CN116096647A - Container - Google Patents
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- CN116096647A CN116096647A CN202180057586.3A CN202180057586A CN116096647A CN 116096647 A CN116096647 A CN 116096647A CN 202180057586 A CN202180057586 A CN 202180057586A CN 116096647 A CN116096647 A CN 116096647A
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- Prior art keywords
- container
- polyethylene terephthalate
- terephthalate resin
- resin
- copolymerized polyethylene
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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
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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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
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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
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D3/00—Rigid or semi-rigid containers having bodies or peripheral walls of curved or partially-curved cross-section made by winding or bending paper without folding along defined lines
- B65D3/22—Rigid or semi-rigid containers having bodies or peripheral walls of curved or partially-curved cross-section made by winding or bending paper without folding along defined lines with double walls; with walls incorporating air-chambers; with walls made of laminated material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
Abstract
The container (1) is mainly composed of a paper base layer (10) and a resin layer (11) laminated on the inner side of the base layer (10). The copolymerized polyethylene terephthalate resin constituting the resin layer (11) is a copolymerized polyethylene terephthalate resin obtained by copolymerization with isophthalic acid, the copolymerization ratio of isophthalic acid in the copolymerized polyethylene terephthalate resin is 1 mol% or more and less than 10 mol%, and the melting point of the copolymerized polyethylene terephthalate resin is 234 ℃ or more and 250 ℃ or less. With this structure, the container is a container having high adhesion between the base material layer (10) and the resin layer (11) and high heat resistance, and thus, can prevent defective molding of the container (1), and is suitable for use even when the content reaches a high temperature or when the content is subjected to a baking process.
Description
Technical Field
The present invention relates to a container, and more particularly, to a container used as a paper cup, a box, or the like for storing beverages, foods, or the like.
Background
Conventionally, as a container for storing beverages, foods, and the like, there is a container using a composite substrate in which synthetic resins are laminated on one or both surfaces of a paper substrate.
Japanese patent No. 4750909 discloses a container using a homo-polyethylene terephthalate (PET) as a resin.
Further, japanese patent No. 5680917 discloses a container using a copolymerized PET resin (a copolymerization component ratio of 10 to 40 mol%) as a resin.
Prior art literature
Patent literature
Patent document 1: japanese patent No. 4750909
Patent document 2: japanese patent No. 5680917
The melting point of the average PET used in japanese patent No. 4750909 is generally about 255 ℃, and in order to uniformly form a film on the surface of a paper substrate by extrusion lamination, it is necessary to extrude the resin at a high temperature exceeding 310 ℃. However, PET resins are susceptible to hydrolysis under high temperature conditions. Therefore, if the PET resin is a homogeneous PET resin having a high melting point, it is easy to assume that the heat resistance is higher, but if the extrusion temperature is too high, hydrolysis occurs in a part of the PET resin on the surface of the container molded after extrusion lamination, and as a result, the heat resistance of the part, even the whole container, is lowered. On the other hand, although the heat resistance is improved when the extrusion temperature is lowered in order to reduce the influence of hydrolysis, the melt viscosity at the time of extrusion lamination becomes high, so that it is difficult to uniformly form a film on the paper surface. Even if the film is formed smoothly, adhesion to paper is deteriorated during pressing against the paper surface due to high melt viscosity of the resin, and when a container is formed using such a composite base material, poor molding of the container or delamination between the paper and PET resin due to the deterioration of adhesion is likely to occur.
Further, since the melting point of the copolymerized PET resin in japanese patent No. 5680917 is 230 ℃ or lower, the extrusion temperature of the resin can be suppressed to be low, hydrolysis under high temperature conditions is less likely to occur, and the decrease in adhesion to paper during extrusion to the paper surface can be reduced. However, since the melting point is as low as 230 ℃ or lower, the heat resistance of the molded container is poor. In particular, in the case of a food such as a filled-in butterscotch (gratin) which is to be cooked by heating, for example, in the case of a butterscotch, it is necessary to perform a baking step under high-temperature conditions after filling in the container to roast the surface, and high heat resistance is required because the temperature is locally high. In addition, since the containers are packaged in a baking process and then distributed on the market as food products, and the containers are heated to a high temperature when the consumers use a microwave oven to heat the foods, high heat resistance is required as well. However, the container of japanese patent No. 5680917, which is poor in heat resistance, cannot sufficiently satisfy such a requirement.
The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a container having high adhesion between a base material layer and a resin layer and high heat resistance.
Disclosure of Invention
In order to achieve the above object, a first aspect of the present invention provides a container comprising a composite substrate comprising a substrate layer comprising paper and a resin layer comprising a copolymerized polyethylene terephthalate resin laminated on at least one side of the substrate layer, wherein the copolymerized polyethylene terephthalate resin is a copolymerized polyethylene terephthalate resin obtained by copolymerization with isophthalic acid, and the copolymerization ratio of isophthalic acid in the copolymerized polyethylene terephthalate resin is 1 mol% or more and less than 10 mol%, and the melting point of the copolymerized polyethylene terephthalate resin is 234 ℃ or more and 250 ℃ or less.
With this structure, the container has high adhesion between the base material layer and the resin layer and high heat resistance.
The container according to the second aspect of the present invention is the structure according to the first aspect of the present invention, wherein the copolymerization ratio of isophthalic acid in the copolymerized polyethylene terephthalate resin is 4.0 mol% or less.
With this structure, the adhesion between the base material layer and the resin layer is suitable, and the heat resistance of the container is also suitable.
In the container according to a third aspect of the present invention, in the structure according to the first or second aspect, the adhesion of the resin layer to the base layer is 4N/50mm or more.
If so constructed, adhesion is suitable.
A fourth aspect of the present invention provides the structure of any one of the first to third aspects, wherein the copolymerization ratio of isophthalic acid in the copolymerized polyethylene terephthalate resin is 1.5 mol% or more and 2.2 mol% or less.
With this structure, the adhesion between the base material layer and the resin layer is more suitable, and the heat resistance of the container is also more suitable.
A fifth aspect of the present invention provides the structure of any one of the first to fourth aspects, wherein the copolymerized polyethylene terephthalate resin is a biomass-derived polyethylene terephthalate resin having a biobased carbon content of 5% or more.
With this configuration, the amount of fossil resources used can be reduced, and the carbon neutral (carbon neutral) property can be improved.
A container according to a sixth aspect of the present invention is the structure of any one of the first to fifth aspects, wherein the container includes a bottom portion and a side wall portion rising from a peripheral edge of the bottom portion, and the bottom portion and the side wall portion are connected by thermal bonding.
If so constructed, the bottom and side wall portions are firmly bonded.
A container according to a seventh aspect of the present invention is the structure of the invention according to any one of the first to fifth aspects, wherein the container is formed by press molding or bending-based molding of one sheet of base paper obtained from a composite base material.
If so constructed, the container is a press-formed article or a formed article formed by bending.
As described above, the container according to the first aspect of the present invention is a container having high adhesion between the base material layer and the resin layer and high heat resistance, and therefore, can be used while preventing defective molding of the container and also being suitable for use when the content reaches a high temperature or when the content is subjected to a baking process.
In addition to the effects of the first aspect, the container of the second aspect of the present invention is convenient to use because the adhesion between the base material layer and the resin layer and the heat resistance of the container are also suitable.
In the container according to the third aspect of the present invention, in addition to the effects of the first or second aspects of the present invention, the adhesion is also suitable, and thus, defective molding of the container can be suitably prevented.
In the container according to the fourth aspect of the present invention, in addition to the effects of the invention according to any one of the first to third aspects, the adhesion between the base material layer and the resin layer and the heat resistance of the container are more suitable, and therefore, the use is more convenient.
In addition to the effects of the invention according to any one of the first to fourth aspects, the container according to the fifth aspect of the present invention can reduce the amount of fossil resources used, and can improve the carbon neutrality, thereby improving the sustainability and contributing to environmental protection.
In the container according to the sixth aspect of the present invention, in addition to the effects of the invention according to any one of the first to fifth aspects, the bottom portion and the side wall portion are firmly bonded, and thus, the container is stably molded.
In the seventh aspect of the present invention, in addition to the effects of the invention according to any one of the first to fifth aspects, the container is a pressed molded article or a molded article formed by bending, and thus is a stably molded container.
Drawings
Fig. 1 is a cross-sectional view showing the overall structure of a container according to a first embodiment of the present invention.
Fig. 2 is an enlarged cross-sectional view of the "X" portion shown in fig. 1.
Fig. 3 is a cross-sectional view showing the overall structure of a container according to a second embodiment of the present invention.
Fig. 4 is a perspective view of a container showing a third embodiment of the present invention for example.
Detailed Description
Fig. 1 is a cross-sectional view showing the overall structure of a container according to a first embodiment of the present invention, and fig. 2 is an enlarged cross-sectional view of an "X" portion shown in fig. 1.
Referring to these drawings, a container 1 is mainly composed of a bottom 2 and a side wall portion 3 rising from the periphery of the bottom 2.
Referring to fig. 2, the side wall portion 3 is composed of a composite base material 7, and the composite base material 7 includes a base material layer 10 made of paper and a resin layer 11 made of a copolymerized polyethylene terephthalate resin laminated on the inner side (the surface in the direction of accommodating the content) of the base material layer 10.
The bottom 2 is also composed of a composite base material 7 having the same structure as the side wall 3, and the bottom 2 and the side wall 3 are connected by thermal bonding. Specifically, after punching out a side wall member (the developed shape of the side wall portion 3) and a bottom surface member (the developed shape of the bottom portion 2) of a predetermined shape from the composite base material 7, the end portions of the both members are bonded to each other by a known method such as thermal bonding, thereby forming a container shape.
The copolymerized polyethylene terephthalate resin of the present invention is a copolymerized polyethylene terephthalate resin obtained by copolymerization with isophthalic acid (IPA), and the copolymerization ratio of isophthalic acid in the copolymerized polyethylene terephthalate resin is 1 mol% or more and less than 10 mol%.
With this configuration, the container having high adhesion between the base material layer 10 and the resin layer 11 and high heat resistance can be obtained, and thus, the container 1 can be prevented from being formed poorly, and can be suitably used even when the content reaches a high temperature or when the content is subjected to a baking process.
The upper limit of the copolymerization ratio of isophthalic acid is preferably 8 mol% or less, more preferably 4.0 mol% or less, and even more preferably 2.2 mol% or less. The lower limit is preferably 1.5 mol% or more. Thus, the range of the upper limit value and the lower limit value is preferably 1.5 mol% or more and 2.2 mol% or less. Accordingly, the effect of improving the adhesion and the effect of improving the heat resistance are more favorably achieved. In general, a polyethylene terephthalate resin is obtained by polycondensing an acid component mainly composed of terephthalic acid and a glycol component mainly composed of ethylene glycol, but the copolymer polyethylene terephthalate resin used in the present invention contains isophthalic acid as an acid component in addition to terephthalic acid, and the copolymer polyethylene terephthalate resin is obtained by copolymerizing the isophthalic acid in a predetermined ratio. In addition, other acid components may be contained as long as the effects of the present invention are not impaired, and components such as diethylene glycol may be contained as the glycol component in addition to ethylene glycol. The copolymerized polyethylene terephthalate resin used in the present invention may be a resin obtained by mixing a plurality of polyethylene terephthalate resins having different copolymerization ratios and adjusting the ratio to a predetermined copolymerization ratio suitable for the present invention. For example, a resin in which a homo-polyethylene terephthalate resin and a co-polyethylene terephthalate resin are mixed in a predetermined ratio and adjusted to a predetermined copolymerization ratio suitable for the present invention, or a resin in which a polyethylene terephthalate resin having a different copolymerization ratio is mixed in a predetermined ratio and adjusted to a predetermined copolymerization ratio suitable for the present invention may be used. In addition, the copolymerization ratio of isophthalic acid can be obtained by supplying a copolymerized polyethylene terephthalate resin based on 1 Qualitative/quantitative analysis of the H-NMR spectrum measurement. Specifically, the method can be obtained as follows: according to the passing through 1 The spectra obtained by H-NMR spectrometry are estimated for the monomer units composed of terephthalic acid and the monomer units composed of isophthalic acid in the copolymerized polyethylene terephthalate resin, respectively, and the composition ratio (molar ratio) of each monomer unit in the copolymerized polyethylene terephthalate resin is calculated from the peak area ratio of the spectra, and the "molar ratio of isophthalic acid monomer unit" is calculated relative to the "molar ratio of terephthalic acid monomer unit and the" molar ratio of isophthalic acid monomer unitThe ratio (%) of the total of (2).
The copolymer polyethylene terephthalate resin of the present invention has a melting point of 234 ℃ to 250 ℃. The melting point is preferably 240 ℃ to 250 ℃, more preferably 243 ℃ to 250 ℃. In such a configuration, the melting point is in a suitable range, and therefore, the extrusion temperature at the time of extrusion lamination is kept low and the melting point itself is sufficiently high, so that the adhesion between the base material layer 10 and the resin layer 11 and the heat resistance of the container 1 are suitable. In addition, the melting point may be determined by Differential Scanning Calorimetry (DSC).
In the copolymerized polyethylene terephthalate resin of the present invention, the crystalline fraction (%) is preferably 2% or more and 15% or less, more preferably 3% or more and 10% or less. With this configuration, the adhesion between the base material layer 10 and the resin layer 11 is suitable, and the molding failure of the container 1 can be reduced. In particular, in the case where the container of the present invention is produced by press-molding a single base paper obtained from the composite base material 7, the shape retention of the container may be reduced with the passage of time due to the rebound of the paper after press-molding, but if the crystalline portion (%) of the copolymerized polyethylene terephthalate resin constituting the composite base material 7 is within the above-described range, the adhesion of the base material layer 10 and the resin layer 11 or the adhesion of the resin layer 11 to each other is appropriate, so that the reduction in shape retention after press-molding can be suppressed. The crystalline fraction (%) of the copolymerized polyethylene terephthalate resin can be obtained by, for example, removing the resin layer from the composite substrate 7 by removing only the resin layer 11 or the like, and measuring the dissolution behavior by Differential Scanning Calorimetry (DSC), and the crystalline fraction (%) can be calculated based on the following formula 1. Further, the crystalline portion is estimated to be an amorphous portion other than the crystalline portion, and the amorphous portion can be calculated by amorphous portion (%) =100-crystalline portion (%).
Formula 1:
[ formula 1]
The adhesion of the resin layer 11 of the present invention to the base layer 10 is preferably 4N/50mm or more. With this configuration, the adhesion is suitable, and thus, defective molding of the container 1 can be prevented appropriately. The higher the value of the adhesion, the better the molding failure, so the preferable upper limit of the adhesion is not particularly limited, but may be about 20N/50mm or less if the container is to be decomposed or disassembled easily for the purpose of reducing the volume of the garbage after use as the container. The adhesion can be measured by a measurement method in examples described later.
The polyethylene terephthalate resin of the present invention is preferably a biomass polyethylene terephthalate resin having a bio-based carbon content of 5% or more and being biologically derived (derived from biomass resources). Polyethylene terephthalate resins are resins obtained by polycondensation of ethylene glycol and terephthalic acid as main components, but most of them (including japanese patent publication No. 4750909 and japanese patent publication No. 5680917) are derived from fossil resources. By using the biomass polyethylene terephthalate resin obtained from a bio-derived raw material such as sugarcane, the amount of fossil-derived resources used can be reduced, and the carbon neutrality can be improved, thereby improving the sustainability and contributing to environmental protection.
In the present invention, the biobased carbon content, which is an index indicating the proportion of the bio-derived raw material in the copolymerized polyethylene terephthalate resin, is preferably 5% or more, and more preferably 15% or more. The higher the bio-based carbon content, the smaller the proportion of raw materials derived from fossil resources, and thus becomes a container beneficial to environmental protection. On the other hand, if the ratio of the bio-based carbon content is increased, the cost is also increased, and thus, it is more preferable to be in an appropriate range. Further, the biobased carbon content may be expressed as a value of C14 content obtained by a radioactive carbon (C14) measurement method based on ISO-16620-2 (equivalent to ASTM-D6866 standard specification). That is, since C14 is contained in a fossil resource in a small amount, and C14 is contained in a biological resource in a certain ratio (105.5 pMC), if the content of C14 in the copolymerized polyethylene terephthalate resin is PC14, the bio-based carbon content can be calculated by the following formula.
Biobased carbon content (%) =pc 14/105.5×100
Next, fig. 3 is a cross-sectional view showing the overall structure of a container according to a second embodiment of the present invention.
The structure of the container 21 according to the second embodiment of the present invention is basically the same as that of the container 1 according to the first embodiment described above, and therefore, differences will be mainly described below.
Referring to fig. 3, the container 21 is formed by press forming of a sheet of base paper obtained from a composite base material 27 (the same structure as the composite base material 7 of the first embodiment described above). Specifically, a container 21 having a bottom 22 and a side wall 23 rising from the periphery of the bottom 22 is formed by punching a sheet of base paper of a predetermined shape obtained from a composite base material 27 and then press-molding the sheet.
Although not shown, the container according to the third embodiment is formed by bending a single piece of base paper obtained from a composite base material (similar to the composite base material 7 according to the first embodiment) and molding the folded piece of base paper into a predetermined container shape. Specifically, a container having a bottom portion and a side wall portion rising from the peripheral edge of the bottom portion is configured by forming the bottom portion and the side wall portion rising from the peripheral edge of the bottom portion by punching a sheet of base paper of a predetermined shape obtained from a composite base material and bending the base paper.
The container according to each embodiment of the present invention can be used for various applications, but the application is not limited thereto, and for example, the container can be used for food storage. In addition, the container is particularly suitable for storing foods which are heated under high temperature conditions after the foods are filled in the container. Specifically, the heat-resistant paper container can be used under a high-temperature heating condition of 100 ℃ or higher, in other words, the heat-resistant paper container. In addition, the heating cooker can be used for heating and cooking in ovens (including bread toasters, grills and the like) with the temperature of more than 200 ℃.
In the container according to the embodiments of the present invention, the structure of the paper constituting the composite base material is not particularly limited, and pure white paper, kraft paper, and the like may be used according to the intended use,Parchment paper, ivory paper, manila paper, card paper, cuppaper, and the like. In addition, the basis weight of the paper is preferably 150g/m 2 ～500g/m 2 . With this configuration, the container can be easily molded, and the cost of the container can be suppressed.
In the container according to the embodiments of the present invention, the lamination method of the polyethylene terephthalate resin to the paper is not particularly limited, and extrusion lamination, thermal lamination, dry lamination, wet lamination, and the like can be exemplified. In the present invention, extrusion lamination is preferable because it is suitable for mass production, is excellent in cost, and can be directly laminated without using an anchor coat (anchor coat). However, the formation of a tie coat on paper before extrusion lamination is not precluded.
In the container according to each embodiment of the present invention, the thickness of the resin layer is not particularly limited, and is preferably 6 μm to 50 μm. Within this range, the container can be given desired heat resistance. In addition, when the resin layers of the composite base material in container molding are thermally bonded to each other, the temperature of the resin can be easily and uniformly increased to make the adhesion uniform. In addition, in the case of thermal bonding, the occurrence of a tunnel (tunnel) or pinholes in the resin layer can be suppressed.
In the container according to the embodiments of the present invention, the resin layer may be formed on at least one surface of the inner surface of the base material layer, or may be formed on both surfaces.
In the container according to each embodiment of the present invention, the tie coat layer may be interposed between the base material layer and the resin layer as described above, or the print layer may be formed, within a range that does not impair the object of the present invention. In addition, the paper of the base material layer may be subjected to corona treatment.
In the container according to the embodiments of the present invention, various additives such as a chain extender, an ultraviolet absorber, a lubricant, an antistatic agent, a heat stabilizer, an antioxidant, a pigment, a dye, a hydrolysis inhibitor, a light stabilizer, and a plasticizer may be contained in the copolymerized polyethylene terephthalate resin in an amount suitable for the purpose of the present invention.
In the container according to the embodiments of the present invention, the method for producing the copolymerized polyethylene terephthalate resin obtained by copolymerization with isophthalic acid is not particularly limited, and the copolymerization may be carried out by a known method and under a known condition, or a plurality of polyethylene terephthalate resins may be mixed as described above, and the copolymerization ratio may be adjusted.
Examples
The present invention will be specifically described below based on examples. In addition, the embodiments of the present invention are not limited to examples.
(production of example 1)
First, a plurality of types of copolymerized polyethylene terephthalate resins are prepared, which are obtained by a method such as copolymerizing isophthalic acid in different proportions, or mixing a plurality of types of polyethylene terephthalate resins having different copolymerization proportions and adjusting to a predetermined copolymerization proportion. Further, a biomass polyethylene terephthalate resin was prepared as the resin used in example 1 and example 3, and a homo-polyethylene terephthalate resin was prepared as the resin used in comparative example 1. By provision on the basis of 1 As a result of the qualitative/quantitative analysis of the H-NMR measurement, the ratio (%) of the "molar ratio of isophthalic acid monomer units" to the "sum of the molar ratio of terephthalic acid monomer units and the molar ratio of isophthalic acid monomer units" was calculated, and as a result, the copolymerization ratio of isophthalic acid in each of the copolymerized polyethylene terephthalate resins was 2.0% (example 1), 1.6% (example 2), 5.0% (example 3), 7.5% (example 4), 9.2% (example 5), 3.0% (example 6), 3.9% (example 7), 14.1% (comparative example 2), and 10.5% (comparative example 3), respectively. Further, the copolymerization ratio of isophthalic acid in the homo-polyethylene terephthalate resin was 0% (comparative example 1). In addition, the melting points of each were measured using a commercially available differential scanning calorimeter. The biobased carbon content is determined by the radioactive carbon (C14) measurement method based on ISO-16620-2 (equivalent to ASTM-D6866 standard), and is obtained by the above-mentioned calculation formula of the biobased carbon content.
Basis weight of paper sheet 230g/m 2 The respective polyethylene terephthalate resins were coated on one side of the paper as a base layer by an extrusion lamination method at the following thicknesses, and the thicknesses of the respective composite base materials were 30 μm in examples 1, 2, 4, 6, 7 and comparative examples 1 to 3, 40 μm in example 3 and 20 μm in example 5. The thickness of the polyethylene terephthalate resin was measured by observing a cross section of the composite substrate using a commercially available microscope.
The containers of examples 1 to 7 and comparative examples 1 to 3 were produced by punching out side wall members and bottom surface members of predetermined shapes of containers capable of accommodating a size of 300g of white juice (white juice) from various composite base materials, respectively, and joining them by heat bonding.
(test of adhesion)
Test pieces having dimensions of 50mm×150mm were cut out from each of the composite substrates prepared in the above, and peel test was performed at a speed of 100mm/min by peeling at 180 °, whereby adhesion between the substrate layer and the resin layer of the composite substrate was tested.
As the measuring apparatus, the number MAX-R2KN-B manufactured by Japanese measuring systems Co., ltd was used. The ideal adhesion is complete paper-to-paper delamination, but if there is strength to perform local paper-to-paper delamination, it is determined that there is no problem. In addition, the adhesion was evaluated as X (unsuitable) below 4N/50mm, as delta (employable) above 4N/50mm and below 7N/50mm, and as O (suitable) above 7N/50 mm.
(Heat resistance test)
The following two heat resistance tests were performed using the various containers prepared in the above.
(1) Heating test based on microwave oven
100g of water was placed in each container, and the container was heated at 500W for 3 minutes by a microwave oven (model: EMO-FM23C, manufactured by Sanyo electric Co., ltd., without a turntable) and taken out, and whether or not water leakage from the container and the surface state of the resin layer constituting the container were present after the container was left for 12 hours with water placed in the container was visually confirmed. Further, the test was performed with n=5 containers. In the water leakage evaluation, the case where no water leakage occurred in all of the 5 cases was judged as good (suitable), and the case where water leakage occurred in even 1 of the 5 cases was judged as× (unsuitable). In the evaluation of the surface state of the resin layer, 5 cases were judged as good (suitable) in which no abnormality such as air bubbles or damage was found on the surface of the resin layer constituting the container, and even 1 case among the 5 cases was judged as x (unsuitable) in which abnormality such as air bubbles or damage was found on the surface of the resin layer constituting the container.
(2) Roasting test after filling white juice into container
After 300g of white juice manufactured by Henry Japan Co., ltd was filled in each container, the filled containers were heated at a heating temperature of 200℃for 5 minutes and at 260℃for 5 minutes and at a heating time of 10 minutes, respectively, using an oven (model number: FSCC 101) manufactured by Fuximark Co., ltd. Further, the test was performed at n number=5 at each temperature. After the baking test, white juice was taken out of the container, and the presence or absence of delamination (peeling at the interface between the paper and the resin layer as the base material layer) of the base material layer (paper) and the resin layer constituting the composite base material of the container was visually confirmed. The case where delamination did not occur in any part of the container was judged as good (suitable), and the case where delamination occurred in any part of the container was judged as X (unsuitable).
Table 1 below shows the structures of the various containers (resins, composite substrates) and the results of the respective tests.
TABLE 1
As shown in table 1, in examples 1 to 7 in which the copolymerization ratio and melting point of isophthalic acid were in the appropriate ranges, the adhesion was appropriate, and the heat resistance was not problematic even in the firing test at a heating temperature of 200 ℃. In particular, heat resistance of examples 1 to 4, 6 and 7, in which the copolymerization ratio of isophthalic acid was 1.5 mol% or more and 8 mol% or less, was also suitable in a baking test at a heating temperature of 260℃for a heating time of 5 minutes. In addition, the copolymerization ratio of isophthalic acid of 4.0 mol% or less of the heat resistance of example 1, example 2, example 6 and example 7 was also suitable in the heating temperature 260 ℃ and the heating time 10 minutes of the baking test.
In example 1 having a biobased carbon content of 17%, example 3 having a biobased carbon content of 6.2%, example 6 having a biobased carbon content of 21.1%, and example 7 having a biobased carbon content of 18.7%, adhesion and heat resistance were also confirmed to be appropriate in the same manner as in the other examples having a biobased carbon content of 0%.
(production of example 2)
As in the case of "example 1" described above, a plurality of types of copolymerized polyethylene terephthalate resins and homo-polyethylene terephthalate resins were prepared. Then, the sheet was quantified to 230g/m 2 As a base material layer, each of the above-mentioned polyethylene terephthalate resins was coated on both surfaces thereof by an extrusion lamination method at a thickness of 30 μm, respectively, to prepare respective composite base materials. The melting point, thickness, and bio-based carbon content of the polyethylene terephthalate resin were measured by the same method as in "example 1". Their values are shown in table 2.
TABLE 2
In table 2, the resins used in examples 1-1, 2-1, 6, 7 and 1 were extrusion laminated under the same extrusion conditions as those in examples 1, 2, 6, 7 and 1 in table 1. On the other hand, in examples 1-2 and 2-2, the resins used in each were the same as in examples 1 and 2, but extrusion conditions were suitably adjusted such as to slow down extrusion speed and the like in terms of extrusion conditions, extrusion lamination was performed so as to be crystalline portions (%) different from examples 1 and 2. Further, the resin layer was removed by removing only the resin layer from the composite base material constituting the paper container after press molding described later, and the dissolution behavior thereof was measured by Differential Scanning Calorimetry (DSC), and the crystalline fraction (%) of the copolymerized polyethylene terephthalate resin was calculated by the above formula 1.
Then, a single piece of base paper of a predetermined shape was punched out from each composite base material, and press molding was performed, whereby a container having a curled portion around as shown in fig. 4 was produced.
Fig. 4 is a perspective view of a container used in the example and showing a third embodiment of the present invention.
Referring to fig. 4, the following dimensions of the container after press molding were as follows.
Length D in the longitudinal direction (including the flange portion): about 177mm
Width W in the short side direction (including flange portion): about 123mm
Height H: about 27mm
Diameter X of hemming portion 1 : about 3mm
Width of flange (including hemmed portion) X 2 : about 7mm
(shape retention test)
The width in the short side direction of the container after the press molding (1) was measured (W in fig. 4), the width in the short side direction of the container after 30 minutes after the molding was measured (2), and the width in the short side direction of the container after 24 hours after the molding was measured (3), and the change with time in the width in the short side direction of the container due to the rebound of the paper was confirmed after 30 minutes and 24 hours, respectively, compared with the container after the molding. Specifically, the ratio of the dimensional change is calculated by equation 2.
Formula 2: width (mm) in the short side direction of the container after the lapse of a predetermined time period/width (mm) in the short side direction of the paper container after the molding x 100=percentage of the opening degree formed by the time rebound of the paper container
Further, the shape retention test was performed using 5 samples each, and an arithmetic average of 5 paper container samples was calculated.
As shown in table 2, in the examples, the dimensional change in the width in the short side direction of the container after 30 minutes and 24 hours from the press molding was as small as 103%, and therefore, it can be said that the shape retention was good. On the other hand, in the comparative example, the increase was 105% after 30 minutes, and the increase was 110% after 24 hours, and the shape retention was poor. In the examples, it is presumed that since the crystal portion (%) of the resin layer is within a predetermined range, adhesion of the resin layer to the pleated portion or the curled portion of the container formed by extrusion by press molding is good, and rebound of the paper after press molding can be suppressed to a minimum. On the other hand, in the comparative example, it is presumed that the crystallization portion (%) of the resin layer is high, so that the adhesiveness of the resin layer in the pleated portion or the curled portion of the container is not so good, and the rebound of the paper after press molding cannot be suppressed, resulting in deterioration of the shape retention of the container.
Industrial applicability
As described above, the container of the present invention is suitable for use as, for example, a paper cup, a box, or the like for containing a beverage, food, or the like.
Claims (7)
1. A container comprising a composite substrate (7), wherein the composite substrate (7) comprises a substrate layer (10) comprising paper and a resin layer (11) comprising a copolymerized polyethylene terephthalate resin laminated on at least one surface of the substrate layer,
the copolymerized polyethylene terephthalate resin is a copolymerized polyethylene terephthalate resin obtained by copolymerization with isophthalic acid,
the copolymerization ratio of isophthalic acid in the copolymerized polyethylene terephthalate resin is 1 mol% or more and less than 10 mol%,
the melting point of the copolymer polyethylene terephthalate resin is 234 ℃ to 250 ℃.
2. The container of claim 1, wherein,
the copolymerization ratio of isophthalic acid in the copolymerized polyethylene terephthalate resin is 4.0 mol% or less.
3. The container according to claim 1 or 2, wherein,
the adhesion of the resin layer to the base material layer is 4N/50mm or more.
4. A container according to any one of claim 1 to 3, wherein,
the copolymerization ratio of isophthalic acid in the copolymerized polyethylene terephthalate resin is 1.5 mol% or more and 2.2 mol% or less.
5. The container according to any one of claims 1 to 4, wherein,
the copolymerized polyethylene terephthalate resin is a biomass polyethylene terephthalate resin which has a bio-based carbon content of 5% or more and is biologically derived.
6. The container according to any one of claims 1 to 5, wherein,
comprises a bottom part (2) and a side wall part (3) rising from the periphery of the bottom part,
the bottom portion and the side wall portion are connected by thermal bonding.
7. The container according to any one of claims 1 to 5, wherein,
the container is formed by press forming or bending-based forming of one sheet of base paper obtained from the composite substrate.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019153927 | 2019-08-26 | ||
| PCT/JP2020/032128 WO2021039822A1 (en) | 2019-08-26 | 2020-08-26 | Container |
| JPPCT/JP2020/032128 | 2020-08-26 | ||
| PCT/JP2021/007147 WO2022044377A1 (en) | 2019-08-26 | 2021-02-25 | Container |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116096647A true CN116096647A (en) | 2023-05-09 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202180057586.3A Pending CN116096647A (en) | 2019-08-26 | 2021-02-25 | Container |
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| Country | Link |
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| JP (2) | JPWO2021039822A1 (en) |
| CN (1) | CN116096647A (en) |
| WO (2) | WO2021039822A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021039822A1 (en) * | 2019-08-26 | 2021-03-04 | 東洋アルミエコープロダクツ株式会社 | Container |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002337840A (en) * | 2001-05-10 | 2002-11-27 | Jujo Central Co Ltd | Packaging container |
| JP2004018101A (en) * | 2002-06-20 | 2004-01-22 | Dainippon Printing Co Ltd | Paper cup and its manufacturing method |
| JP5680917B2 (en) * | 2010-09-17 | 2015-03-04 | 株式会社日本デキシー | Paper container |
| JP6041097B2 (en) * | 2012-09-21 | 2016-12-07 | 東洋製罐株式会社 | Packaging material and packaging structure using the same |
| JP2018001611A (en) * | 2016-07-01 | 2018-01-11 | 大日本印刷株式会社 | Laminate equipped with polyester resin layer and packing product equipped with the same |
| WO2021039822A1 (en) * | 2019-08-26 | 2021-03-04 | 東洋アルミエコープロダクツ株式会社 | Container |
-
2020
- 2020-08-26 WO PCT/JP2020/032128 patent/WO2021039822A1/en active Application Filing
- 2020-08-26 JP JP2021542953A patent/JPWO2021039822A1/ja active Pending
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2021
- 2021-02-25 CN CN202180057586.3A patent/CN116096647A/en active Pending
- 2021-02-25 WO PCT/JP2021/007147 patent/WO2022044377A1/en active Application Filing
- 2021-02-25 JP JP2022545279A patent/JPWO2022044377A1/ja active Pending
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| Publication number | Publication date |
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| WO2022044377A1 (en) | 2022-03-03 |
| JPWO2022044377A1 (en) | 2022-03-03 |
| JPWO2021039822A1 (en) | 2021-03-04 |
| WO2021039822A1 (en) | 2021-03-04 |
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