WO2023042753A1 - Feuille de résine et récipient formé - Google Patents

Feuille de résine et récipient formé Download PDF

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Publication number
WO2023042753A1
WO2023042753A1 PCT/JP2022/033789 JP2022033789W WO2023042753A1 WO 2023042753 A1 WO2023042753 A1 WO 2023042753A1 JP 2022033789 W JP2022033789 W JP 2022033789W WO 2023042753 A1 WO2023042753 A1 WO 2023042753A1
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Prior art keywords
resin
resin sheet
layer
mass
less
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PCT/JP2022/033789
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English (en)
Japanese (ja)
Inventor
和也 杉本
敬司 ▲高▼野
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デンカ株式会社
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Priority to CN202280055446.7A priority Critical patent/CN117794988A/zh
Priority to JP2023548445A priority patent/JPWO2023042753A1/ja
Publication of WO2023042753A1 publication Critical patent/WO2023042753A1/fr

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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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS 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
    • B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS 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
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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 resin sheet containing polystyrene resin and a molded container comprising the same.
  • HIPS high impact polystyrene
  • Japanese Patent Application Laid-Open No. 2011-51264 discloses a foam sheet for deep drawing molding in which at least one layer of oxygen barrier layer, at least one layer of moisture-proof layer, at least one layer of impact resistant auxiliary layer and polystyrene foam sheet are laminated.
  • the oxygen barrier layer contains a modified ethylene-vinyl alcohol copolymer (hereinafter sometimes abbreviated as modified EVOH) containing 0.1 to 20 mol% of structural units (I) other than ethylene units and vinyl alcohol units.
  • modified EVOH modified ethylene-vinyl alcohol copolymer
  • a foam sheet for deep draw molding is disclosed, characterized in that the moisture-proof layer is made of polypropylene and the impact-resistant auxiliary layer is made of high-impact polystyrene.
  • the foamed sheet for deep drawing described in the publication has excellent gas barrier properties and moisture resistance against oxygen, and can be deep drawn and thermoformed at a high magnification, and the sheet is formed by deep drawing. It is stated that a foam container can be provided.
  • a core layer mainly composed of high-impact polystyrene and a mixture of polystyrene and a laminated sheet consisting of outer layers mainly composed of high-impact polystyrene arranged on both sides of the core layer describes that by setting the thickness of the outer layer relative to the total thickness and the amount of polybutadiene in the core layer and the outer layer within specific ranges, a laminated sheet having excellent notch folding resistance, impact resistance and moldability can be obtained.
  • JP-A-2020-164600 in a polystyrene resin foam sheet for a container having a foam layer containing a polystyrene resin and a polyphenylene ether resin, the ratio of each resin component, the average cell diameter in the foam layer, It is described that excellent moldability and heat resistance can be obtained by defining the density of the foam layer within a predetermined range.
  • Polylactic acid resin which is a type of biomass plastic, is inexpensive and has excellent rigidity and high transparency. For this reason, polylactic acid resin is expected to be applied as a material for molded containers such as packs, cups and trays for beverages, foods, cosmetics, household appliances and other daily necessities.
  • polylactic acid resin has poor compatibility with polystyrene resin, and when a resin sheet contains both polystyrene resin and polylactic acid resin, it is difficult to achieve both excellent notch folding resistance and excellent impact resistance. difficult.
  • the present invention was created in view of the above circumstances, and in one embodiment, a resin sheet containing a polystyrene resin and a polylactic acid resin, which has both excellent notch foldability and excellent impact resistance.
  • the task is to provide Another object of the present invention is to provide a molded container comprising such a resin sheet.
  • the present inventors have made intensive studies to solve the above problems, and found that adjusting the median diameter and content of the butadiene rubber contained in the polystyrene resin to an appropriate range is effective for solving the above problems. , led to the present invention exemplified below.
  • a substrate layer containing a polystyrene resin containing butadiene rubber and a polylactic acid resin is provided, the median diameter of the butadiene rubber in the substrate layer is less than 6 ⁇ m, and the content of the butadiene rubber in the substrate layer is A resin sheet having a content of 3.0% by mass or more and 7.0% by mass or less.
  • the polylactic acid resin constitutes a plurality of dispersed phases dispersed in the polystyrene resin.
  • [4] The resin sheet according to any one of [1] to [3], wherein the total content of the polystyrene resin and the polylactic acid resin in the base material layer is 90% by mass or more.
  • [5] A skin layer containing a polystyrene-based resin laminated on one surface of the substrate layer, and a lower skin layer containing a polystyrene-based resin laminated on the surface of the substrate layer opposite to the surface having the skin layer.
  • a resin sheet according to one embodiment of the present invention contains a polylactic acid resin and has both excellent notch foldability and excellent impact resistance. Therefore, by using the resin sheet, it is possible to manufacture various molded products having both environmental performance and practicality, such as molded containers such as packs and trays for beverages, foods, cosmetics, household appliances and other daily necessities. becomes.
  • FIG. 1 is a cross-sectional view schematically showing a laminated structure of resin sheets according to an embodiment of the present invention
  • FIG. 4 is a cross-sectional view schematically showing a laminated structure of resin sheets according to another embodiment of the present invention.
  • the resin sheet according to the present invention comprises a base layer containing a polystyrene resin containing butadiene rubber and a polylactic acid resin.
  • the resin sheet may have a single-layer structure consisting of only the base material layer.
  • a skin layer containing a polystyrene-based resin laminated on one surface of the layer, and a base layer containing a polystyrene-based resin laminated on the surface of the substrate layer opposite to the surface having the skin layer It is preferable to have a multi-layered structure by further including it.
  • FIG. 1 schematically shows the cross-sectional structure of a resin sheet 10 according to one embodiment of the present invention.
  • the resin sheet 10 has a laminate structure in which a surface layer 11/base layer 12/under layer 13 are laminated in this order from top to bottom of the paper surface.
  • the skin layer 11 and the base layer 12 are directly bonded without an adhesive layer
  • the base layer 12 and the lower layer 13 are directly bonded without an adhesive layer.
  • each layer will be described in order of the base material layer 12, the skin layer 11, and the bottom layer 13, and then the resin sheet 10 itself and the food packaging container as a molded container molded therefrom will be exemplified.
  • the base material layer contains a polystyrene resin containing butadiene rubber and a polylactic acid resin.
  • the butadiene rubber can be present in a state in which a plurality of butadiene rubber particles are dispersed in the polystyrene resin.
  • a method for dispersing a plurality of butadiene rubber particles in a polystyrene resin includes, but is not limited to, a method of polymerizing a styrene monomer in the presence of polybutadiene.
  • a graft polymer having a structure in which a plurality of butadiene rubber particles graft-polymerized with a styrene-based monomer are dispersed in a polystyrene-based resin.
  • Styrenic monomers include, for example, styrene, ⁇ -methylstyrene, p-methylstyrene, dimethylstyrene, pt-butylstyrene, chlorostyrene and the like.
  • the base material layer can appropriately contain a polystyrene resin that does not contain butadiene rubber.
  • a polystyrene resin that does not contain butadiene rubber.
  • homopolymers of styrene monomers such as styrene, ⁇ -methylstyrene, p-methylstyrene, dimethylstyrene, pt-butylstyrene and chlorostyrene, and copolymerization of these styrene monomers with other monomers.
  • Polystyrene-based resins such as Coalesce can be mentioned.
  • Copolymers of styrene-based monomers and other monomers include, for example, polystyrene-acrylonitrile copolymers (AS resins).
  • AS resins polystyrene-acrylonitrile copolymers
  • Polystyrene resins containing butadiene rubber are commercially available. Examples include high impact polystyrene (HIPS resin), polystyrene-acrylonitrile graft polymer (ABS resin), and the like.
  • High impact polystyrene (HIPS resin) is obtained by polymerizing styrene monomer in the presence of a rubbery polymer (typically polybutadiene). It has a sea-island structure with dispersed phases (islands) of graft-polymerized rubber-like polymers.
  • ABS resin is obtained by polymerizing styrene and acrylonitrile monomers in the presence of a rubbery polymer (typically polybutadiene). It has a sea-island structure in which a dispersed phase (island) is a rubber-like polymer obtained by graft polymerization of a part of a monomer and an acrylonitrile monomer.
  • the use of a mixture of general-purpose polystyrene (GPPS resin) and high-impact polystyrene (HIPS resin) for the base material layer is advantageous from the viewpoint of rigidity and thermoformability of molded products such as molded containers obtained by molding resin sheets.
  • GPPS resin general-purpose polystyrene
  • HIPS resin high-impact polystyrene
  • Mixing with GPPS resin also has the advantage of being able to adjust the rubber content.
  • the mixing ratio of the GPPS resin may be adjusted according to the desired rubber content.
  • the median diameter of the rubber particles in the HIPS resin can be adjusted by controlling the shear force by controlling the speed of the rotor blades in the polymerization vessel, controlling the polymerization time, controlling polymerization by additives, and the like.
  • the median diameter of the butadiene rubber in the base material layer is preferably less than 6 ⁇ m. Furthermore, the rubber median diameter is more preferably 1 ⁇ m or more and 5 ⁇ m or less, and even more preferably 2 ⁇ m or more and 4 ⁇ m or less. By setting the rubber median diameter to preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, it is possible to obtain appropriate impact resistance, and when a molded product such as a molded container obtained by molding a resin sheet is dropped, It is possible to make it difficult to cause damage to the molded product.
  • the rubber median diameter refers to the median diameter (D50) based on the volume-based particle size distribution measured with a Coulter counter.
  • the content of butadiene rubber in the base material layer is preferably 3.0% by mass or more and 7.0% by mass or less, and more preferably 4.0% by mass or more and 6.5% by mass or less.
  • the impact resistance can be improved, so that the resin sheet is molded.
  • the molded product can be made less likely to be damaged.
  • setting the content of butadiene rubber in the base material layer to preferably 7.0% by mass or less, more preferably 6.5% by mass or less is advantageous for improving crack propagating properties.
  • Polylactic acid resin can be produced from plants such as corn, sugar cane, and sugar radish as raw materials without using petroleum as a raw material, and is completely biodegradable into water and carbon dioxide by microorganisms in the soil. High environmental performance.
  • Polylactic acid resins include, for example, homopolymers such as poly(L-lactic acid) and poly(D-lactic acid), as well as copolymers having structural units of both L-lactic acid and D-lactic acid (DL-lactic acid), Furthermore, mixtures thereof are also included.
  • the polymerization method for the polylactic acid resin known methods such as condensation polymerization and ring-opening polymerization can be employed.
  • L-lactic acid, D-lactic acid, or a mixture thereof can be directly subjected to dehydration condensation polymerization to obtain a polylactic acid resin having an arbitrary composition.
  • various additives may be blended within a range that does not impair the effects of the present invention.
  • non-aliphatic dicarboxylic acids such as terephthalic acid, non-aliphatic diols such as ethylene oxide adducts of bisphenol A, and the like can be appropriately added for the purpose of improving heat resistance.
  • a chain extender such as a diisocyanate compound, an epoxy compound, an acid anhydride, or the like can be added as appropriate.
  • the content of the polylactic acid resin in the substrate layer is preferably 1% by mass or more and 25% by mass or less, more preferably 5% by mass or more and 20% by mass or less, and 10% by mass or more and 15% by mass or less. is even more preferred.
  • the environmental performance of the resin sheet can be improved. can.
  • the content of the polylactic acid resin in the base material layer is set to preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.
  • notch folding resistance and impact resistance are improved. Easy to improve.
  • the polylactic acid resin is dispersed in the polystyrene resin in the substrate layer by mixing the polylactic acid resin and the polystyrene resin. It may be present so as to constitute a plurality of dispersed phases.
  • the presence of the polylactic acid resin constituting a plurality of dispersed phases in this way is advantageous in that a molded product with a good appearance can be obtained when the container is molded.
  • the base layer preferably contains 1 phr or more and 5 phr or less of a white pigment. Furthermore, it is more preferable that the white pigment contained in the substrate layer is 1.5 phr or more and 4 phr or less.
  • the unit phr used herein refers to parts by weight of white pigment per 100 parts by weight of all resin components in the substrate layer. Containing 1 phr or more of the white pigment in the base material layer provides concealment, and when the resin sheet and its molded product are subjected to printing processing, it is possible to improve the printing color development, and furthermore, the light-shielding property is obtained.
  • the white pigment examples include titanium oxide (titanium white), zinc white (zinc white), lithopone, and lead white, among which titanium oxide is preferred.
  • the said white pigment may be used individually by 1 type, and may be used in combination of 2 or more types.
  • additive components include, in addition to the white pigment described above, a crystal nucleating agent for promoting crystallization of the polylactic acid resin, a compatibilizing agent for making different components compatible, other pigments, coloring agents such as dyes, and silicone oil. release agents such as alkyl esters, fibrous reinforcing agents such as glass fibers, granular lubricants such as talc, clay, silica, salt compounds of sulfonic acid and alkali metals, antistatic agents such as polyalkylene glycol, and ultraviolet rays Additives such as absorbents and antibacterial agents are included. Scrap resin generated in the manufacturing process of the resin sheet and the molded container according to one embodiment of the present invention can also be mixed.
  • the total content of polystyrene resin (butadiene rubber is also included in the polystyrene resin when it contains butadiene rubber) and polylactic acid resin in the base material layer is 90% by mass or more, typically is 95% by mass or more, more typically 98% by mass or more, and can be 100% by mass.
  • the thickness of the base layer is preferably 160-1200 ⁇ m, more preferably 180-1000 ⁇ m. Setting the thickness of the base material layer to 160 ⁇ m or more is advantageous in that the strength of the molded product obtained by molding the resin sheet can be ensured. Setting the thickness of the base material layer to 1200 ⁇ m or less is advantageous in that the cost of the resin sheet and its molded product such as a thermoformed container can be suppressed.
  • the skin layer is laminated on one side of the substrate layer.
  • the skin layer plays a role of protecting the substrate layer, and is preferably provided from the viewpoint of improving the impact resistance of the resin sheet.
  • the skin layer contains polystyrene resin. Containing a polystyrene-based resin in the skin layer in the same manner as the base layer is advantageous in terms of enhancing the impact resistance of the molded container and obtaining sufficient interlaminar adhesive strength with the base layer.
  • the skin layer contains a polystyrene-based resin containing butadiene rubber in order to increase the effect of improving the impact resistance of the resin sheet.
  • Embodiments of polystyrene-based resins suitable for the skin layer are the same as those for the base material layer, including polystyrene-based resins containing butadiene rubber, and detailed description thereof will be omitted.
  • the graft polymer described in the description of the base material layer that is, a polymer obtained by polymerizing a styrene monomer in the presence of polybutadiene, is used.
  • Obtained graft polymers such as high impact polystyrene (HIPS resin), polystyrene-acrylonitrile graft polymer (ABS resin), and the like can be used.
  • HIPS resin high impact polystyrene
  • ABS resin polystyrene-acrylonitrile graft polymer
  • One type of polystyrene resin may be used alone, or two or more types may be used in combination.
  • the skin layer may be appropriately blended with a polystyrene-based resin that does not contain butadiene rubber.
  • GPPS resin general-purpose polystyrene
  • HIPS resin high-impact polystyrene
  • a preferred embodiment of the butadiene rubber including the median diameter and content of the butadiene rubber in the skin layer is the same as that of the substrate layer, so the description is omitted.
  • additive components include compatibilizers that make different components compatible, colorants such as pigments and dyes, release agents such as silicon oil and alkyl esters, fibrous reinforcing agents such as glass fibers, talc, clay, and silica. and additives such as antistatic agents such as salt compounds of sulfonic acid and alkali metals, polyalkylene glycol, ultraviolet absorbers, and antibacterial agents.
  • compatibilizers that make different components compatible
  • colorants such as pigments and dyes
  • release agents such as silicon oil and alkyl esters
  • fibrous reinforcing agents such as glass fibers, talc, clay, and silica
  • additives such as antistatic agents such as salt compounds of sulfonic acid and alkali metals, polyalkylene glycol, ultraviolet absorbers, and antibacterial agents.
  • antistatic agents such as salt compounds of sulfonic acid and alkali metals, polyalkylene glycol, ultraviolet absorbers, and antibacterial agents.
  • the skin layer does not contain a poly
  • the total content of polystyrene-based resin (butadiene rubber is also included in the polystyrene-based resin when it contains butadiene rubber) in the skin layer is 80% by mass or more, typically 90% by mass or more. and more typically 95% by mass or more, and may be 100% by mass.
  • the total content of HIPS and GPPS in the skin layer is 80% by mass or more, typically 90% by mass or more, more typically 95% by mass or more, and 100% by mass. can also be
  • the average thickness of the skin layer is preferably 1% or more and 15% or less, more preferably 3% or more and 13% or less, and 5% or more and 10% or less of the average total thickness of the resin sheet. is even more preferred.
  • the average thickness of the skin layer is preferably 1% or more, more preferably 3% or more, and even more preferably 5% or more of the average total thickness of the resin sheet, thereby improving the impact resistance of the resin sheet. can be significantly exhibited.
  • the average thickness of the skin layer is preferably 15% or less, more preferably 13% or less, and even more preferably 10% or less with respect to the average total thickness of the resin sheet. Since the content of lactic acid resin is increased, it has the advantage of containing more biomass plastic material and being environmentally friendly.
  • the undercoat layer is laminated on the surface of the substrate layer opposite to the surface having the skin layer.
  • the undercoat layer plays a role of protecting the base layer in the same manner as the skin layer, and is preferably provided from the viewpoint of improving the impact resistance of the resin sheet.
  • the underlayer contains a polystyrene-based resin. Containing a polystyrene-based resin in the undercoat layer in the same manner as the base layer is advantageous in terms of enhancing the impact resistance of the molded container and obtaining sufficient interlaminar adhesive strength with the base layer.
  • the undercoat layer contains polystyrene resin containing butadiene rubber in order to increase the effect of improving the impact resistance of the resin sheet.
  • the lower skin layer may be provided symmetrically with the outer skin layer with the base material layer interposed therebetween.
  • the resin sheet has a symmetrical laminated structure in the thickness direction, so that when the resin sheet is attached to another article, it can be used without worrying about the front and back sides of the article, which improves ease of handling.
  • Embodiments of polystyrene-based resins suitable for the undercoat layer are the same as those for the base material layer, including polystyrene-based resins containing butadiene rubber, and detailed description thereof will be omitted.
  • a polystyrene resin containing butadiene rubber that can be suitably used for the undercoat layer
  • the graft polymer described in the description of the base material layer that is, a polymer obtained by polymerizing a styrene monomer in the presence of polybutadiene, can be used.
  • Obtained graft polymers such as high impact polystyrene (HIPS resin), polystyrene-acrylonitrile graft polymer (ABS resin), and the like can be used.
  • HIPS resin high impact polystyrene
  • ABS resin polystyrene-acrylonitrile graft polymer
  • One type of polystyrene resin may be used alone, or two or more types may be used in combination.
  • the undercoat layer may be appropriately blended with a polystyrene-based resin that does not contain butadiene rubber.
  • GPPS resin general-purpose polystyrene
  • HIPS resin high-impact polystyrene
  • a preferred embodiment of the butadiene rubber, including the median diameter and content of the butadiene rubber in the undercoat layer, is the same as that of the base material layer, so description thereof will be omitted.
  • additive components include compatibilizers that make different components compatible, colorants such as pigments and dyes, release agents such as silicon oil and alkyl esters, fibrous reinforcing agents such as glass fibers, talc, clay, and silica. and additives such as antistatic agents such as salt compounds of sulfonic acid and alkali metals, polyalkylene glycol, ultraviolet absorbers, and antibacterial agents.
  • compatibilizers that make different components compatible
  • colorants such as pigments and dyes
  • release agents such as silicon oil and alkyl esters
  • fibrous reinforcing agents such as glass fibers, talc, clay, and silica
  • additives such as antistatic agents such as salt compounds of sulfonic acid and alkali metals, polyalkylene glycol, ultraviolet absorbers, and antibacterial agents.
  • antistatic agents such as salt compounds of sulfonic acid and alkali metals, polyalkylene glycol, ultraviolet absorbers, and antibacterial agents.
  • the undercoat layer does not contain a
  • the total content of polystyrene-based resin (butadiene rubber is also included in the polystyrene-based resin when it contains butadiene rubber) in the undercoat layer is 80% by mass or more, typically 90% by mass or more. and more typically 95% by mass or more, and may be 100% by mass.
  • the total content of HIPS and GPPS in the hypodermal layer is 80% by weight or more, typically 90% by weight or more, more typically 95% by weight or more, and 100% by weight. can also be
  • the average thickness of the undercoat layer is preferably 1% or more and 15% or less, more preferably 3% or more and 13% or less, and 5% or more and 10% or less of the average total thickness of the resin sheet. is even more preferred.
  • the average thickness of the undercoat layer is preferably 1% or more, more preferably 3% or more, and even more preferably 5% or more of the average total thickness of the resin sheet, thereby improving the impact resistance of the resin sheet. can be significantly exhibited.
  • the average thickness of the undercoat layer is preferably 15% or less, more preferably 13% or less, and even more preferably 10% or less with respect to the average total thickness of the resin sheet. Since the content of lactic acid resin is increased, it has the advantage of containing more biomass plastic material and being environmentally friendly.
  • the average thickness of the hypodermis layer can match the average thickness of the epidermis layer.
  • the average total thickness of the resin sheet is preferably 200 ⁇ m or more and 1300 ⁇ m or less, more preferably 300 ⁇ m or more and 1200 ⁇ m or less, and 500 ⁇ m or more and 900 ⁇ m, regardless of whether the resin sheet has a single-layer structure or a multi-layer structure. It is even more preferred that: By setting the average total thickness of the resin sheet to preferably 200 ⁇ m or more, more preferably 300 ⁇ m or more, and even more preferably 500 ⁇ m or more, the strength of the molded product obtained by molding the resin sheet can be ensured. For example, the sides or bottom of a container obtained by thermoforming can have a sufficient thickness, and a sufficient strength of the container can be obtained.
  • the thickness of the resin sheet By setting the thickness of the resin sheet to 1,300 ⁇ m or less, more preferably 1,200 ⁇ m or less, and even more preferably 900 ⁇ m or less, the cost of the resin sheet and its molded product such as a thermoformed container can be suppressed.
  • the resin sheet preferably has a biomass content of 0.1% by mass or more and 20% by mass or less, more preferably 3% by mass or more and 15% by mass or less, and preferably 5% by mass or more and 13% by mass or less. Even more preferred.
  • the biomass content of the resin sheet is preferably 0.1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, the environmental performance of the resin sheet can be enhanced.
  • the biomass degree of the resin sheet is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably. is 13% by mass or less.
  • the biomass degree of the resin sheet refers to the ratio of the biobased carbon content to the total carbon content (TO) measured by the biobased concentration test in accordance with ASTM D6866-05.
  • the resin sheet preferably has a DuPont impact strength of 2.0 J or more, more preferably 2.5 J or more, and even more preferably 2.9 J or more, as measured according to JIS K7211-1:2006.
  • the upper limit of the DuPont impact strength is not particularly limited, but can be, for example, 4.0 J or less, typically 3.5 J or less. Therefore, in one embodiment, the resin sheet has a DuPont impact strength of 2.0 to 4.0 J as measured according to JIS K7211-1:2006.
  • the DuPont impact strength is measured under a drop load of 300 g and a measurement environment of 23° C. ⁇ 50%R. H. refers to the 50% breaking energy E50 (J) when subjected to the DuPont impact test below.
  • the resin sheet conforms to JIS P8115:2001, and when a test piece whose longitudinal direction is parallel to the MD direction is taken and subjected to the folding endurance test method, the average number of reciprocating bending times until breakage is less than 300 times. is preferably less than 200 times, more preferably less than 100 times, even more preferably less than 50 times, and most preferably less than 10 times.
  • the resin sheet conforms to JIS P8115: 2001, and when a test piece whose longitudinal direction is parallel to the TD direction is taken and subjected to the folding endurance test method, the number of reciprocating bending times until breakage is less than 300 times on average. is preferably less than 200 times, more preferably less than 100 times, even more preferably less than 50 times, and most preferably less than 10 times.
  • the folding endurance when a test piece whose longitudinal direction is parallel to the MD direction is taken from the resin sheet and the above-mentioned folding endurance test method is performed (hereinafter, also referred to as "folding endurance in the MD direction” ) is the folding endurance when a test piece whose longitudinal direction is parallel to the TD direction is taken from the resin sheet and the above folding endurance test method is performed (hereinafter, also referred to as "folding endurance in the TD direction” ) tends to be larger than
  • the layer structure of the resin sheet is not limited to the laminated structure shown in FIG.
  • each layer may have a configuration of two or more layers.
  • the resin sheet is composed of a layer that is finely pulverized and returned, or a recycled material that is repelletized after heat melting, without discarding the part called scrap generated in the process of manufacturing molded products such as resin sheets and molded containers. You may provide a new layer to return inside.
  • FIG. 2 schematically shows the cross-sectional structure of a resin sheet 20 according to another embodiment of the invention.
  • the resin sheet 20 has a layered structure in which skin layer 11/adhesive layer 14a/oxygen barrier layer 15/adhesive layer 14b/base layer 12/back layer 13 are laminated in this order from the top to the bottom of the page.
  • the oxygen barrier layer 15 is laminated to the skin layer 11 and the base layer 12 via the adhesive layers 14a and 14b, while the base layer 12 and the base layer 13 are laminated directly.
  • the skin layer 11, the base material layer 12, and the underlayer 13 are as described in detail in relation to the embodiment shown in FIG.
  • the adhesive layers 14a and 14b of this embodiment contain an adhesive.
  • the adhesive is not limited, a polyolefin-based adhesive is preferable from the viewpoint of laminating different resin layers.
  • the polyolefin-based adhesive preferably contains a modified polyolefin-based polymer, and representative examples thereof include modified homopolymers of olefins having about 2 to 8 carbon atoms such as ethylene, propylene and butene-1, Those olefins and other olefins (e.g.
  • olefins of about 2 to 20) and/or modified copolymers with vinyl compounds (e.g., vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, polystyrene, etc.), and Modified polyolefin rubbers such as ethylene-butene-1 copolymer and propylene-butene-1 copolymer can be mentioned.
  • vinyl compounds e.g., vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, polystyrene, etc.
  • Modified polyolefin rubbers such as ethylene-butene-1 copolymer and propylene-butene-1 copolymer can be mentioned.
  • Modification methods include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and tetrahydrophthalic acid, or their acid halides, amides, imides, Derivatives such as anhydrides and esters, specifically malenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate, etc., are used for acid modification under graft reaction conditions. is mentioned.
  • One type of adhesive may be used alone, or two or more types may be used in combination.
  • modified polyolefin polymers include, among others, ethylene-based resins, propylene-based resins, ethylene-propylene copolymer rubbers and ethylene-butene-1 copolymers modified with unsaturated dicarboxylic acids or their anhydrides, especially maleic acid or their anhydrides. It is preferable to use one or more selected from polymer rubbers.
  • each of the adhesive layers 14a and 14b is preferably 2-30 ⁇ m, more preferably 5-20 ⁇ m.
  • the thickness of the adhesive layers 14a and 14b is preferably 2-30 ⁇ m, more preferably 5-20 ⁇ m.
  • additives other than adhesives may be added to the adhesive layers 14a and 14b as long as they do not impair the effects of the present invention.
  • additive components include colorants such as pigments and dyes, release agents such as silicon oil and alkyl esters, fibrous reinforcing agents such as glass fibers, granular lubricants such as talc, clay and silica, sulfonic acid and alkali metals.
  • Antistatic agents such as salt compounds such as polyalkylene glycol, ultraviolet absorbers, and additives such as antibacterial agents.
  • the adhesive content in the adhesive layers 14a, 14b is 80% by mass or more, typically 90% by mass or more, more typically 95% by mass or more, and 100% by mass or more.
  • the content of the modified polyolefin polymer in the adhesive layers 14a and 14b is 80% by mass or more, typically 90% by mass or more, and more typically 95% by mass or more. , 100 mass %.
  • the oxygen barrier layer 15 of this embodiment contains an oxygen barrier resin in order to impart oxygen barrier properties to the multilayer resin sheet.
  • oxygen barrier resins include, but are not limited to, ethylene-vinyl alcohol copolymer, polyamide, polyvinyl alcohol, and polyvinylidene chloride.
  • the oxygen barrier resin may be used alone or in combination of two or more. Among them, ethylene-vinyl alcohol copolymer resin is preferable in terms of extrusion moldability.
  • Ethylene-vinyl alcohol copolymers are usually obtained by saponifying ethylene-vinyl acetate copolymers. , preferably 20 to 50 mol%, and a degree of saponification of 90 mol% or more, preferably 95 mol% or more.
  • polyamides include lactam polymers such as caprolactam and laurolactam, polymers of aminocarboxylic acids such as 6-aminocaproic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, hexamethylenediamine, decamethylenediamine, dodeca aliphatic diamines such as methylenediamine, 2,2,4- or 2,4,4-trimethylhexamethylenediamine, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis(p-aminocyclohexylmethane) Diamine units such as alicyclic diamines such as m- or p-xylylenediamine, aromatic diamines such as m- or p-xylylenediamine, aliphatic dicarboxylic acids such as adipic acid, suberic acid and sebacic acid, alicyclic dicarboxylic acids such as cyclohexane
  • polyamide resins include nylon 6, nylon 9, nylon 11, nylon 12, nylon 66, nylon 610, nylon 611, nylon 612, nylon 6T, nylon 6I, nylon MXD6, nylon 6/66, nylon 6/ 610, nylon 6/6T, nylon 6I/6T, etc. Among them, nylon 6 and nylon MXD6 are preferable.
  • the oxygen barrier layer 15 may contain a resin other than the oxygen barrier resin described above, and may contain various additive components other than the resin component, as long as the effects of the present invention are not hindered. be done.
  • additive components include colorants such as pigments and dyes, release agents such as silicon oil and alkyl esters, fibrous reinforcing agents such as glass fibers, granular lubricants such as talc, clay and silica, sulfonic acid and alkali metals.
  • Antistatic agents such as salt compounds such as polyalkylene glycol, ultraviolet absorbers, and additives such as antibacterial agents.
  • the content of the oxygen barrier resin in the oxygen barrier layer 15 is 80% by mass or more, typically 90% by mass or more, and more typically 95% by mass or more. It can also be 100% by mass.
  • the content of the ethylene-vinyl alcohol copolymer resin in the oxygen barrier layer 15 is 80% by mass or more, typically 90% by mass or more, and more typically 95% by mass or more. and can be 100% by mass.
  • the thickness of the oxygen barrier layer 15 is preferably 1-50 ⁇ m, more preferably 5-30 ⁇ m. Setting the thickness of the oxygen barrier layer 15 to 1 ⁇ m or more is advantageous from the viewpoint of enhancing the oxygen barrier properties of the multilayer resin sheet. In addition, by setting the thickness of the oxygen barrier layer 15 to 50 ⁇ m or less, the oxygen barrier layer 15 is easily stretched when the multilayer resin sheet is molded into a container or the like, and a smoother thickness of the molded product can be secured, resulting in a better appearance. It is possible to obtain a molded product with
  • the method for producing the resin sheet according to the present invention is not particularly limited, and a general method for molding a resin sheet can be used.
  • a general method for molding a resin sheet can be used.
  • it can be produced by a melt extrusion molding method or a melt co-extrusion molding method in which one or more resins are adhesively laminated in a molten state using one or more extruders.
  • a multilayer resin sheet is obtained, specifically, three or more single-screw or twin-screw extruders are used to melt-extrude raw materials for each layer, and a feed block with a selector plug and a T-die are used to form a multilayer resin sheet. and a method of obtaining a multilayer resin sheet using a multi-manifold die.
  • the resin sheet according to the invention is thermoformable. Accordingly, according to one embodiment of the present invention, there is provided a molded article comprising a resin sheet.
  • the type of molded article is not particularly limited, but examples include molded containers such as packs, cups and trays for beverages, foods (including seasonings), cosmetics, home appliances and other daily necessities.
  • the resin sheet can form part or all of the molded container in one embodiment.
  • packaging containers for foods are mentioned as a preferred embodiment.
  • Some packaging containers for food are provided with a connecting part for connecting a plurality of containers, and a notch (hereinafter referred to as "notch") is formed in the connecting part for separating the respective containers. be.
  • Dispensing package in which a notch is formed in the lid in order to discharge the food packaged inside the packaging container to the outside of the packaging container.
  • Dispensing packages can easily extract liquid, paste, granular or powdery contents such as food products such as seasonings and beverages as well as cosmetics and medicines by pinching and bending with fingers. It is a small food packaging container that can be
  • the resin sheet that constitutes the molded container according to one embodiment of the present invention may have notches.
  • the notch may be formed from either surface of the substrate layer in the case of a single-layer resin sheet, and may be formed from either the skin layer or the bottom layer in the case of a multilayer resin sheet.
  • the outer skin layer 11 or the lower skin layer 13 may be placed on the outer surface side.
  • part or all of the molded container is constructed such that the skin layer 11 is positioned on the outer surface side of the molded container and the lower skin layer 13 is positioned on the inner surface side of the molded container.
  • the distribution package includes a hard material lid having a notch called a "half-cut portion" in the center of the surface and a protrusion for facilitating extraction of the contents, and the lid. It is common to have a flexible member container body having a peripheral edge secured to the back surface and forming pockets on either side of the fold line.
  • the resin sheet according to the present invention can be molded into a lid of a dispensing package.
  • the skin layer 11 is positioned on the back side of the lid (the side that comes into contact with food), and the subskin layer 13 is positioned on the front side of the lid. It is preferred to manufacture the dispensing package at
  • Thermoforming methods for resin sheets include general vacuum forming and pressure forming.
  • a method called so-called match mold molding, in which a pair of male and female molds are brought into contact with each other to carry out thermoforming, may be used, but the present invention is not limited to these methods.
  • a known sheet heating method such as radiation heating by an infrared heater, which is non-contact heating, can be applied.
  • the resin sheet is produced by consistently performing a thermoforming step, a step of filling the contents, and a step of heat-sealing a cover film as a lid material, and then punching out a packaging container to produce a product. It can be suitably used for so-called form-fill-seal (FFS) packaging.
  • FFS form-fill-seal
  • each raw material of the base layer shown in Tables 1 and 2 according to the test number is melt-extruded by the T-die method, cooled and solidified with a cooling roll, and then transported with a take-up machine. Then, it was wound into a roll with a winder. As a result, a single-layer resin sheet having a flow direction (MD direction) of 30 m and a width direction (TD direction) of 800 mm was obtained.
  • MD direction flow direction
  • TD direction width direction
  • MIT testing machine Model MIT-D manufactured by Toyo Seiki Co., Ltd. Measurement conditions: With a load (500 g) applied, reciprocating bending is performed by bending the test piece at an angle of 135 ⁇ 2 ° C to the left and right of the vertical line at a speed of 175 ⁇ 10 times per minute, and the test The number of times of reciprocating bending (number of folding endurance) until the piece broke was measured. Each test was performed on five test pieces, and an average value was obtained.
  • the folding endurance of the resin sheet before thermoforming was evaluated here, it was found that the folding endurance of the resin sheet before thermoforming has the same tendency as the fragility of the thermoformed product provided with the resin sheet. is known.
  • the folding endurance was evaluated according to the following three levels.
  • the multilayer resin sheets of Comparative Examples 1 and 2 contain polylactic acid resin and are excellent in environmental performance. However, in the multilayer resin sheets of Comparative Examples 1 and 2, since the content of the butadiene rubber in the base material layer was excessive, the number of folding endurances increased (that is, the notch folding resistance was poor). On the other hand, the multilayer resin sheets of Examples 1 to 8 had an appropriate content of butadiene rubber in the substrate layer and an appropriate median diameter. However, the folding endurance was low (that is, the notch folding property was good) and the impact strength was high.
  • the single-layer resin sheets of Comparative Examples 3 and 4 contain polylactic acid resin and are excellent in environmental performance.
  • the content of butadiene rubber in the base material layer was excessive, and crack propagation during bending was inhibited by the butadiene rubber, resulting in increased folding endurance.
  • the single-layer resin sheet of Comparative Example 4 had insufficient impact strength because the content of butadiene rubber in the substrate layer was too small.
  • the single-layer resin sheet of Comparative Example 5 has a biomass degree of 0% and is insufficient in environmental performance.
  • the median diameter of the butadiene rubber in the base material layer was large, and the number of times of folding endurance was increased (that is, the notch folding resistance was poor).
  • the single-layer resin sheet of Example 9 both the content of butadiene rubber in the substrate layer and the median diameter were appropriate. From this, the single-layer resin sheet of Example 9 had excellent environmental performance, but had a small number of times of folding (that is, good notch folding resistance) and high impact strength.
  • Examples 1 to 8 are multilayer resin sheets having a skin layer and a bottom layer, so compared with Example 9, It can be seen that the impact resistance was improved. Further, when comparing the examples, it can be seen that the example with a lower content of polylactic acid resin tends to have a lower number of folding endurances.

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Abstract

La présente invention aborde le problème de la fourniture d'une feuille de résine comprenant une résine à base de polystyrène et une résine d'acide polylactique, la feuille de résine étant excellente en termes de capacité de pliage de partie entaillée et de résistance aux chocs. La feuille de résine comprend une couche de base qui comprend à la fois une résine à base de polystyrène contenant du caoutchouc de butadiène et une résine d'acide polylactique, et dans laquelle le caoutchouc de butadiène a un diamètre médian inférieur à 6 µm et dont la teneur en caoutchouc de butadiène est de 3,0 à 7,0 % en masse.
PCT/JP2022/033789 2021-09-17 2022-09-08 Feuille de résine et récipient formé WO2023042753A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008050426A (ja) * 2006-08-23 2008-03-06 Ps Japan Corp スチレン系樹脂とポリ乳酸からなる樹脂組成物
JP2018048248A (ja) * 2016-09-21 2018-03-29 東洋スチレン株式会社 樹脂組成物、樹脂組成物の製造方法、樹脂組成物から得られる成形体および成形体の製造方法
WO2020137842A1 (fr) * 2018-12-26 2020-07-02 東洋スチレン株式会社 Feuille de composition de résine styrénique et article moulé
JP2021011524A (ja) * 2019-07-04 2021-02-04 Ｐｓジャパン株式会社 樹脂組成物および成形体
WO2021111815A1 (fr) * 2019-12-03 2021-06-10 デンカ株式会社 Feuille de résine multicouche et récipient de moulage
JP2021155650A (ja) * 2020-03-30 2021-10-07 デンカ株式会社 シート及び容器本体

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008050426A (ja) * 2006-08-23 2008-03-06 Ps Japan Corp スチレン系樹脂とポリ乳酸からなる樹脂組成物
JP2018048248A (ja) * 2016-09-21 2018-03-29 東洋スチレン株式会社 樹脂組成物、樹脂組成物の製造方法、樹脂組成物から得られる成形体および成形体の製造方法
WO2020137842A1 (fr) * 2018-12-26 2020-07-02 東洋スチレン株式会社 Feuille de composition de résine styrénique et article moulé
JP2021011524A (ja) * 2019-07-04 2021-02-04 Ｐｓジャパン株式会社 樹脂組成物および成形体
WO2021111815A1 (fr) * 2019-12-03 2021-06-10 デンカ株式会社 Feuille de résine multicouche et récipient de moulage
JP2021155650A (ja) * 2020-03-30 2021-10-07 デンカ株式会社 シート及び容器本体

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