WO2017145290A1 - Feuille pour thermoformage, et plateau pour aliment - Google Patents

Feuille pour thermoformage, et plateau pour aliment Download PDF

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Publication number
WO2017145290A1
WO2017145290A1 PCT/JP2016/055459 JP2016055459W WO2017145290A1 WO 2017145290 A1 WO2017145290 A1 WO 2017145290A1 JP 2016055459 W JP2016055459 W JP 2016055459W WO 2017145290 A1 WO2017145290 A1 WO 2017145290A1
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WO
WIPO (PCT)
Prior art keywords
sheet
tray
polypropylene
extruder
acid
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Ceased
Application number
PCT/JP2016/055459
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English (en)
Japanese (ja)
Inventor
弘明 高畑
坂口　正英
史和 松下
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Totaku Industries Inc
Nagase and Co Ltd
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Totaku Industries Inc
Nagase and Co Ltd
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Publication date
Application filed by Totaku Industries Inc, Nagase and Co Ltd filed Critical Totaku Industries Inc
Priority to PCT/JP2016/055459 priority Critical patent/WO2017145290A1/fr
Publication of WO2017145290A1 publication Critical patent/WO2017145290A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters

Definitions

  • the present invention relates to a thermoforming sheet and a food tray.
  • Polypropylene is generally used as a container for storing the frozen food.
  • Polypropylene is excellent in thermoformability required for thermoforming the tray and heat resistance required for cooking in a microwave oven.
  • Patent Document 1 discloses an olefin-based sheet containing polypropylene having excellent heat resistance and cold resistance.
  • heat resistance when a sheet is heated at 130 ° C. is evaluated.
  • the present invention provides a thermoforming sheet that can sufficiently prevent punching of a tray when cooked and cooked, and a food tray using the same even when the frozen food contains a large amount of oily components. For the purpose.
  • thermoforming sheet in which two or more layers are laminated, wherein one outermost layer in the thermoforming sheet contains a crystalline polyester and the other outermost layer contains polypropylene. Sheet for molding.
  • thermoforming sheet according to [1] wherein the outermost layer containing the crystalline polyester has a thickness of 10 ⁇ m or more, and the thermoforming sheet has a thickness of 200 ⁇ m or more.
  • a food tray for containing food having the thermoforming sheet according to [1] or [2], and an outermost layer containing crystalline polyester positioned on a surface in contact with the food Tray for food.
  • thermoforming sheet that can sufficiently prevent punching of a tray when heated and cooked even when the frozen food contains a large amount of oily components, and a food tray using the same. can do.
  • thermoforming sheet of the present embodiment (hereinafter also simply referred to as “sheet”) is formed by laminating two or more layers.
  • one outermost layer contains crystalline polyester and the other outermost layer contains polypropylene.
  • polyesters As the crystalline polyester, conventionally known polyesters can be used. Specific examples thereof include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polypropylene naphthalate and polybutylene naphthalate. Among these, polyethylene terephthalate is preferable from the viewpoint of further improving the tray hole opening suppressing effect.
  • dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, diphenylcarboxylic acid, Diphenoxyethanedicarboxylic acid, diphenylsulfonecarboxylic acid, anthracenedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, Malonic acid,
  • Diols include ethylene glycol, propylene glycol, hexamethylene glycol, neopentyl glycol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, decamethylene glycol, 1,3-propanediol, 1,4-butane. Examples thereof include diol, 1,5-pentanediol, 1,6-hexadiol, 2,2-bis (4-hydroxyphenyl) propane, and bis (4-hydroxyphenyl) sulfone.
  • the dicarboxylic acid component and the diol component constituting the polyester resin may each be used alone or in combination of two or more. Further, other acid components such as trimellitic acid and other hydroxyl components such as trimethylolpropane may be appropriately added.
  • Polyester copolymerized using isophthalic acid as the dicarboxylic acid and 1,4-cyclohexanedimethanol as the diol and copolymerized within a range having crystallinity can also be used.
  • the content of the crystalline polyester in the outermost layer containing the crystalline polyester is preferably 70% by mass or more, more preferably 85% by mass or more, further preferably 95% by mass or more, and the outermost layer is crystalline. It is particularly preferable that the polyester consists only of a reactive polyester.
  • the thickness of the outermost layer containing crystalline polyester is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and even more preferably 20 ⁇ m or more, from the viewpoint of further improving the tray hole opening suppressing effect.
  • the upper limit of the thickness of this outermost layer is not specifically limited, For example, it can be 150 micrometers or less.
  • a conventionally well-known thing can be used as a polypropylene.
  • a random copolymer with an ⁇ -olefin containing ethylene that can be copolymerized with propylene may be used.
  • the amount of the copolymer component increases, the melting point of polypropylene decreases, and there is a concern that the heat resistance when used as a tray decreases.
  • the polypropylene of this embodiment preferably has a melting point of 135 ° C. or higher determined by the DSC method, and within this range, the comonomer species and amount can be selected, and similarly, stereoregularity such as isotactic, syndiotactic, or atactic. And the degree thereof can be selected.
  • a block copolymer containing various elastomers such as ethylene-propylene copolymer rubber can be used as the polypropylene of the present embodiment.
  • the polypropylene of the present embodiment is a block copolymer having an elastomer component, and has a melting point as a resin of 150 ° C. or higher and an MFR of 2 (g / 10 min) or lower at 230 ° C. and a load of 2.16 kg.
  • Polypropylene is preferable from the viewpoint of heat resistance, impact resistance, or thermoformability.
  • the outermost layer containing polypropylene of the present embodiment is preferably formed by forming a polypropylene film containing 90% by weight or more of a structural unit made of propylene into a film.
  • the polypropylene may be a homopolymer of propylene, or may be a copolymer of propylene and another monomer copolymerizable therewith. These may be used in combination.
  • Examples of other monomers copolymerizable with propylene include ethylene and ⁇ -olefin.
  • the ⁇ -olefin has 4 or more carbon atoms, preferably an ⁇ -olefin having 4 to 12 carbon atoms.
  • ⁇ -olefin having 4 to 12 carbon atoms include linear monoolefins such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and 1-decene; Branched monoolefins such as 3-methyl-1-butene, 3-methyl-1-pentene and 4-methyl-1-pentene; vinylcyclohexane and the like.
  • the copolymer of propylene and other monomers copolymerizable therewith may be a random copolymer or a block copolymer.
  • polypropylene is a copolymer
  • specific examples of the copolymer include propylene-ethylene random copolymer, propylene-1-butene random copolymer, and propylene-ethylene-1-butene random copolymer.
  • examples thereof include binary to ternary copolymers of propylene, ethylene, and one or more monomers selected from the group consisting of C 4-12 ⁇ -olefins.
  • the structural unit derived from propylene can be selected according to characteristics such as heat resistance.
  • characteristics such as heat resistance.
  • the content rate of the structural unit derived from the said other monomer in a copolymer is infrared (IR) according to the method described on page 616 of "Polymer Analysis Handbook" (1995, published by Kinokuniya). ) It can be obtained by performing a spectrum measurement.
  • the stereoregularity of the propylene homopolymer and propylene copolymer may be isotactic, syndiotactic, or atactic. However, from the viewpoint of excellent balance of rigidity and transparency after being formed into a film, Highly tactic polypropylene is preferred.
  • polypropylene may be a polymer or copolymer polymerized using a known polymerization catalyst
  • the polymerization catalyst include the following.
  • C Metallocene catalyst.
  • solid catalyst component (A) examples include catalyst systems described in JP-A-61-218606, JP-A-61-287904, JP-A-7-216017, and the like.
  • organoaluminum compound in the catalyst system of (B) include triethylaluminum, triisobutylaluminum, a mixture of triethylaluminum and diethylaluminum chloride, tetraethyldialumoxane, etc.
  • Examples include cyclohexylethyldimethoxysilane, tert-butylpropyldimethoxysilane, tert-butylethyldimethoxysilane, dicyclopentyldimethoxysilane, and the like.
  • Examples of the metallocene catalyst (C) include catalyst systems described in Japanese Patent No. 2587251, Japanese Patent No. 2627669, Japanese Patent No. 2668732, and the like.
  • Polypropylene is, for example, a solution polymerization method using an inert solvent typified by a hydrocarbon compound such as hexane, heptane, octane, decane, cyclohexane, methylcyclohexane, benzene, toluene, and xylene, and a bulk using a liquid monomer as a solvent. It can be produced by a polymerization method or a gas phase polymerization method in which a gaseous monomer is polymerized as it is. Polymerization by these methods may be carried out batchwise or continuously.
  • an inert solvent typified by a hydrocarbon compound such as hexane, heptane, octane, decane, cyclohexane, methylcyclohexane, benzene, toluene, and xylene, and a bulk using a liquid monomer as a solvent. It can be produced by a
  • the polypropylene of this embodiment forms a part of the multilayer sheet of this embodiment and is mainly thermoformed and used as a tray.
  • Thermoforming includes forming methods such as vacuum forming, pressure forming, vacuum / pressure forming, and match molding. For example, when vacuum forming is applied, after heating with a heater from the top and bottom of the sheet, it is pressed against the mold in a vacuum and formed into a shape along the mold. In this heater heating process, dripping occurs (draw down) )
  • the polypropylene of this embodiment may have a melt flow rate (MFR) measured at a temperature of 230 ° C. and a load of 21.18 N in a range of 10 g / 10 min or less in accordance with JIS K7210. Preferably, it is in the range of 0.01 to 8 g / 10 minutes.
  • MFR melt flow rate
  • polyethylene can be added to the polypropylene of this embodiment.
  • a composition containing about 5 to 30% by weight of polyethylene not only can dripping be suppressed in thermoforming such as vacuum molding, but it can be used at -20 ° C or lower as a food tray after molding. This is preferable because the impact properties can be greatly improved.
  • this polyethylene general polyethylene such as linear low density polyethylene, low density polyethylene, and high density polyethylene can be used.
  • polyethylene having an MFR value measured at 190 ° C. and a load of 2.16 kg in accordance with JIS K7210 is preferably 0.02 to 4 g / 10 min or less, and more preferably. Is 0.05 to 2 g / 10 min or less.
  • a nucleating agent may be added to polypropylene in order to further enhance the effect of this embodiment.
  • a nucleating agent either an inorganic nucleating agent or an organic nucleating agent may be used.
  • the inorganic nucleating agent include talc, clay, calcium carbonate and the like.
  • the organic nucleating agent include metal salts such as aromatic carboxylic acid metal salts and aromatic phosphoric acid metal salts, poly-3-methylbutene-1, polycyclopentene, and polyvinylcyclohexane.
  • organic nucleating agents are preferable, and the above-described metal salts and high density polyethylene are more preferable.
  • the addition amount of the nucleating agent with respect to polypropylene is preferably 0.01 to 3% by weight, more preferably 0.05 to 1.5% by weight. A plurality of these additives may be used in combination. Further, it is preferable to contain talc in an amount of 5 to 30% by weight, not as a nucleating agent, in order to give rigidity at high temperatures.
  • a well-known additive may be mix
  • the additive include an antioxidant, an ultraviolet absorber, an antistatic agent, a lubricant, an antifogging agent, and an antiblocking agent.
  • antioxidants include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, hindered amine light stabilizers, and the like, and for example, phenolic antioxidant mechanisms in one molecule. It is also possible to use a composite antioxidant having a unit having both a phosphorus-based antioxidant mechanism and a phosphorus-based antioxidant mechanism.
  • UV absorber examples include known UV absorbers such as 2-hydroxybenzophenone derivatives and hydroxyphenylbenzotriazole derivatives, UV absorbers, benzoate UV blockers, and the like.
  • the antistatic agent may be polymer type, oligomer type or monomer type.
  • the lubricant include higher fatty acid amides such as erucic acid amide and oleic acid amide, higher fatty acids such as stearic acid, and salts thereof.
  • the anti-blocking agent fine particles having a spherical shape or a shape close thereto can be used regardless of inorganic type or organic type.
  • the outermost layer containing polypropylene may be a foamed layer.
  • the expansion ratio is not particularly limited, but can be 2 to 10 times.
  • the thickness of the foamed layer can be 0.5 to 2 mm.
  • the content of polypropylene in the outermost layer containing polypropylene is preferably 70% by mass or more, more preferably 85% by mass or more, still more preferably 95% by mass or more, and the outermost layer is made of only polypropylene. Is particularly preferred.
  • the thickness of the outermost layer containing polypropylene is not particularly limited, but can be, for example, 100 ⁇ m or more, and can be 200 ⁇ m or more and 2000 ⁇ m or less.
  • the outermost layer containing crystalline polyester and the outermost layer containing polypropylene may be directly laminated, but are preferably bonded via an intermediate layer for bonding them.
  • a commercially available adhesive or a layer made of an adhesive resin can be used.
  • the adhesive used for the intermediate layer conventionally known adhesives can be used, and specific examples thereof include aliphatic polyester adhesives, aromatic polyester adhesives, aliphatic polyether adhesives, aromatics. Examples include polyether adhesives and polyethyleneimine. Of these, aliphatic polyester-based adhesives are most preferable from the viewpoint of high adhesiveness and ease of use for food applications.
  • the thickness of the intermediate layer in the case where an adhesive is used as the intermediate layer is not particularly limited.
  • the thickness in the sheet up to thermoforming can be 0.5 ⁇ m or more and 4 ⁇ m or less.
  • middle layer is a layer which consists of adhesive resin.
  • Specific examples thereof include a binary or ternary copolymer of ethylene and (meth) acrylic acid, (meth) acrylic acid ester, vinyl acetate, glycidyl (meth) acrylate, and maleic anhydride-modified polyethylene. Further, maleic anhydride-modified polyolefin such as maleic anhydride polypropylene can be used.
  • the thickness of the intermediate layer in the case where an adhesive resin is used as the intermediate layer is not particularly limited. For example, the thickness in the sheet until thermoforming can be 3 ⁇ m or more and 100 ⁇ m or less.
  • the sheet of the present embodiment includes a layer other than the above-mentioned two outermost layers and an intermediate layer, for example, a gas barrier resin layer such as ethylene-vinyl alcohol copolymer and polyamide, and a gas barrier resin layer and a re-outer layer as necessary.
  • the intermediate layer may be the same as the above intermediate layer for adhesion, or another intermediate layer may be used.
  • the thickness of the sheet according to the present embodiment can be 200 ⁇ m or more, preferably 300 ⁇ m or more, more preferably 400 ⁇ m or more, and more preferably 500 ⁇ m or more, from the viewpoint of rigidity when a tray is formed. Is more preferable.
  • seat is not specifically limited, For example, it can be 2100 micrometers or less.
  • the polypropylene or other resin constituting the sheet of this embodiment is composed of parts other than the both ends of the sheet cut and removed for width adjustment at the time of manufacturing the sheet and the part formed on the tray in thermoforming.
  • a so-called lossy sheet-like material crushed or remelted (recycled material) can also be included as long as the effects of the present invention are not impaired.
  • the addition ratio of the recycled material is preferably about 40 wt% or less, and the resin to which the recycled material is added is a resin that forms a polypropylene layer or an intermediate layer when an adhesive resin is used for the intermediate layer. It is preferable to add to the resin.
  • this recycled material is a composition composed of a large number of resins, there is a possibility that the breaking strength as a resin, impact strength may be low, in which case, a resin called a compatibilizing agent is added and remelted. It can also be pelletized. Further, an extruder for recycled material may be installed at the time of sheet forming, and a recycled layer made of recycled material may be provided. In this case, the content of the recycled material is preferably 10 wt% or more.
  • the moisture content in the resin is 3000 ppm or less, preferably 1000 ppm or less by drying the resin. More preferably, it is 300 ppm or less. It is a viewpoint which can suppress the hydrolysis by the water
  • the means for drying the resin is not limited, and a general dryer, a dehumidifying dryer, a vacuum dryer, an N 2 reflux dehumidifying dryer, or the like can be used as appropriate.
  • the sheet of this embodiment can be manufactured by a known lamination molding method such as a co-extrusion T-die melt extrusion method, an extrusion lamination method, or a dry lamination method.
  • the intermediate layer using the adhesive resin described above can be applied to the co-extrusion T-die melt extrusion method or the extrusion lamination method, and the intermediate layer using the adhesive can be applied to dry lamination. .
  • forming by the co-extrusion T-die melt extrusion method is preferable in terms of cost and productivity.
  • This co-extrusion T-die melt extrusion method includes a necessary number of extruders, each extruder is connected to one T-die, and a resin is laminated from the T-die to form a film, and a cooling roll This is a method for producing a multilayer sheet by cooling and solidification.
  • a polypropylene / maleic anhydride modified polyolefin / crystalline polyester component is described below as an example.
  • the three extruders are heated to about 180 to 330 ° C., respectively, and polypropylene, maleic anhydride-modified polyolefin, and crystalline polyester powder or pellets are supplied to each extruder. Melted and kneaded by the screw of each extruder, supplied to a feed block or converting adapter installed upstream of the T die, entered into the T die in the order of the multilayer structure of the final film, and sheet-like in the T die Then, after being melt coextruded into a sheet shape from the slit at the tip of the T die, the multilayer sheet is manufactured by contacting with a cooling roll by various means and cooling.
  • the temperature of the molten sheet containing polypropylene to be coextruded is preferably about 180 to 300 ° C. If the temperature of the molten sheet-like material at this time is lower than 180 ° C., the spreadability is not sufficient, the thickness of the obtained film becomes non-uniform, and there is a possibility that the film has retardation unevenness. Further, when the temperature exceeds 300 ° C., the resin is easily deteriorated or decomposed, and bubbles may be generated in the sheet or carbides may be contained.
  • Each of the three extruders may be a single screw extruder or a twin screw extruder, and the extruders may not be unified. Further, when the size of the extruder is selected depending on the composition ratio of the multilayer sheet of each layer, it may be preferable because it can be manufactured with the most stable extrusion amount.
  • Each resin melt-kneaded by each extruder passes through a temperature-controlled single pipe called an adapter and is sent to a T die.
  • the T-die can be selected from a type in which the internal flow path has one type or a plurality of flow paths.
  • each of the extruders passes through a single pipe and is then supplied to the converting adapter, where it is rearranged into a predetermined layer configuration and then the corresponding flow in the T die.
  • Each is sent to the road. Then, each is individually expanded to the width of the T die and then laminated and extruded from the T die in a sheet form. The latter is called a multi-manifold type.
  • the crystalline polyester resin and the resin containing polypropylene have greatly different melt viscosities, so that they have a good appearance and have a predetermined layer structure. It is preferable to use this type of T-die in order to reliably manufacture.
  • a gear pump is installed between each extruder and the T die to stabilize the pressure and supply the resin to the T die. can do.
  • the pressure at this time is preferably within 0.3 MPa as a fluctuation value.
  • a metal mesh held by a breaker plate or a sintered mesh made of metal fibers can be attached to the tip of each extruder.
  • a metal mesh a metal mesh of 400 mesh or less can be used, and in the case of a metal fiber sintered mesh, one having a filtration accuracy of 200 ⁇ m or less can be used.
  • the molten sheet-like multilayer sheet extruded from the T-die is subsequently cooled by being brought into contact with a metal cooling roll (also referred to as a chill roll or a casting roll) and closely contacting the cooling roll.
  • a metal cooling roll also referred to as a chill roll or a casting roll
  • the close contact with the cooling roll affects the thickness accuracy of the sheet.
  • an adhesion means of the cooling roll for example, a) A method in which static electricity is applied to a multilayer sheet-like material in the form of a molten sheet, and the surface state is brought into close contact with a mirror-like cooling roll for cooling b) A method for cooling a molten sheet-like multilayer sheet-like material by sandwiching the surface state between a cooling roll and a surface state between a rubber roll (also referred to as a touch roll) and closely contacting the cooling roll, c) When a molten sheet-like multilayer sheet-like material is brought into contact with the cooling roll, it can be carried out by a known method such as an air chamber or a method in which the molten sheet is brought into close contact with the cooling roll with air blown from an air knife.
  • a general rubber such as silicon rubber or neoprene rubber having a rubber hardness of 60-100 can be used.
  • the cooling roll used in the above three types of systems is preferably adjusted to have a surface temperature in the range of 20 to 80 ° C., for example.
  • a surface temperature of the cooling roll exceeds 80 ° C., it takes time to cool and solidify the molten multilayer sheet material, so that the polypropylene in the multilayer sheet material is not sufficiently cooled, and the sheet is manufactured against the take-up tension of the sheet. May deform in the direction.
  • the surface temperature of the cooling roll is lower than 20 ° C., the surface of the cooling roll is dewed and water droplets are attached, which tends to deteriorate the appearance of the resulting film.
  • the processing speed when producing the multilayer sheet of the present embodiment can be carried out within a general range, but generally 2 to 20 m / min is preferable.
  • either side of the outer layer made of polypropylene and crystalline polyester may be arranged on the cooling roll side during production, but the crystal promotion can be improved by arranging the crystalline polyester side on the cooling roll side. This is preferable. This is from the viewpoint that if a large amount of crystalline component having a high melting point is produced in the subsequent molding of the tray, the crystalline polyester layer lacks elongation at the molding temperature of polypropylene, and the thermoformability may be impaired.
  • the ratio of the crystallization peak enthalpy ⁇ H (crystallization) to the melting peak enthalpy ⁇ H (melting) in the crystalline polyester ( ⁇ H (crystallization) / ⁇ H (melting)).
  • enthalpy ratio is preferably greater than 0, more preferably 0.10 or more, further preferably 0.2 or more, and more preferably 0.30 or more. Even more preferred. Note that this ratio exceeding 0 indicates that there is crystalline polyester that is not crystallized in the state of the sheet or food tray, and that this ratio is 0.20 or more or 0.30 or more. This indicates that the amount of crystalline polyester that is not crystallized in the state of the sheet or food tray is large.
  • An example of such a crystalline polyester is A-PET.
  • Examples of the method of increasing the amount of the non-crystallized component of the polyester layer of the sheet of the present invention and the food tray immediately after thermoforming include, for example, conditions for producing a multilayered sheet, and thermoforming the sheet. There are methods for controlling the conditions for the trays.
  • the former method when manufacturing a multilayer sheet, when cooling a molten sheet-like material extruded from a die, the surface temperature of a cooling roll for cooling and solidifying the sheet is set to 70 ° C. or less, and the polyester layer is rapidly cooled. The amount of components that are not crystallized can be increased.
  • the surface temperature of the cooling roll is affected by the total thickness of the sheet and the line speed.
  • the conditions such as the heater position (distance), temperature, time, etc., at which the crystal of the crystalline polyester layer in the sheet melts (near the melting point) are set.
  • the amount of the non-crystallized component of the polyester layer can be increased.
  • the crystalline polyester in the food tray of the present embodiment may be crystallized by aging at, for example, 100 to 160 ° C. after obtaining a liquid crystal polyester layer containing a component that is not crystallized by thermoforming,
  • food may be stored in a state where there is crystalline polyester that has not been crystallized, and this may be crystallized when cooking. Thereby, heat resistance can be improved.
  • the tray is inserted into a mold that can hold the shape of the tray, or sandwiched between two upper and lower molds.
  • the crystalline polyester in the tray may be crystallized by adjusting the temperature to from °C to 230 °C and holding for about 2 seconds to 30 seconds, that is, by heat treatment in a subsequent step.
  • the crystalline polyester may be crystallized by holding a tray in a heating furnace such as a temperature-controlled gear oven.
  • the food tray for containing the food according to the present embodiment is formed by molding the above-described sheet so that the outermost layer containing the crystalline polyester is located on the surface in contact with the food by a conventionally known thermoforming method. Is obtained.
  • the shape of the tray can be conventionally known and is not particularly limited.
  • the laminated sheet 1 was obtained by aging at 40 ° C. for 2 days.
  • the laminated sheet 1 is attached to a batch-type vacuum forming machine, heated for 12 seconds from the top and bottom with a heater set at 508 ° C., and when the sheet surface temperature reaches 190 ° C., the heater is released to form a tray (50 mm ⁇ 120 mm ⁇ An evaluation tray was obtained by vacuum-forming the polyester surface to the inside at a depth of 40 mm.
  • the sheet surface temperature was measured by using a plurality of commercially available thermolabels with temperature indications in increments of 10 ° C. and having different measurement temperature ranges.
  • the polyester layer inside the tray was peeled off and measured using DSC at a heating rate of 10 ° C./min and a nitrogen flow of 50 ml / min, and a peak associated with crystallization and a peak associated with melting were determined.
  • Example 2 Dry lamination + crystallization by heat treatment
  • a tray was prepared in the same manner as in Example 1 except that the laminated sheet 1 was used and the heater temperature was 550 ° C., the heating time was 10 seconds, and the sheet surface temperature was 190 ° C.
  • the enthalpy ratio measured by DSC of the obtained tray was 0.50. Thereafter, evaluation was performed in the same manner as in Example 1 except that the molded tray was placed in a gear oven heated to 150 ° C. and crystallized by heat treatment for 15 minutes. DSC measurement of the sheet after heat treatment was also performed. Since the enthalpy ratio after heat treatment is 0, it can be seen that the tray is crystallized.
  • Example 3 Extrusion Lami
  • a modified polyolefin resin manufactured by Mitsui Chemicals, Admer SF731
  • Admer SF731 modified polyolefin resin
  • the laminated sheet 2 was obtained by niping between the metal roll and the rubber roll which were temperature-controlled at 40 degreeC.
  • a tray was prepared by vacuum forming in the same manner as in Example 1 except that the heater temperature was 530 ° C., the heating time was 11 seconds, and the sheet surface temperature was 190 ° C. Evaluation was performed in the same manner as in Example 1.
  • Example 4 Coextrusion
  • a polyester resin (PET: manufactured by SHINKONG, SHINPET TM 5522W) dried at 150 ° C. for 4 hours in a 50 mm ⁇ extruder set at 270 ° C. (extruder A) was also set at 260 ° C. (extruder B).
  • Adhesive resin Mitsubishi Chemical Co., Ltd. Admer SF731
  • a tray was prepared in the same manner as in Example 1 except that the heater temperature was 530 ° C., the heating time was 17 seconds, and the sheet surface temperature was 210 ° C. Evaluation was performed in the same manner as in Example 1.
  • Example 5 Coextrusion
  • a polyester resin (PET: manufactured by SHINKONG, SHINPET TM 5522W) dried at 150 ° C. for 4 hours in a 50 mm ⁇ extruder set at 270 ° C. (extruder A) was also set at 260 ° C. (extruder C).
  • Adhesive resin (Mitsui Chemical Co., Ltd.
  • the laminated sheet 3 was obtained by sandwiching and cooling between the metal rolls.
  • a tray was prepared in the same manner as in Example 1 except that the heater temperature was 530 ° C., the heating time was 14 seconds, and the sheet surface temperature was 220 ° C. Evaluation was performed in the same manner as in Example 1.
  • a tray was prepared in the same manner as in Example 1 except that the heater temperature was 530 ° C., the heating time was 14 seconds, and the sheet surface temperature was 220 ° C. Evaluation was performed in the same manner as in Example 1.
  • Example 6 Coextrusion
  • a tray was prepared in the same manner as in Example 1 except that the heater temperature was 530 ° C., the heating time was 10 seconds, and the sheet surface temperature was 210 ° C. Evaluation was performed in the same manner as in Example 1.
  • Example 7 Coextrusion
  • a tray was prepared in the same manner as in Example 1 except that the heater temperature was 530 ° C., the heating time was 17 seconds, and the sheet surface temperature was 200 ° C. Evaluation was performed in the same manner as in Example 1.
  • Example 8 Coextrusion
  • a tray was prepared in the same manner as in Example 1 except that the heater temperature was 530 ° C., the heating time was 17 seconds, and the sheet surface temperature was 210 ° C. Evaluation was performed in the same manner as in Example 1.
  • Example 9 Coextrusion
  • a tray was prepared in the same manner as in Example 1 except that the heater temperature was 530 ° C., the heating time was 14 seconds, and the sheet surface temperature was 210 ° C. Evaluation was performed in the same manner as in Example 1.
  • Example 10 Coextrusion
  • a tray was prepared in the same manner as in Example 1 except that the heater temperature was 530 ° C., the heating time was 46 seconds, and the sheet surface temperature was 220 ° C. Evaluation was performed in the same manner as in Example 1.
  • Example 11 Coextrusion
  • a tray was prepared in the same manner as in Example 1 except that the heater temperature was 380 ° C., the heating time was 63 seconds, and the sheet surface temperature was 160 ° C. Evaluation was performed in the same manner as in Example 1.
  • Comparative Example 1 As a comparison object, using the polypropylene sheet used when the laminated sheet 1 was manufactured, a tray was formed in the same manner as in Example 1, and the evaluation using a microwave oven was similarly performed using salad oil as in Example 1. It was.
  • Table 1 shows the structure and production conditions of the sheets obtained in Examples and Comparative Examples, and Table 2 shows the test results.

Landscapes

  • Laminated Bodies (AREA)
  • Wrappers (AREA)

Abstract

L'invention concerne une feuille pour thermoformage qui possède deux couches ou plus d'un stratifié. Plus précisément, l'invention fournit une feuille pour thermoformage dont une des couches les plus externes comprend un polyester cristallin, et dont une autre couche parmi les plus externes comprend un polypropylène.
PCT/JP2016/055459 2016-02-24 2016-02-24 Feuille pour thermoformage, et plateau pour aliment Ceased WO2017145290A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS589738U (ja) * 1981-07-13 1983-01-21 三菱樹脂株式会社 成形容器
JPH04147858A (ja) * 1990-10-11 1992-05-21 Toppan Printing Co Ltd シート成形用積層体
JPH05220913A (ja) * 1992-02-12 1993-08-31 Toppan Printing Co Ltd 絞り成形容器用多層シート
JPH10202733A (ja) * 1997-01-23 1998-08-04 Fujimori Kogyo Kk 成形容器の製造方法
JP2001035454A (ja) * 1999-07-16 2001-02-09 Dainippon Printing Co Ltd 積層体及びそれを用いたポリマー電池用包装材料
JP2007168794A (ja) * 2005-11-22 2007-07-05 Sun A Kaken Co Ltd 密封容器

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS589738U (ja) * 1981-07-13 1983-01-21 三菱樹脂株式会社 成形容器
JPH04147858A (ja) * 1990-10-11 1992-05-21 Toppan Printing Co Ltd シート成形用積層体
JPH05220913A (ja) * 1992-02-12 1993-08-31 Toppan Printing Co Ltd 絞り成形容器用多層シート
JPH10202733A (ja) * 1997-01-23 1998-08-04 Fujimori Kogyo Kk 成形容器の製造方法
JP2001035454A (ja) * 1999-07-16 2001-02-09 Dainippon Printing Co Ltd 積層体及びそれを用いたポリマー電池用包装材料
JP2007168794A (ja) * 2005-11-22 2007-07-05 Sun A Kaken Co Ltd 密封容器

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