WO2017221375A1 - Feuille en résine multicouche et récipient façonné - Google Patents

Feuille en résine multicouche et récipient façonné Download PDF

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Publication number
WO2017221375A1
WO2017221375A1 PCT/JP2016/068681 JP2016068681W WO2017221375A1 WO 2017221375 A1 WO2017221375 A1 WO 2017221375A1 JP 2016068681 W JP2016068681 W JP 2016068681W WO 2017221375 A1 WO2017221375 A1 WO 2017221375A1
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layer
resin
sheet
resin layer
thickness
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PCT/JP2016/068681
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English (en)
Japanese (ja)
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徳永　久次
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デンカ株式会社
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Priority to JP2018523231A priority Critical patent/JP6800972B2/ja
Priority to PCT/JP2016/068681 priority patent/WO2017221375A1/fr
Publication of WO2017221375A1 publication Critical patent/WO2017221375A1/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
    • 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

Definitions

  • the present invention relates to a multilayer resin sheet having high barrier properties and a container formed by thermoforming it.
  • polystyrene resins having excellent thermoformability and rigidity have been used as containers for soft drinks, fruit juice drinks, and favorite foods and drinks.
  • a polystyrene resin layer is used as the outermost layer, and an ethylene-vinyl alcohol copolymer resin layer is provided in the middle through an adhesive layer such as a modified polyolefin resin to provide oxygen barrier properties.
  • Multilayer resin sheets that suppress deterioration in quality and multilayer containers comprising the same have become widespread (see Patent Document 1).
  • a gas barrier material containing a silicon-containing polymer and a thermoplastic resin is used, the glass transition temperature of the thermoplastic resin is set to a value of 100 ° C. or higher, and plasma ion implantation is performed for the gas barrier material.
  • the silicon-containing polymer is a polysilazane compound
  • the thermoplastic resin is at least one selected from the group consisting of a polycarbonate resin, a cyclopolyolefin resin, and a polysulfone resin.
  • Patent Document 3 Furthermore, an optical resin sheet having barrier properties and solvent resistance against gases such as oxygen and water vapor and moisture has been proposed (see Patent Document 3).
  • the thickness is determined by performing heat curing treatment on the coating film.
  • a gas barrier layer having a thickness of 0.02 to 5 ⁇ m is provided.
  • Patent Document 4 discloses a fragrance-holding resin layer made of a mixture of a terephthalic acid, ethylene glycol and 1,4-cyclohexanedimethanol terpolymer resin and a polybutylene terephthalate resin, and an impact resistance made of a polyamide resin.
  • a composite sheet in which an application layer, a water vapor barrier resin layer, a gas barrier resin layer, and a thermoplastic support resin layer are sequentially laminated.
  • Patent Document 5 a polypropylene resin is laminated on one side of a barrier resin layer, and the total thickness of the polypropylene resin layer is 10 to 40% of the total thickness of the sheet. Sheets having excellent properties (particularly oxygen barrier properties), moldability, and mechanical properties such as rigidity and strength have been proposed.
  • Patent Document 5 an oil-resistant polypropylene resin is formed on the outermost surface of a sheet, and a resin composition layer composed of a styrene resin, a styrene-diene copolymer and an olefin resin is formed as a support layer.
  • a sheet configuration has been proposed. However, by laminating a crystalline polypropylene resin and an amorphous styrene resin, warping is likely to occur after container molding, resulting in problems such as poor sealing with the lid material and poor appearance as a container. There is a possibility.
  • Patent Documents 1 to 5 mainly describe the characteristics of blocking components that affect the contents of the container such as oxygen and water vapor. However, it is not configured to cover additional performance such as the above-described oil resistance and warpage affecting the appearance and functionality of the container.
  • the present invention has been made in view of the above circumstances, and has a high barrier property multilayer resin that has excellent thermoformability, oxygen barrier property, water vapor barrier property, and oil resistance, and suppresses warpage after the sheet and thermoforming.
  • An object is to provide a sheet and a molded container formed by molding the sheet.
  • the present inventor has intensively studied for the purpose of having the above characteristics, and as a result, is a multilayer resin sheet formed by laminating a plurality of resin layers, and a polyolefin-based resin layer serving as a skin layer and an adhesive Layer, an oxygen-barrier resin layer, and a resin layer including a polystyrene-based resin layer serving as an undercoat layer.
  • the thickness of the entire sheet is 200 to 1300 ⁇ m
  • the thickness of the polyolefin-based resin layer is the thickness of the entire sheet.
  • the polyolefin resin layer is formed of a block polypropylene resin.
  • the block polypropylene resin refers to one in which a homopropylene block is a continuous phase and ethylene propylene rubber (EPR) forms a dispersion layer.
  • EPR ethylene propylene rubber
  • the thickness of the polyolefin-based resin layer is 5% or more and less than 10% with respect to the thickness of the entire sheet.
  • the thickness of the oxygen barrier resin layer is preferably 10 to 50 ⁇ m, and the oxygen permeability is preferably 10 cc / m 2 ⁇ day or less.
  • transmittance of the multilayer resin sheet comprised as mentioned above is 10 g / m ⁇ 2 > * day or less.
  • the present invention provides a molded container obtained by thermoforming the multilayer resin sheet configured as described above so that the polyolefin resin layer is positioned on the inner surface of the container.
  • the multilayer resin sheet configured as described above and a molded container formed by molding the same have excellent thermoformability, oxygen barrier property, water vapor barrier property, oil resistance, and warp after the sheet and thermoforming. Can be suppressed.
  • an oxygen barrier resin layer 12 is laminated with a polyolefin-based resin layer 10 serving as a skin layer on the outermost surface through an adhesive layer 11a.
  • a polystyrene resin layer is laminated on the opposite side through the adhesive layer 11b.
  • the thickness of the entire sheet is 200 to 1300 ⁇ m, and the thickness of the polyolefin resin layer is set to 1 to 30% of the layer composition ratio with respect to the thickness of the entire sheet. More preferably, the thickness of the polyolefin resin layer is 2% or more and less than 10% with respect to the thickness of the entire sheet. More preferably, the thickness of the polyolefin resin layer is 5% or more and less than 10% with respect to the thickness of the entire sheet.
  • the multilayer resin sheet according to an embodiment of the present invention has a layer structure of polyolefin resin layer / adhesive layer / oxygen barrier resin layer / adhesive layer / polystyrene resin layer, and is simply a skin layer / adhesive layer / The notation is oxygen barrier layer / adhesive layer / undercoat layer.
  • the lower skin layer is a layer that is finely pulverized or re-pelletized after heat melting and returned as a recycled product without discarding the part called scrap generated in the process of producing the multilayer resin sheet or molded container of the present invention. It is good also as a structure which provided newly.
  • a configuration may be adopted in which a printing surface is provided by a method such as direct printing or laminating printed films.
  • the thickness of the entire sheet in the present invention is preferably 200 to 1300 ⁇ m. If the thickness of the container after thermoforming is less than 200 ⁇ m, a thin portion of the container is formed, and the content of the container on the inner surface of the container is reduced due to a decrease in container strength representing resistance to compression and pressure called buckling strength. There is a possibility that deformation or breakage of the container may occur due to vibration or compression when the object is stored and transported. When it exceeds 1300 ⁇ m, heat is not sufficiently transmitted in the thickness direction of the sheet during thermoforming, and molding defects may occur.
  • the container is allowed to stand on a smooth surface with the flange portion of the molded container at the bottom, and deformation is confirmed by placing a weight with a constant load on the bottom surface of the container.
  • a method of measuring a load that deforms a container using a device called a push-pull gauge that measures a load applied to tension or compression is not limited to this, and is evaluated by a suitable method. Can do.
  • the film forming method of the multilayer resin sheet of the present embodiment is not particularly limited, and a general film forming method can be used.
  • a coextrusion method in which each raw resin is melt-extruded using four or more single-screw or twin-screw extruders, and a multilayer resin sheet is obtained by a feed block and a T-die incorporating a selector plug, or a multi-manifold
  • dye is mentioned.
  • the polyolefin-based resin layer 10 preferably has a layer composition ratio of 1 to 30% with respect to the thickness of the entire sheet. More preferably, the layer composition ratio is 2% or more and less than 10%. More preferably, the layer composition ratio is 5% or more and less than 10%.
  • the layer composition ratio described here is calculated as a percentage from a value obtained by dividing the thickness of the polyolefin resin layer by the thickness of the entire sheet. When the layer composition ratio with respect to the entire sheet is less than 1%, particularly when the entire sheet thickness is thin, a sufficient thickness as a polyolefin-based resin layer cannot be secured, and functions such as water vapor barrier properties may not be exhibited.
  • the crystalline polyolefin resin layer that forms the skin layer tends to increase in heat shrinkage during thermoforming, whereas the non-crystalline polystyrene resin that forms the lower skin layer. Since the heat shrinkage of the layer is small, a difference in the heat shrinkage rate between the skin layer and the lower skin layer may cause warpage of the sheet or the container after thermoforming.
  • the skin layer 10 composed of the polyolefin-based resin described in the present invention is basically located on the inner surface (the surface in contact with the contents) of a container formed by thermoforming a sheet. It is formed for the purpose of imparting oil resistance. Moreover, it is preferable to provide a heat resistance by selecting a resin that can withstand a hot water temperature of 90 ° C. or higher for a container into which hot water is poured.
  • the multilayer resin sheet configured as described above preferably has a water vapor transmission rate of 10 g / m 2 ⁇ day or less, and more preferably 5 g / m 2 ⁇ day or less. If it exceeds 10 g / m 2 ⁇ day, there is a possibility that a sufficient suppression function will not be exhibited when the contents of the thermoformed container are altered or discolored due to the permeation of moisture.
  • polyolefin resin in the constitution of the present invention examples include, but are not limited to, a homopolymer of a polyolefin having about 2 to 8 carbon atoms such as ethylene, propylene and butene-1.
  • polyethylene resin high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), and the like that are commonly used can be applied.
  • polypropylene resin any of homopolymer, random copolymer and block copolymer can be applied.
  • block copolymer is particularly preferably used.
  • the block copolymer has a viscosity (Pa ⁇ s) at a measurement temperature of 190 ° C., a shear rate of 100 to 300 (1 / sec) of 50,000 to 1,000,000, and a viscosity change at 190 to 230 ° C. of 0.5 to 15 Pa ⁇ . More preferably, a resin having a range of s / ° C. is used.
  • the polyolefin resin to be used can be appropriately blended to such an extent that the appearance of the sheet and the container after thermoforming is not impaired.
  • Typical examples of the oxygen barrier resin constituting the oxygen barrier resin layer 12 of the present embodiment include ethylene-vinyl alcohol copolymer resin, polyamide resin, polyvinyl alcohol, and polyvinylidene chloride. It is not limited to these. Among these, ethylene-vinyl alcohol copolymer resin is preferable in terms of extrusion moldability.
  • the ethylene-vinyl alcohol copolymer resin is usually obtained by saponifying an ethylene-vinyl acetate copolymer, and has an ethylene content of 10 to 65 mol in order to provide oxygen barrier properties and extrusion moldability. %, Preferably 20 to 50 mol%, and a saponification degree of 90% or more, preferably 95% or more.
  • polyamide resin examples 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, Aliphatic diamines such as dodecamethylenediamine, 2,2,4- or 2,4,4-trimethylhexamethylenediamine, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis (p-aminocyclohexylmethane) ), Alicyclic diamines such as m- or p-xylylenediamine, diamine units such as aromatic diamines, aliphatic dicarboxylic acids such as adipic acid, suberic acid and sebacic acid, and alicyclics such as cyclohexanedicarboxylic acid Aromatic dicarboxylic acid, terephthalate
  • polyamide resin examples 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 which nylon 6 and nylon MXD6 are preferred.
  • the thickness of the oxygen barrier resin layer 12 is preferably 10 to 50 ⁇ m, more preferably 20 to 40 ⁇ m. If the thickness is less than 10 ⁇ m, the thickness of the oxygen barrier resin layer in the container after thermoforming the sheet becomes extremely thin, so that the oxygen contained in the container can be prevented from deterioration due to oxidative degradation. There is a possibility that the barrier performance cannot be obtained, and when it exceeds 50 ⁇ m, there is a possibility that a so-called appearance defect called “hibari burr” occurs at the time of punching of the container applied after thermoforming.
  • the oxygen permeability of the oxygen barrier resin layer 12 is preferably 10 cc / m 2 ⁇ day or less, and more preferably 5 cc / m 2 ⁇ day or less. When it exceeds 10 cc / m 2 ⁇ day, there is a possibility that a sufficient suppression function is not exhibited when the contents of the thermoformed container are subject to oxidative degradation.
  • a modified polyolefin polymer is preferable.
  • the modified polyolefin polymer constituting the adhesive layer include homopolymers of polyolefins having about 2 to 8 carbon atoms such as ethylene, propylene and butene-1, and these polyolefins and ethylene, propylene, butene-1, 3-methylbutene.
  • polystyrene resins such as copolymers with vinyl compounds such as acrylic acid esters, methacrylic acid esters, polystyrene, ethylene-propylene copolymers, ethylene-propylene-diene copolymers, ethylene-butene-1 copolymers, Polyolefin rubber such as propylene-butene-1 copolymer is used for acrylic acid, Unsaturated carboxylic acids such as rillic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, or derivatives thereof such as acid halides, amides, imides, anhydrides, esters, and other polyolefins having about 2 to 20 carbon atoms, vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid, Polyolefin resins such as copolymers with vinyl compounds such as acrylic acid esters, methacrylic acid esters, poly
  • maleyl chloride maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like can be cited as representative examples.
  • modified polyolefin polymer among them, an ethylene resin, a propylene resin, or an ethylene-propylene or butene-1 copolymer rubber modified with an unsaturated dicarboxylic acid or an anhydride thereof, particularly maleic acid or an anhydride thereof is preferable. It is.
  • the thickness of the adhesive layer is preferably 5 to 50 ⁇ m, more preferably 10 to 30 ⁇ m in any layer. If the thickness is less than 5 ⁇ m, sufficient adhesion strength between layers may not be obtained. If the thickness exceeds 50 ⁇ m, an appearance defect called so-called whirling may occur at the time of punching a container applied after thermoforming. There is sex.
  • the polystyrene resin constituting the polystyrene resin layer 13 of the present embodiment includes polystyrene monomers such as polystyrene, ⁇ -methyl polystyrene, p-methyl polystyrene, dimethyl polystyrene, pt-butyl polystyrene, chloropolystyrene.
  • HIPS resin high impact polypolystyrene
  • ABS resin polystyrene-acrylonitrile Rugurafuto polymer
  • Polystyrene (GPPS resin) and high-impact polypolystyrene (HIPS resin) are preferable from the viewpoint of the rigidity and moldability of the molded container, and the blend ratio can be adjusted as appropriate. It can be used by blending.
  • the polystyrene resin preferably contains 4 to 8% by mass of a butadiene rubber component.
  • the butadiene rubber component content is a simple method of adjusting by blending GPPS and HIPS, but it may be adjusted at the manufacturing stage of HIPS. If it is less than 4% by mass, there is a possibility that practically sufficient container strength may not be obtained, and if it exceeds 8% by mass, there is a possibility of causing problems such as adhesion of a hot plate, particularly during thermoforming using a hot platen. .
  • the polystyrene resin layer 13 may have a colorant such as a pigment or a dye, a release agent such as silicon oil or an alkyl ester, or a fiber such as glass fiber as long as the effect of the present invention is not impaired.
  • a colorant such as a pigment or a dye, a release agent such as silicon oil or an alkyl ester, or a fiber such as glass fiber as long as the effect of the present invention is not impaired.
  • Additives such as reinforcing agents, granular lubricants such as talc, clay, silica, salt compounds of sulfonic acid and alkali metals, antistatic agents such as polyalkylene glycol, UV absorbers, and antibacterial agents can be added .
  • the thickness of the polystyrene resin layer 13 of this embodiment is preferably 200 to 900 ⁇ m, more preferably 300 to 700 ⁇ m. If it is less than 200 ⁇ m, the thickness of each part of the container after molding may not be more uniform, and there is a possibility that excellent thermoformability may not be expressed. If it exceeds 900 ⁇ m, in the thickness direction of the sheet during thermoforming Heat may not be sufficiently transmitted, and molding defects may occur.
  • FIG. 3 shows an example of the molded container of the present invention.
  • the molded container of the present invention is obtained by thermoforming the multilayer resin sheet of the present invention.
  • Thermoforming methods include general vacuum forming, pressure forming, and plug assist method in which plugs are formed by contacting a plug on one side of the sheet, and male and female molds that form a pair on both sides of the sheet. Examples of the method include so-called match mold molding, which is performed by bringing them into contact with each other, but is not limited thereto.
  • a known sheet heating method such as radiant heating by an infrared heater or the like which is non-contact heating, or hot plate heating to soften the sheet by directly touching the heated hot plate is applied. can do.
  • the molding temperature at the time of thermoforming is appropriately set in consideration of the melting point of the resin, etc., but if the sheet heating temperature is too low, the molded state of the container after thermoforming is insufficient, and conversely the sheet heating If the temperature is too high, there is a risk that a defect such as a fusing to the hot platen may occur, so it is preferable to set the temperature appropriately.
  • the resin raw materials used in the examples are as follows.
  • Polyolefin-based resin layer PP resin “3080” (Formosa Polypropylene Co., Ltd., MI: 8.5 g / 10 min. (190 ° C., 2.16 kgf), Block-PP)
  • Adhesive layer Modified polyolefin polymer modified PO
  • Modic F502C Mitsubishi Chemical Corporation, MI: 1.3 g / 10 min. (190 ° C., 2.16 kgf)
  • Polystyrene resin layer HIPS resin “4241” (Total Petrochemicals, MI: 4.0 g / 10 min. (200 ° C, 5.0 kgf))
  • the multilayer resin sheet was thermoformed under the following conditions to obtain a container shown in FIG.
  • Equipment used Vacuum pressure forming machine manufactured by Asano Laboratories Heating heater: Non-contact far infrared heater Sheet surface temperature: Adjust sheet surface temperature as appropriate according to the sheet configuration
  • various evaluations of multilayer resin sheets and containers are performed by the following methods. It was. The results are shown in Table 1.
  • PP resin was used as polyolefin resin by a feed block method.
  • the water vapor transmission rate of the multilayer resin sheet obtained as described above is 0.8 g / m 2 ⁇ day.
  • the oxygen permeability is 0.5 cc / m 2 ⁇ day.
  • the warpage of the multilayer resin sheet was 13 mm.
  • the layer composition ratio of the resin layer was 17%, the total thickness was 900 ⁇ m, and other methods were obtained in the same manner as in Example 1 to obtain a multilayer resin sheet.
  • the water vapor transmission rate of the multilayer resin sheet obtained as described above As a result of measuring the water vapor transmission rate of the multilayer resin sheet obtained as described above, as shown in Table 1, the water vapor transmission rate is 0.7 g / m 2 ⁇ day. As a result of measuring the oxygen permeability, as shown in Table 1, the oxygen permeability is 0.4 cc / m 2 ⁇ day. Further, when the oil resistance of the multilayer resin sheet was evaluated, the oil resistance was evaluated as A rank. As a result of evaluating the warpage of the multilayer resin sheet, the warpage of the multilayer resin sheet was 15 mm.
  • Polyolefin-based resin layer (10) 80 ⁇ m / adhesive layer (11a) 15 ⁇ m / oxygen barrier resin layer (12) 40 ⁇ m / adhesive layer (11b) 15 ⁇ m / polystyrene-based resin layer (13) 950 ⁇ m
  • a multilayer resin sheet was obtained in the same manner as in Example 1 except that the resin layer had a layer composition ratio of 7% and a total thickness of 1100 ⁇ m.
  • the water vapor transmission rate of the multilayer resin sheet obtained as described above As a result of measuring the water vapor transmission rate of the multilayer resin sheet obtained as described above, as shown in Table 1, the water vapor transmission rate is 0.7 g / m 2 ⁇ day. As a result of the oxygen permeability measurement, as shown in Table 1, the oxygen permeability is 0.6 cc / m 2 ⁇ day. Further, when the oil resistance of the multilayer resin sheet was evaluated, the oil resistance was evaluated as A rank, and as a result of evaluating the warpage of the multilayer resin sheet, the warpage of the multilayer resin sheet was 9 mm.
  • the layer composition ratio of the resin layer was 5%, the total thickness was 1000 ⁇ m, and other methods were obtained in the same manner as in Example 1 to obtain a multilayer resin sheet.
  • the water vapor transmission rate of the multilayer resin sheet obtained as described above As a result of measuring the water vapor transmission rate of the multilayer resin sheet obtained as described above, as shown in Table 1, the water vapor transmission rate is 0.7 g / m 2 ⁇ day. As a result of measuring the oxygen transmission rate, as shown in Table 1, the oxygen transmission rate is 0.7 cc / m 2 ⁇ day. Further, when the oil resistance of the multilayer resin sheet was evaluated, the oil resistance was evaluated as A rank. As a result of evaluating the warpage of the multilayer resin sheet, the warpage of the multilayer resin sheet was 7 mm.
  • the layer composition ratio of the resin layer was 3%, the total thickness was 1200 ⁇ m, and other methods were obtained in the same manner as in Example 1 to obtain a multilayer resin sheet.
  • the water vapor transmission rate is in the 0.7g / m 2 ⁇ day.
  • the oxygen permeability is 0.6 cc / m 2 ⁇ day.
  • the warpage of the multilayer resin sheet was 5 mm.
  • the moldability of the container molded using the multilayer resin sheet was evaluated, the moldability was evaluated as A rank, and as a result of evaluating the warpage of the molded container, the warpage of the molded container was 0. It has become.
  • PP resin was used as the polyolefin resin.
  • the polyolefin resin may be any one of, for example, a homopolymer of a polyolefin having about 2 to 8 carbon atoms such as ethylene, propylene, and butene-1.
  • a resin may be used. In this case, substantially the same effects as those of the first to fifth embodiments can be obtained.
  • Example 1 Compared with Example 1, the modification which makes the total thickness of a polyolefin-type resin layer, the thickness of the polystyrene-type resin layer used as a skin layer, etc. small, or forms a water vapor
  • each performance was evaluated as follows. ⁇ Comparative Example 1>
  • a single-layer sheet having a polystyrene resin layer of 450 ⁇ m was obtained with one 65 mm single-screw extruder.
  • the characteristic of this comparative example is that the resin sheet is composed of a single layer composed of only a polystyrene-based resin layer.
  • the water vapor transmission rate of the single layer resin sheet obtained from the comparative example is 7.0 g / m 2 ⁇ day.
  • the oxygen transmission rate is 350 cc / m 2 ⁇ day.
  • the oil resistance of the single layer resin sheet was evaluated, the oil resistance was evaluated as C rank, and as a result of evaluating the warp of the single layer resin sheet, the warp of the single layer resin sheet was 12 mm.
  • the moldability of a container molded using the single-layer resin sheet was evaluated, the moldability was evaluated as A rank, and as a result of evaluating the warpage of the molded container, the warpage of the molded container was 0. It has become.
  • a multilayer resin sheet was obtained in the same manner as in Example 1 except that the skin layer was made of polystyrene resin.
  • the water vapor transmission rate of the multilayer resin sheet obtained from the comparative example is 4.2 g / m 2 ⁇ day.
  • the oxygen transmission rate is 1.2 cc / m 2 ⁇ day.
  • the oil resistance of the multilayer resin sheet was evaluated, the oil resistance was evaluated as C rank.
  • the warpage of the multilayer resin sheet was 15 mm.
  • the moldability of the container molded using the multilayer resin sheet was evaluated, the moldability was evaluated as A rank, and as a result of evaluating the warpage of the molded container, the warpage of the molded container was 0. It has become.
  • a multilayer resin sheet was obtained in the same manner as in Example 1 except that the layer composition ratio of the resin layer was 33% and the total thickness was 600 ⁇ m.
  • the water vapor transmission rate of the multilayer resin sheet obtained from the comparative example As a result of measuring the water vapor transmission rate of the multilayer resin sheet obtained from the comparative example, as shown in Table 2, the water vapor transmission rate is 0.7 g / m 2 ⁇ day. As a result of measuring the oxygen transmission rate, as shown in Table 2, the oxygen transmission rate is 0.8 cc / m 2 ⁇ day. Further, when the oil resistance of the multilayer resin sheet was evaluated, the oil resistance was evaluated as A rank. As a result of evaluating the warpage of the multilayer resin sheet, the warpage of the multilayer resin sheet was 43 mm. Furthermore, when the moldability of the container molded using the multilayer resin sheet was evaluated, the moldability was evaluated as C rank, and as a result of evaluating the warpage of the molded container, the warpage of the molded container was 12 mm. It has become.
  • the warp of the multilayer resin sheet is 43 mm, and the warpage of the container molded using the multilayer resin sheet is 12 mm.
  • the molded container is not acceptable because the moldability as in the mold is not obtained.
  • Polyolefin-based resin layer (10) 25 ⁇ m / adhesive layer (11a) 10 ⁇ m / oxygen barrier resin layer (12) 30 ⁇ m / adhesive layer (11b) 10 ⁇ m / polystyrene-based resin layer (13) 120 ⁇ m
  • the layer composition ratio of the resin layer was 13%, the total thickness was 195 ⁇ m, and other methods were obtained in the same manner as in Example 1 to obtain a multilayer resin sheet.
  • the water vapor transmission rate of the multilayer resin sheet obtained from the comparative example is 0.9 g / m 2 ⁇ day.
  • the oxygen permeability is 1.0 cc / m 2 ⁇ day.
  • the moldability of a container molded using the multilayer resin sheet was evaluated, the moldability was evaluated as B rank, and as a result of evaluating the warpage of the molded container, the warpage of the molded container was 0 mm. It has become.
  • a multilayer resin sheet was obtained in the same manner as in Example 1 except that the polyolefin resin layer had a layer composition ratio of 84% and a total thickness of 450 ⁇ m.
  • the water vapor transmission rate of the multilayer resin sheet obtained from the comparative example As a result of measuring the water vapor transmission rate of the multilayer resin sheet obtained from the comparative example, as shown in Table 2, the water vapor transmission rate is 0.7 g / m 2 ⁇ day. As a result of measuring the oxygen transmission rate, as shown in Table 2, the oxygen transmission rate is 0.8 cc / m 2 ⁇ day. Further, when the oil resistance of the multilayer resin sheet was evaluated, the oil resistance was evaluated as A rank, and as a result of evaluating the warpage of the multilayer resin sheet, the warpage of the multilayer resin sheet was 9 mm.
  • the moldability of a container molded using the multilayer resin sheet was evaluated, the moldability was evaluated as B rank, and as a result of evaluating the warpage of the molded container, the warpage of the molded container was 0 mm. It has become.
  • the formability was evaluated as B rank, and during use, the thin part of the container after molding may be broken, and the barrier property may be reduced due to the intrusion of water vapor or oxygen There is.
  • a plurality of resin layers including a resin layer, the thickness of the entire sheet is 200 to 1300 ⁇ m, and the thickness of the polyolefin resin layer is 1% to 30% with respect to the thickness of the entire sheet.
  • a multilayer resin sheet formed by laminating resin layers has excellent thermoformability and oil resistance, and can suppress warpage of the sheet.
  • the oxygen barrier resin layer has a thickness of 10 to 50 ⁇ m and an oxygen permeability of 10 cc / m 2 ⁇ day or less.
  • the multilayer resin sheet having the above configuration has a water vapor transmission rate of 10 g / m 2 ⁇ day or less.
  • the multilayer resin sheet configured as described above, it has excellent thermoformability, oxygen barrier property, water vapor barrier property, and oil resistance, and can suppress warpage of the sheet.
  • the molded container formed by molding the multilayer resin sheet configured as described above has excellent thermoformability, oxygen barrier property, water vapor barrier property, oil resistance, and suppresses warping after thermoforming. Can do.

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  • Laminated Bodies (AREA)

Abstract

L'invention concerne une feuille en résine multicouche qui présente simultanément une excellente aptitude au façonnage thermique, des propriétés de barrière à l'oxygène, des propriétés de barrière à la vapeur et une résistance à l'huile, et qui supprime le gauchissement dans la feuille et après le façonnage thermique. L'invention concerne également un récipient façonné obtenu en façonnant ladite feuille en résine multicouche. La feuille en résine multicouche selon l'invention, formée par stratification de multiples couches en résine, est caractérisée en ce qu'elle est formée à partir d'une couche en résine de polyoléfine qui devient la couche de surface, une couche adhésive, une couche en résine barrière à l'oxygène et une couche en résine qui contient une couche en résine de polyéthylène qui devient une couche de surface inférieure. L'épaisseur de la feuille entière est de 200 à 1300 µm, le rapport de composition de couche entre l'épaisseur de la couche en résine de polyoléfine et l'épaisseur de la feuille entière est de 1 à 30 %, la couche en résine de polyoléfine est de préférence formée à partir d'une résine de polypropylène en bloc, l'épaisseur de la couche en résine de barrière à l'oxygène est de préférence de 10 à 50 µm, la perméabilité à l'oxygène est de préférence inférieure ou égale à 10 cc/m2·jour, et la perméabilité à la vapeur d'eau est de préférence inférieure ou égale à 10 g/m2·jour.
PCT/JP2016/068681 2016-06-23 2016-06-23 Feuille en résine multicouche et récipient façonné WO2017221375A1 (fr)

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JP2018523231A JP6800972B2 (ja) 2016-06-23 2016-06-23 多層樹脂シート及び成形容器
PCT/JP2016/068681 WO2017221375A1 (fr) 2016-06-23 2016-06-23 Feuille en résine multicouche et récipient façonné

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021111815A1 (fr) * 2019-12-03 2021-06-10 デンカ株式会社 Feuille de résine multicouche et récipient de moulage
WO2022054567A1 (fr) * 2020-09-11 2022-03-17 デンカ株式会社 Feuille de résine multicouche et récipient moulé

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59120453A (ja) * 1982-12-28 1984-07-12 出光興産株式会社 樹脂積層体
JPH10315370A (ja) * 1997-05-19 1998-12-02 Daicel Chem Ind Ltd 積層体およびその成形用シート、並びに容器
JP2006021409A (ja) * 2004-07-07 2006-01-26 Idemitsu Unitech Co Ltd 積層シート、当該積層シートからなる容器、及び当該容器の製造方法
JP2006181797A (ja) * 2004-12-27 2006-07-13 Dainippon Ink & Chem Inc 再封止性共押出多層フィルムおよび再封止性ラミネートフィルム
WO2014087696A1 (fr) * 2012-12-07 2014-06-12 電気化学工業株式会社 Feuille de résine thermoplastique dotée de propriétés hydrofuges, et article moulé
WO2014087695A1 (fr) * 2012-12-07 2014-06-12 電気化学工業株式会社 Feuille de résine thermoplastique dotée de propriétés hydrofuges, et article moulé

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59120453A (ja) * 1982-12-28 1984-07-12 出光興産株式会社 樹脂積層体
JPH10315370A (ja) * 1997-05-19 1998-12-02 Daicel Chem Ind Ltd 積層体およびその成形用シート、並びに容器
JP2006021409A (ja) * 2004-07-07 2006-01-26 Idemitsu Unitech Co Ltd 積層シート、当該積層シートからなる容器、及び当該容器の製造方法
JP2006181797A (ja) * 2004-12-27 2006-07-13 Dainippon Ink & Chem Inc 再封止性共押出多層フィルムおよび再封止性ラミネートフィルム
WO2014087696A1 (fr) * 2012-12-07 2014-06-12 電気化学工業株式会社 Feuille de résine thermoplastique dotée de propriétés hydrofuges, et article moulé
WO2014087695A1 (fr) * 2012-12-07 2014-06-12 電気化学工業株式会社 Feuille de résine thermoplastique dotée de propriétés hydrofuges, et article moulé

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021111815A1 (fr) * 2019-12-03 2021-06-10 デンカ株式会社 Feuille de résine multicouche et récipient de moulage
WO2022054567A1 (fr) * 2020-09-11 2022-03-17 デンカ株式会社 Feuille de résine multicouche et récipient moulé

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