from the multilayer structure of the present invention by thermoforming or the like, 1.
- the above is a preferable guideline. Although this standard value may increase or decrease depending on the application, 0.4 1 ⁇ 9 dry / 1 5 The peel strength below the above does not meet the required performance of most product shapes and applications.
- thermoplastic resin constituting the adhesive layer (Mitsumi)> Thermoplasticity using Akiyupic ⁇ ⁇ 1 3 4 0 manufactured by Shimadzu Corporation under the condition of equipment temperature 25 ° ⁇ (Sat 1 ° ⁇ ) The resin pellet was measured by a dry measurement method using a gas (helium gas). The same test was performed a total of three times, and the average value was used as the density value.
- thermoplastic resin 4 0 0 9 constituting the adhesive layer (Mitsumi) was weighed into an Erlenmeyer flask, and xylene 80 I was added. The temperature was raised by stirring to 130 ° ⁇ to dissolve the thermoplastic resin. Add a small amount of phenolphthalein to the solution, ⁇ . 0 5 ⁇ ⁇ /
- the material of the starch layer (8) was prepared by the following method. Modified starch in the materials that make up the starch layer (8) ( ⁇ ) [Mi (30 I) (Registered trademark), ⁇ n ⁇ 0 2021/048795 ⁇ (: 17132020/058441
- the starch layer () was obtained by extruding from the die of the extruder, cooling, and setting the take-up rate so that the thickness after drying was 150.
- Starch layer () The cylinder temperature during production was set to the temperature profile shown in Table 2 below. 0 5 to 0 9 are cooking processing areas.
- Example 1 As the material of the base material layer ( ⁇ ), Mitsui (polyethylene terephthalate) (IV! & ⁇ Chemicals Co., Ltd. “3 Soi Dry Drying 7300) was used. Polyolefin as a material for (Mitsui) (manufactured by Mitsui Chemicals, Inc.) "3 0 0 0) was used. The material of the base material layer ( ⁇ ) was the cylinder temperature 250 ° ⁇ ⁇ 270 ° ⁇ , the adapter temperature 270 ° ⁇ , and the die temperature 275 ° ⁇ .
- the adhesive layer (Mino) and the base material layer (laminated film consisting of ⁇ [contact layer (Mino) thickness 2 0 111 / base material layer ( ⁇ ) thickness 150 ⁇ 111] were obtained.
- the adhesive layer (Snake) side of the film is obtained by the above ⁇ Preparation of starch layer (8)>. ⁇ 020 21/048795 ⁇ (: 17132020/058441
- the material of the adhesive layer is polyolefin (Mitsui Chemicals, Inc. 8 0! 6 "3 Snake".
- a multilayer structure was produced in the same manner as in Example 1 except that it was changed to 8 10).
- the material of the adhesive layer is polyolefin (Mitsui Chemicals, Inc. 8 0! 6 "3"
- a multilayer structure was prepared in the same manner as in Example 1 except that it was changed to 7 4 1).
- the material of the adhesive layer is polyolefin (Mitsui Chemicals, Inc. 8 0! 6 "3"
- a multilayer structure was prepared in the same manner as in Example 1 except that it was changed to 7 2 5).
- Example 5 The material of the base material layer ( ⁇ ) is (Polyptylene succinate) (Mitsubishi Chemical Corporation, 3 F Z9]), except that it was extruded at a cylinder temperature of 1 80 ° ⁇ to 200 ° ⁇ , an adapter temperature of 200 ° ⁇ , and a die temperature of 200 ° ⁇ .
- a multilayer structure was produced in the same manner as in Example 4.
- Example 6 The material of the base material layer ( ⁇ ) was changed to PLA (polylactic acid) (Mitsubishi Chemical Corporation Ecologue 38 1 04), and the extrusion conditions were changed (extruder cylinder temperature 1). 80 ° ⁇ ⁇ 200 ° ⁇ , Adapter temperature 200 ° ⁇ , Die temperature 200 ° ⁇ . Also, polyolefin (manufactured by Mitsui Chemical Corporation), which is the material of the adhesive layer (Mi) The extrusion conditions of "3 7 2 5) were changed (extruder cylinder temperature 175 to 200 ° ⁇ , adapter temperature 200 ° ⁇ , die temperature 200 ° ⁇ ). Other than that, the multilayer was the same as in Example 4. The structure was made.
- PLA polylactic acid
- Mi polyolefin
- PHA 3-hydroxybutyrate-3-hydroxyhexanoate copolymer
- Example 9 The material of the base material layer (C) is changed to P BAT (polyputilene ajibe 1-cylinder ptylene telephthalate copolymer) (B AS F E c ⁇ V i ⁇ FT 234 1) and extruded.
- the conditions were changed (extruder cylinder temperature 1 60 ° C to 200 ° C, polymer temperature 200 ° C, die temperature 200 ° C).
- a multilayer structure was produced in the same manner as in Example 4 except for the above.
- Example 10> The material of the base material layer (C) was changed to LDPE (polyolefin) (Novatec LDLJ 400 manufactured by Japan Polyethylene Corporation), and the extrusion conditions were changed (extruder cylinder temperature 1 60 ° C ⁇ . 200 ° C, adapter temperature 200 ° C, die temperature 22 ⁇ ° C).
- ⁇ 020 21/048795 ⁇ (: 17132020/058441
- the die temperature was set according to the one with the higher required temperature (here, the adhesive layer (Snake)).
- a multilayer structure was produced in the same manner as in Example 4 except for the above.
- Example 1 As a material for the adhesive layer (Snake), polyolefin (Mitsui Chemicals, Inc. 8 0! 6 "
- a multilayer structure was prepared in the same manner as in Example 4 except that 3 7 2 5) and another polyolefin (Mitsui Chemicals Co., Ltd. 816 “567) were dry-blended at a mass ratio of 75:25.
- Example 1 2 As a material for the adhesive layer (Snake), with polyolefin (Mitsui Chemicals Co., Ltd. 8 0! 6 "3 Snake 800") A multilayer structure was produced in the same manner as in Example 4 except that (polyolefin) (Novatec manufactured by Japan Polyethylene Corporation! _ 0! _ 600 8) was dry-blended at a mass ratio of 75:25.
- polyolefin Mitsubishi manufactured by Japan Polyethylene Corporation! _ 0! _ 600 8
- Example 1 The multilayer structure is the same as in Example 1 except that the material of the adhesive layer (Snake) is changed to polyolefin (manufactured by Arkema! _ ⁇ I 3 ⁇ 16 “4 5 0 3)”. Made.
- Example 2 A multilayer structure was produced in the same manner as in Example 1 except that the material of the adhesive layer (Snake) was changed to polyolefin (Dow Chemical Co., Ltd. Hachi II Dry V Ding 4 3 5 1). did.
- Example 3 A multilayer structure was produced in the same manner as in Example 1 except that the material of the adhesive layer (Snake) was changed to polyolefin (DuPont 6 V n 6 I 2 1 Snake 8 30). ..
- the material of the base material layer ( ⁇ ) was extruded at a cylinder temperature of 250 ° ⁇ to 270 ° ⁇ , an adapter temperature of 270 ° ⁇ , and a die temperature of 275 ° ⁇ to prepare a sheet with a thickness of 150 ° C.
- the material of the adhesive layer (Snake) was applied to the base material layer ( ⁇ ) to a thickness of 15 by the dry lamination method.
- a starch layer (8) film with a thickness of 150 obtained from the above ⁇ Preparation of starch layer (8)> on the adhesive layer (Mi) side of the layered film consisting of the adhesive layer (Mi) and the base material layer ( ⁇ ).
- a multi-layer structure starch layer (8) thickness 150 ⁇ / adhesive layer (mi) thickness 150 ⁇ / base material layer ( ⁇ ) thickness 1 50 ⁇ ) was prepared.
- the multilayer structure was allowed to stand in a constant temperature room of 40 ° ⁇ 15% [3 ⁇ 4 1 to 1 for 48 hours, and as a result, the adhesive layer as shown in Examples 1 to 12 (as shown in Examples 1 to 12).
- the material constituting the Snake comprises 0.9 2 0 9 / ⁇ 3 or less of the thermoplastic resin, the acid value of the material, ⁇ .
- the rate of decrease in peel strength was low, and it was confirmed that the peel strength was maintained even when stored under low humidity. In addition, it had a good appearance without yellowing.
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Abstract
Description
Claims
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US17/641,990 US20230241864A1 (en) | 2019-09-13 | 2020-09-11 | Multilayer structure, method of producing the same, and packaging container |
AU2020344251A AU2020344251A1 (en) | 2019-09-13 | 2020-09-11 | Multilayer structure, production method therefor, and packaging container |
CN202080064032.1A CN114340889A (zh) | 2019-09-13 | 2020-09-11 | 多层结构体、其制备方法及包装容器 |
JP2021544977A JPWO2021048795A1 (ja) | 2019-09-13 | 2020-09-11 | |
EP20863709.0A EP4043207A4 (en) | 2019-09-13 | 2020-09-11 | MULTILAYER STRUCTURE, ITS PRODUCTION METHOD AND PACKAGING CONTAINER |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US20070292665A1 (en) * | 2004-09-30 | 2007-12-20 | Nippon Paper Industries, Co., Ltd. | Laminated Sheet |
JP2015508341A (ja) | 2011-12-22 | 2015-03-19 | プランチック テクノロジーズ リミテッド | 多層フィルム |
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