CN111469497A - Multilayer resin sheet for deep drawing and molded container - Google Patents
Multilayer resin sheet for deep drawing and molded container Download PDFInfo
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- CN111469497A CN111469497A CN202010135269.6A CN202010135269A CN111469497A CN 111469497 A CN111469497 A CN 111469497A CN 202010135269 A CN202010135269 A CN 202010135269A CN 111469497 A CN111469497 A CN 111469497A
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Abstract
The invention provides a method for manufacturing deep drawing forming container, a multilayer resin sheet for deep drawing forming and a forming container, the multilayer resin sheet for deep drawing forming has the advantages of thermal forming, rigidity and oxygen resistance, is easy to provide groove breaking performance after thermal forming, and is difficult to be thermally adhered with a heat source even if high heat is provided when the multilayer resin sheet is formed into a container with complicated shape and deep drawing. The method for producing a multilayer resin sheet, which comprises molding a multilayer resin sheet at a hot plate temperature of 170 ℃ or higher and less than 185 ℃, is characterized in that the multilayer resin sheet is a multilayer resin sheet which is picked up by using a roller subjected to embossing to impart surface roughness and is formed by laminating styrene resin layers on both surfaces of an oxygen barrier resin layer with a modified olefin polymer layer interposed therebetween, and has a groove formed on one surface side, wherein the total thickness of the modified olefin polymer layer and the styrene resin layer on the one surface side is 40 to 350 [ mu ] m, and the surface roughness (Ra) on the one surface side of the styrene resin layer is 0.1 to 5.0 [ mu ] m.
Description
The present application is a divisional application of the application having an application date of 2013, 22.02 and 2013, an application number of CN201310057159.2, and an invention name of "multilayer resin sheet for deep drawing molding and molded container".
Technical Field
The present invention relates to a multilayer resin sheet for deep drawing and a molded container molded from the same.
Background
Heretofore, as containers for soft drinks, fruit drinks, favorite foods and the like, styrene-based resins excellent in thermoformability and rigidity have been used. However, in recent years, a multilayer resin sheet in which an ethylene-vinyl alcohol copolymer resin layer is provided with a styrene resin layer as the outermost layer and an adhesive layer such as a modified olefin resin interposed therebetween to impart oxygen barrier properties and suppress deterioration in quality due to oxidation of the contents, and a multilayer container comprising the same have become widespread (patent document 1).
In recent years, there have been increasing cases where these containers are manufactured through consecutive steps such as molding, filling of contents, and sealing of a covering material. Patent document 2 proposes a multilayer resin sheet in which a polystyrene resin layer and a polyolefin resin layer are laminated to prevent resin burrs from being generated during press working in a step before a final product is formed.
Further, patent document 3 proposes a multilayer resin sheet which solves a problem of insufficient groove fracture property after thermoforming due to toughness of an oxygen barrier resin by a specific layer structure.
In addition, in recent years, containers having complicated design shapes and deep drawn shapes have been increasing, and in general, when dealing with such container shapes, it is necessary to apply a large amount of heat to the sheet at the time of thermoforming to sufficiently soften the sheet for molding. However, in the case of the multilayer resin sheets described in patent documents 1 to 3, when a direct heating method in which a heat source is brought into contact with a sheet is employed, if the hot plate temperature is increased, there is a possibility that the sheet surface is thermally bonded to the heat source, and there is a problem that the multilayer resin sheets cannot be used for deep drawing which requires a higher temperature than a conventional hot plate.
Patent document 1: japanese laid-open patent publication No. 11-58619
Patent document 3: japanese patent No. 4758926
Disclosure of Invention
The present invention has been made in view of the above circumstances, and an object thereof is to provide a multilayer resin sheet for deep drawing molding which has thermoformability, rigidity, and oxygen barrier properties, is easy to impart snap-off properties to a groove after thermoforming, and is not easily thermally bonded to a heat source even when a high heat is applied to the sheet when a container having a complicated shape and deep drawing is molded, and a molded container obtained by molding the same.
That is, the present inventors have made extensive studies to develop a multilayer resin sheet having the above-mentioned properties and suitable for deep drawing and molding, and as a result, have found that: the present inventors have found that the above problems can be solved by simultaneously adjusting the thicknesses of the modified olefin polymer layer and the styrene resin layer on the groove-forming surface side and the surface roughness (Ra) of the styrene resin layer on the groove-forming surface side in a multilayer resin sheet in which styrene resin layers are laminated on both surfaces of an oxygen barrier resin layer with a modified olefin polymer layer interposed therebetween, and have completed the present invention.
Therefore, according to one aspect of the present invention, there is provided a multilayer resin sheet for deep drawing molding, which is obtained by laminating styrene-based resin layers on both surfaces of an oxygen-barrier resin layer with a modified olefin-based polymer layer interposed therebetween, and which has a groove formed from one surface side, wherein the sum of the thicknesses of the modified olefin-based polymer layer and the styrene-based resin layer on the one surface side is 40 to 350 μm, and the surface roughness (Ra) of one surface of the styrene-based resin layer is 0.1 to 5.0 μm.
In the above, in one embodiment of the invention, the oxygen-blocking resin layer is composed of an ethylene-vinyl alcohol copolymer resin. In one embodiment, the modified olefin-based polymer layer has a thickness of 10 to 50 μm. In one embodiment, the thickness of the oxygen barrier resin layer is 10 to 50 μm. In one embodiment, the styrene-based resin layer is composed of a styrene-based resin containing 4 to 8 mass% of a butadiene rubber component. In one embodiment, the multilayer resin sheet has a thickness of 500 to 1200 μm.
In addition, according to another aspect of the present invention, there is provided a molded container obtained by thermoforming the multilayer resin sheet for deep drawing, the molded container having the concave groove formed from one surface side.
The multilayer resin sheet for deep drawing molding of the present invention has thermoformability, rigidity, oxygen barrier properties, and rupture property of a groove after thermoforming, and is not easily thermally bonded to a heat source even when a large amount of heat is applied during thermoforming, so that it can be easily molded into a more complicated shape or a deep drawn container.
Drawings
Fig. 1 is a schematic longitudinal sectional view showing a laminated structure of a multilayer resin sheet for high heat thermoforming according to an embodiment of the present invention.
Fig. 2 is a schematic perspective view showing an example of the molded container of the present invention.
FIG. 3 is a schematic side view showing an example of the molded container of the present invention.
Fig. 4 is a schematic diagram for explaining a container pressing process.
Description of the reference numerals
1 groove, 2 bending direction, 3 cutting position, 4 advancing direction.
Detailed Description
A multilayer resin sheet for deep drawing molding in one embodiment of the present invention is a thermoplastic multilayer resin sheet, and as shown in FIG. 1, styrene resin layers (12a, 12b) are laminated on both sides of an oxygen barrier resin layer (10) with modified olefin polymer layers (11a, 11b) interposed therebetween. Grooves are formed from one surface side (upper styrene-based resin layer 12a side in fig. 1) of the resin sheet, the total thickness of the modified olefin polymer layer (11a) and the styrene-based resin layer (12a) on the one surface side is 40 to 350 μm, and the surface roughness (Ra) of the exposed surface on which the styrene-based resin layer (12a) is formed is 0.1 to 5.0 μm.
Here, "for deep drawing forming" means that the sheet has properties suitable for deep drawing forming, and deep drawing is defined as a drawing ratio of 0.5 or more, which is a ratio of a depth to a width (if the shape has a plurality of widths, the maximum width is selected) of the formed container, regardless of the shape of the formed container. Here, the deep drawing formed container is a container in which the drawing ratio is 0.5 or more, preferably 0.9 or more, more preferably 1 or more, and most preferably 1.5 or more.
The thermoplastic multilayer resin sheet and the molded container produced by molding the resin sheet will be described in detail below.
< oxygen barrier resin layer (10) >)
Examples of the oxygen barrier resin constituting the oxygen barrier resin layer include ethylene-vinyl alcohol copolymer resins, polyamide resins, and the like. Among them, an ethylene-vinyl alcohol copolymer resin is preferable in view of processability and 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%, preferably 20 to 50 mol%, and a saponification degree of 90% or more, preferably 95% or more, for imparting oxygen barrier properties, processability, and moldability.
Examples of the polyamide resin include: lactam polymers such as caprolactam and laurolactam; polymers of aminocarboxylic acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid; polycondensates of a diamine unit such as an aliphatic diamine such as hexamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2, 4-or 2,4, 4-trimethylhexamethylenediamine or the like, an alicyclic diamine such as 1, 3-or 1, 4-bis (aminomethyl) cyclohexane, bis (p-aminocyclohexyl) methane or the like, an aromatic diamine such as m-or p-xylylenediamine or the like, and a dicarboxylic acid unit such as an aliphatic dicarboxylic acid such as adipic acid, suberic acid, sebacic acid or the like, an alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid or the like, an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid or the like; and copolymers thereof, and the like.
Specific examples of the polyamide resin 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, and nylon 6I/6T, and among them, nylon 6 and nylon MXD6 are preferable.
The thickness of the oxygen barrier resin layer is preferably 10 to 50 μm, more preferably 20 to 40 μm. If the thickness is less than 10 μm, the oxygen barrier property to suppress the deterioration of the quality due to the oxidation of the contents of the molded container may not be obtained, and if the thickness exceeds 50 μm, resin burr may be generated at the time of pressing the thermoformed container, or the notch breakability may be insufficient.
< modified olefin polymer layer (11a, 11b) >
Typical examples of the modified olefin polymer constituting the modified olefin polymer layer include homopolymers of olefins having 2 to 8 carbon atoms such as ethylene, propylene and 1-butene, olefin resins such as copolymers of these olefins with other olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 3-methyl-1-butene, pentene-1, 4-methylpentene-1, hexene-1, octene-1 and decene-1, vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid, acrylic ester, methacrylic ester and styrene, olefin rubbers such as ethylene-propylene copolymers, ethylene-propylene-diene copolymers, ethylene-1-butene copolymers and propylene-1-butene copolymers, specifically, the modified polymer is formed by modifying 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 derivatives thereof such as acid halides, amides, imines, anhydrides, and esters, specifically, maleic acid chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, and glycidyl maleate under grafting reaction conditions.
Among the modified olefin polymers, preferred are ethylene resins, propylene resins, and ethylene-propylene or 1-butene copolymer rubbers modified with an unsaturated dicarboxylic acid or an anhydride thereof, particularly maleic acid or an anhydride thereof.
The thickness of the modified olefin-based polymer layer is preferably 10 to 50 μm, more preferably 20 to 40 μm, on either side. If the thickness is less than 10 μm, a sufficient interlayer adhesion strength may not be obtained, and if the thickness exceeds 50 μm, resin burrs may be generated at the time of pressing the thermoformed container, or the notch breakability may be insufficient.
< styrenic resin layer (12a, 12b) >
Examples of the styrenic resin constituting the styrenic resin layer include homopolymers or copolymers of styrenic monomers such AS styrene, α -methylstyrene, p-methylstyrene, dimethylstyrene, p-tert-butylstyrene and chlorostyrene, copolymers of these styrenic monomers with other monomers such AS styrene-acrylonitrile copolymers (AS resins), graft polymers obtained by graft polymerizing the styrenic monomers with other polymers such AS polybutadiene, styrene-butadiene copolymers, and diene rubber polymers such AS polyisoprene and polychloroprene, such AS high impact polystyrene (HIPS resins) and styrene-acrylonitrile graft polymers (ABS resins).
Among the styrene-based resins, polystyrene (GPPS resin) and high impact polystyrene (HIPS resin) are preferable from the viewpoint of rigidity and moldability of the molded container.
The styrene-based resin preferably contains 4 to 8 mass% of a butadiene rubber component. The adjustment of the butadiene rubber content by mixing GPPS with HIPS is a simple method, but can be adjusted at the stage of the production of HIPS. If the content is less than 4% by mass, a practically sufficient strength of the container may not be obtained, and if the content exceeds 8% by mass, there is a possibility that a problem such as blocking of a hot plate may occur at the time of thermoforming.
In the styrene-based resin layer, a colorant such as a pigment or a dye may be added as necessary within a range not impairing the effects of the present invention; releasing agents such as silicone oils and alkyl esters; fibrous reinforcing agents such as glass fibers; particulate lubricants such as talc, clay, silica and the like; salt compounds of sulfonic acid and alkali metals, antistatic agents such as polyalkylene glycol, and ultraviolet absorbers; additives such as antibacterial agents. In addition, the scrap resin generated in the production process of the multilayer resin sheet or molded container of the present invention may be mixed and used.
The thickness of the styrenic resin layer (12a) on the side of the surface on which the grooves are formed is preferably 30 to 300. mu.m, and more preferably 100 to 200. mu.m. If the thickness is less than 30 μm, the styrene-based resin layer may be broken when it is subjected to thermoforming and stretching, and the modified olefin-based polymer layer may be exposed, thereby impairing the printing accuracy on the surface of the container. In addition, if it exceeds 300. mu.m, the depth of the blade needs to be increased when forming the groove, and there is a possibility that the shape retaining property of the container and the strength of the container may be deteriorated.
The thickness of the styrenic resin layer (12b) on the side of the surface on which the grooves are not formed is preferably 300 to 800. mu.m, and more preferably 400 to 700. mu.m. If the thickness is less than 300. mu.m, the rigidity of the container obtained by thermoforming may be insufficient, and if the thickness exceeds 800. mu.m, the groove fracture property after forming the groove may be reduced.
The surface roughness (Ra) of the exposed surface of the styrene-based resin layer (12a) on the side of the surface on which the grooves are formed is 0.1 to 5.0 [ mu ] m, preferably 0.5 to 3.0 [ mu ] m. If the thickness is less than 0.1 μm, the resin layer tends to be thermally bonded to a heat source during thermoforming, and if the thickness exceeds 5.0. mu.m, the resulting molded article tends to lose its surface gloss, thereby lowering the commercial value.
The surface roughness (Ra) of the exposed surface of the styrene-based resin layer (12b) on the side of the surface on which the grooves are not formed is not particularly limited, but is preferably less than 0.1 μm so as not to reduce the commercial value.
< multilayer resin sheet for deep drawing Molding >
The thermoplastic multilayer resin sheet for deep drawing molding according to one embodiment of the present invention has a layer structure of styrene resin layer/modified olefin polymer layer/oxygen barrier resin layer/modified olefin polymer layer/styrene resin layer as described above, and for example, a layer of the multilayer resin sheet of the present invention or a scrap resin generated in a process of producing a molded container may be laminated on the opposite side of the formation of the concave groove.
In the thermoplastic multilayer resin sheet for deep drawing molding according to one embodiment of the present invention, the sum of the thicknesses of the modified olefin polymer layer (11a) and the styrene resin layer (12a) on the side of the surface on which the grooves are formed is 40 to 350 μm, preferably 120 to 240 μm. If the thickness is less than 40 μm, the thickness of the styrenic resin layer on the side of the surface on which the grooves are formed becomes relatively small, and the styrenic resin layer may be broken when it is stretched by thermoforming, thereby impairing the appearance, strength, etc. of the container. In addition, if it exceeds 350 μm, the depth of blade insertion at the time of forming the groove needs to be increased, and there is a possibility that the holding performance of the container shape and the container strength are lowered.
The thickness of the thermoplastic multilayer resin sheet for deep drawing is preferably 500 to 1200. mu.m, and more preferably 700 to 1000. mu.m. If the thickness is less than 500. mu.m, the strength of the thermoformed container may be insufficient, and if the thickness exceeds 1200. mu.m, the production cost of the container may be increased.
The method for molding the thermoplastic multilayer resin sheet for deep drawing is not particularly limited, and a general method can be employed. For example, there are a method of melt-extruding the respective raw material resins using 4 or more single-screw extruders and obtaining a multilayer resin sheet by a feed jacket and a T-die; a method for obtaining a multilayer resin sheet using a manifold mold.
The method for imparting a predetermined surface roughness to the styrene-based resin layer in the thermoplastic multilayer resin sheet for deep drawing molding of the present invention, particularly to the exposed surface of the styrene-based resin layer (12a) on the side of the surface on which the grooves are formed, is not particularly limited, and a general method can be employed. For example, in picking up the molten resin, a method of picking up the molten resin by using a roll or a wheel belt which is preliminarily subjected to unevenness processing is exemplified.
< molded container >
Fig. 2 and 3 show an example of a molded container of the present invention.
The molded container of the present invention is obtained by thermoforming the thermoplastic multilayer resin sheet of the present invention. Examples of the thermoforming method include general vacuum forming and pressure forming, and a plug assist method in which one surface of a sheet is brought into contact with a plug to form the sheet; and a method of forming a so-called match mold (match mold) in which both surfaces of a sheet are brought into contact with a pair of female and male molds to form the sheet. As a method for heating and softening the sheet before molding, a known sheet heating method such as radiant heating using an infrared heater or the like which is heated in a non-contact manner can be applied.
The molding temperature at the time of thermoforming may be appropriately set in accordance with the melting point of the resin or the like, and when deep drawing is performed with a drawing ratio of 0.5 or more using the resin sheet according to the present invention, the hot plate temperature is set to 170 ℃ or more, preferably 175 to 180 ℃. If the hot plate temperature is less than 170 ℃, the molding state of the container is insufficient due to insufficient heating, and if it is too high, there is a possibility that the container is thermally bonded to the hot plate, which is not preferable.
In addition, the molding container of the present invention has a groove. The groove has a V-shaped cross section, and can be formed by heating the one surface side, i.e., the side where the sum of the thicknesses of the modified olefin polymer layer and the styrene resin layer is 50 to 400 μm, by a hot plate method or the like and then inserting a V-shaped blade.
Examples
The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the examples.
The resin raw materials used in the examples are as follows.
(1) Oxygen barrier resin layer
Ethylene-vinyl alcohol copolymer "EVA L J-102B" (manufactured by Colorado, having an ethylene content of 32 mol% and a degree of saponification of 99% or more)
(2) Modified olefin polymer layer
"MODIC F502" (manufactured by Mitsubishi chemical corporation)
(3) Styrene resin layer
HIPS resin "TOYOSTYRO L H850" (manufactured by TOYO STYRENE Co., L td., butadiene content 9.0 mass%)
GPPS resin "HRM 23" (manufactured by TOYO STYRENE Co., L td.)
< example 1 >
The following multilayer resin sheets were obtained by a feed-bushing method using 240 mm single-screw extruders and 165 mm single-screw extruder: the multilayer resin sheet is provided with a layer structure comprising a styrene-based resin layer (12a) having a thickness of 165 [ mu ] m/modified olefin-based polymer layer (11a) having a thickness of 35 [ mu ] m/oxygen barrier resin layer (10) having a thickness of 15 [ mu ] m/modified olefin-based polymer layer (11b) having a thickness of 35 [ mu ] m/styrene-based resin layer (12b) having a thickness of 650 [ mu ] m, wherein the total thickness of the styrene-based resin layer (12a) and the modified olefin-based polymer layer (11a) is 200 [ mu ] m, and wherein the surface roughness (Ra) of the styrene-based resin layer (12a) is 0.23 [ mu ] m by using a metal roll which is subjected to embossing processing with a surface roughness (Ra) of.
< example 2 >
Using the same method as in example 1, the following multilayer resin sheet was obtained: the coating composition comprises a styrene-based resin layer (12a) having a thickness of 40 μm/modified olefin-based polymer layer (11a) having a thickness of 20 μm/oxygen barrier resin layer (10) having a thickness of 20 μm/modified olefin-based polymer layer (11b) having a thickness of 20 μm/styrene-based resin layer (12b) having a thickness of 800 μm (total thickness of the styrene-based resin layer (12a) and the modified olefin-based polymer layer (11a) being 60 μm), and the styrene-based resin layer (12a) having a surface roughness (Ra) of 0.25 μm.
< example 3 >
Using the same method as in example 1, the following multilayer resin sheet was obtained: the coating composition comprises a styrene-based resin layer (12a) having a thickness of 1000 μm (the total thickness of the styrene-based resin layer (12a) and the modified olefin-based polymer layer (11a) being 300 μm), a modified olefin-based polymer layer (11a) having a thickness of 15 μm/an oxygen barrier resin layer (10) having a thickness of 20 μm/a modified olefin-based polymer layer (11b) having a thickness of 15 μm/a styrene-based resin layer (12b) having a thickness of 665 μm, and the styrene-based resin layer (12a) having a surface roughness (Ra) of 0.30 μm.
< example 4 >
Using the same method as in example 1, the following multilayer resin sheet was obtained: comprising a styrene-based resin layer (12a) having a thickness of 30 μm/modified olefin-based polymer layer (11a) having a thickness of 15 μm/oxygen-blocking resin layer (10) having a thickness of 20 μm/modified olefin-based polymer layer (11b) having a thickness of 15 μm/styrene-based resin layer (12b) having a thickness of 820 μm (total thickness of styrene-based resin layer (12a) and modified olefin-based polymer layer (11a) being 45 μm), and styrene-based resin layer (12a) having a surface roughness (Ra) of 0.33. mu.m.
< example 5 >
Using the same method as in example 1, the following multilayer resin sheet was obtained: the coating composition comprises a styrene-based resin layer (12a) having a thickness of 325 μm/modified olefin-based polymer layer (11a) having a thickness of 15 μm/oxygen barrier resin layer (10) having a thickness of 20 μm/modified olefin-based polymer layer (11b) having a thickness of 15 μm/styrene-based resin layer (12b) having a thickness of 525 μm, wherein the total thickness of the styrene-based resin layer (12a) and the modified olefin-based polymer layer (11a) is 340 μm, and the styrene-based resin layer (12a) has a surface roughness (Ra) of 0.28 μm.
< example 6 >
The following multilayer resin sheet was obtained in the same manner as in example 1, except that a metal roll having an uneven surface roughness (Ra) of 0.3 μm was used: the coating composition comprises a styrene-based resin layer (12a) having a thickness of 165 μm/modified olefin-based polymer layer (11a) having a thickness of 20 μm/oxygen barrier resin layer (10) having a thickness of 20 μm/modified olefin-based polymer layer (11b) having a thickness of 20 μm/styrene-based resin layer (12b) having a thickness of 675 μm, wherein the total thickness of the styrene-based resin layer (12a) and the modified olefin-based polymer layer (11a) is 185 μm, and the styrene-based resin layer (12a) has a surface roughness (Ra) of 0.15 μm.
< examples 7 to 9 >
The following multilayer resin sheet was obtained in the same manner as in example 1, except that metal rolls each having an uneven surface with a surface roughness (Ra) of 2, 5, and 10 μm were used: the coating composition comprises a styrene-based resin layer (12a) having a thickness of 900 μm (the total thickness of the styrene-based resin layer (12a) and the modified olefin-based polymer layer (11a) being 200 μm), a modified olefin-based polymer layer (11a) having a thickness of 35 μm/an oxygen barrier resin layer (10) having a thickness of 15 μm/a modified olefin-based polymer layer (11b) having a thickness of 35 μm/a styrene-based resin layer (12b) having a thickness of 650 μm, and the styrene-based resin layer (12a) having a surface roughness (Ra) of 0.95, 2.40 or 4.70 μm, respectively.
< comparative example 1 >
In the same manner as in example 1, the following multilayer resin sheet was obtained: the coating layer is composed of a styrene resin layer (12a) with a thickness of 15 [ mu ] m/modified olefin polymer layer (11a) with a thickness of 15 [ mu ] m/oxygen barrier resin layer (10) with a thickness of 20 [ mu ] m/modified olefin polymer layer (11b) with a thickness of 15 [ mu ] m/styrene resin layer (12b) with a thickness of 835 [ mu ] m, wherein the total thickness of the styrene resin layer (12a) and the modified olefin polymer layer (11a) is 30 [ mu ] m, and the surface roughness (Ra) of the styrene resin layer (12 a.
< comparative example 2 >
In the same manner as in example 1, the following multilayer resin sheet was obtained: has a layer structure comprising a styrene-based resin layer (12a) of 360 [ mu ] m/modified olefin-based polymer layer (11a) of 15 [ mu ] m/oxygen barrier resin layer (10) of 20 [ mu ] m/modified olefin-based polymer layer (11b) of 15 [ mu ] m/styrene-based resin layer (12b) of 490 [ mu ] m, and has a thickness of 900 [ mu ] m (the total thickness of the styrene-based resin layer (12a) and the modified olefin-based polymer layer (11a) is 375 [ mu ] m), and the surface roughness (Ra) of the styrene-based resin layer (12a) is 0.28 [ mu ] m.
< comparative examples 3 to 6 >
The following multilayer resin sheet was obtained in the same manner as in example 1, except that metal rolls each having an uneven surface roughness (Ra) of 0.1, 0.2, 12, 15 μm were used: the coating composition comprises a styrene-based resin layer (12a) having a thickness of 900 μm (the total thickness of the styrene-based resin layer (12a) and the modified olefin-based polymer layer (11a) being 200 μm), a modified olefin-based polymer layer (11a) having a thickness of 35 μm/an oxygen barrier resin layer (10) having a thickness of 15 μm/a modified olefin-based polymer layer (11b) having a thickness of 35 μm/a styrene-based resin layer (12b) having a thickness of 650 μm, and the styrene-based resin layer (12a) having a surface roughness (Ra) of 0.04, 0.07, 5.65 or 7.60 μm, respectively.
< comparative example 7 >
In the same manner as in example 1, the following multilayer resin sheet was obtained: the procedure of example 1 was repeated except that the thickness of the styrene-based resin layer (12a) was 1000. mu.m (the total thickness of the styrene-based resin layer (12a) and the modified olefin-based polymer layer (11a) was 600. mu.m), and the thickness of the modified olefin-based polymer layer (11a) was 30 μm/the oxygen barrier resin layer (10) was 20 μm/the modified olefin-based polymer layer (11b) was 20 μm/the styrene-based resin layer (12b) was 360. mu.m.
Further, as the styrene-based resin, a resin obtained by mixing a HIPS resin and a GPPS resin at 80/20(HIPS/GPPS) by mass ratio (butadiene rubber component content: 7.2 mass%) was used.
The multilayer resin sheet was processed in a series of steps of molding, forming grooves, and pressing a container (fig. 4) under the following conditions, to obtain a container shown in fig. 2. The grooves are formed from the styrene-based resin layer 12a side, and the depth of the grooves is adjusted according to the heating temperature of the groove-formed portion.
Using a machine: CFF-300(CKD corporation)
Upper hot plate temperature: 170 deg.C
Lower hot plate temperature: 170 deg.C
Groove portion heating temperature: 160 deg.C
Depth of the groove: 350 μm
Container punching blade upper side structure: outer blade
Structure under the container punching blade: inner blade
Gap between upper and lower sides of container punching blade: 20 μm
Various evaluations of the obtained multilayer resin sheet and container were carried out according to the following methods. The results are shown in Table 1.
(1) Surface roughness (Ra)
The surface roughness (Ra) of the sheet was measured by the following method, and evaluated according to the following criteria.
[ measuring method ] method 0601 according to JIS B
Using a machine: SURFCOM 120A, manufactured by Tokyo precision Co., Ltd
(2) In the formed state
Moldability in thermoforming the container was evaluated by the following criteria.
○ good formability
× it was found that the molding was poor and the surface layer was damaged due to the adhesion of the hot plate.
(3) Groove breakability
The groove-forming portion was bent in the bending direction shown in fig. 3, and evaluated by the following criteria.
○ it can be broken by one bending.
△ it can be broken by bending for many times.
× it can not be broken even after being bent for many times.
(4) Surface gloss of containers
The surface gloss of the bottom surface of the molded container was measured.
[ evaluation method ]
The determination method comprises the following steps: method according to JIS K7105
Using a machine: digital gloss meter manufactured by Nippon Denshoku K.K
[ evaluation standards ]
○ the glossiness is more than 20%
× the glossiness is less than 20%
(5) Comprehensive judgment
When all the evaluation results were ○, the total was ○, and the other was ×.
TABLE 1
Claims (8)
1. A method for producing a deep-drawn container, comprising molding a multilayer resin sheet at a hot plate temperature of 170 ℃ or higher and less than 185 ℃, wherein the multilayer resin sheet is a multilayer resin sheet which is picked up by a roll subjected to embossing to impart surface roughness and in which a styrene resin layer is laminated on both surfaces of an oxygen-barrier resin layer with a modified olefin polymer layer interposed therebetween to form a recess on one surface side, the total thickness of the modified olefin polymer layer and the styrene resin layer on the one surface side is 40 to 350 [ mu ] m, and the surface roughness (Ra) of the styrene resin layer on the one surface side is 0.1 to 5.0 [ mu ] m.
2. A multilayer resin sheet for deep drawing molding, which is obtained by laminating styrene resin layers on both surfaces of an oxygen barrier resin layer with a modified olefin polymer layer interposed therebetween and has a groove formed on one surface side, wherein the total thickness of the modified olefin polymer layer and the styrene resin layer on the one surface side is 40 to 350 [ mu ] m, the surface roughness (Ra) of the styrene resin layer on the one surface side is 0.1 to 0.95 [ mu ] m, the thickness of the styrene resin layer on the surface side on which the groove is not formed is 300 to 800 [ mu ] m, and the surface roughness (Ra) of the styrene resin layer on the surface side on which the groove is not formed is less than 0.1 [ mu ] m.
3. The multilayer resin sheet for deep drawing molding according to claim 2, wherein the oxygen barrier resin layer is formed of an ethylene-vinyl alcohol copolymer resin.
4. The multilayer resin sheet for deep drawing molding according to claim 2 or 3, wherein the modified olefin polymer layer has a thickness of 10 to 50 μm.
5. The multilayer resin sheet for deep drawing molding according to any one of claims 2 to 4, wherein the thickness of the oxygen-barrier resin layer is 10 to 50 μm.
6. The multilayer resin sheet for deep drawing molding according to any one of claims 2 to 5, wherein the styrene resin layer is formed of a styrene resin containing 4 to 8 mass% of a butadiene rubber component.
7. The multilayer resin sheet for deep drawing molding according to any one of claims 2 to 6, wherein the thickness is 500 to 1200 μm.
8. A molded container obtained by thermoforming the multilayer resin sheet for deep drawing molding according to any one of claims 2 to 7, wherein the molded container has the recessed groove formed from one surface side.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010135269.6A CN111469497A (en) | 2013-02-22 | 2013-02-22 | Multilayer resin sheet for deep drawing and molded container |
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| CN201310057159.2A CN104002509A (en) | 2013-02-22 | 2013-02-22 | Multilayer resin sheet for deep drawing molding, and molded container |
| CN202010135269.6A CN111469497A (en) | 2013-02-22 | 2013-02-22 | Multilayer resin sheet for deep drawing and molded container |
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| CN201310057159.2A Division CN104002509A (en) | 2013-02-22 | 2013-02-22 | Multilayer resin sheet for deep drawing molding, and molded container |
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| CN111469497A true CN111469497A (en) | 2020-07-31 |
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| CN201310057159.2A Pending CN104002509A (en) | 2013-02-22 | 2013-02-22 | Multilayer resin sheet for deep drawing molding, and molded container |
| CN202010135269.6A Pending CN111469497A (en) | 2013-02-22 | 2013-02-22 | Multilayer resin sheet for deep drawing and molded container |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2016163361A1 (en) * | 2015-04-08 | 2016-10-13 | デンカ株式会社 | Multilayered thermoplastic resin sheet and container comprising same |
| CN106273952A (en) * | 2015-05-14 | 2017-01-04 | 电气化学工业株式会社 | Multi-layer resinous thin film and container molding |
| CN106273953A (en) * | 2015-05-14 | 2017-01-04 | 电气化学工业株式会社 | Multi-layer resinous thin film and container molding |
| TWI736536B (en) * | 2016-06-21 | 2021-08-21 | 日商電化股份有限公司 | Multilayer resin film and molded container |
| CN112895644A (en) * | 2019-12-03 | 2021-06-04 | 电化株式会社 | Multilayer resin sheet and molded container |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1791506A (en) * | 2003-05-26 | 2006-06-21 | 山内株式会社 | Sheet for thermal pressing |
| JP2008213355A (en) * | 2007-03-06 | 2008-09-18 | Denki Kagaku Kogyo Kk | Thermoplastic multi-layer resin sheet and molded container |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10100338A (en) * | 1996-10-03 | 1998-04-21 | Idemitsu Petrochem Co Ltd | Multilayered sheet and container |
| CN203172088U (en) * | 2013-02-22 | 2013-09-04 | 电气化学工业株式会社 | Multi-layer resin sheet for deep drawing forming and forming container |
-
2013
- 2013-02-22 CN CN201310057159.2A patent/CN104002509A/en active Pending
- 2013-02-22 CN CN202010135269.6A patent/CN111469497A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1791506A (en) * | 2003-05-26 | 2006-06-21 | 山内株式会社 | Sheet for thermal pressing |
| JP2008213355A (en) * | 2007-03-06 | 2008-09-18 | Denki Kagaku Kogyo Kk | Thermoplastic multi-layer resin sheet and molded container |
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| CN104002509A (en) | 2014-08-27 |
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