CN112203835B - Molded body including gas barrier layer, method for producing same, and packaging container - Google Patents
Molded body including gas barrier layer, method for producing same, and packaging container Download PDFInfo
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- CN112203835B CN112203835B CN201880023564.3A CN201880023564A CN112203835B CN 112203835 B CN112203835 B CN 112203835B CN 201880023564 A CN201880023564 A CN 201880023564A CN 112203835 B CN112203835 B CN 112203835B
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- foamed sheet
- molded article
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D22/00—Producing hollow articles
- B29D22/003—Containers for packaging, storing or transporting, e.g. bottles, jars, cans, barrels, tanks
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D22/00—Producing hollow articles
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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
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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
- B32B27/065—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 foam
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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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
- B29K2067/003—PET, i.e. poylethylene terephthalate
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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
- B32B2266/00—Composition of foam
- B32B2266/02—Organic
- B32B2266/0214—Materials belonging to B32B27/00
- B32B2266/0264—Polyester
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
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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
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
Abstract
The present invention relates to a molded article including a gas barrier layer, a packaging container including the same, and a method for producing the molded article, wherein the molded article of the present invention includes a first foamed sheet and a second foamed sheet on both surfaces of the gas barrier layer, respectively, so that oxygen permeability and water permeability can be minimized, and when the molded article is used in a food packaging container, food decay due to oxygen and moisture can be prevented, so that food can be easily stored.
Description
Technical Field
The present invention relates to a molded article including a gas barrier layer, a packaging container including the same, and a method for producing the molded article.
Background
Products used as general food packaging containers are classified into foamed type and non-foamed type. A foamed food packaging container is obtained by mixing and extruding polystyrene and a foaming gas, and has advantages such as shape maintenance, heat insulation, and price advantage because the product can maintain a large thickness. In contrast, such foamed products have the disadvantage that harmful substances are detected at high temperatures.
As a non-foamed food packaging container, a product prepared by forming a film from polypropylene that is stable to heat is used. On the other hand, the non-foamed food packaging container has advantages that the form change rate is low at high temperature and harmful substances are not detected. But has the disadvantages of high price and poor heat insulation effect.
On the other hand, as the life of modern society is more and more convenient, the amount of disposable products used increases, and as the number of households increases, the demand for take-out foods and simple food products also increases. Accordingly, the demand for food packaging containers has increased, and further, the consumer demand for new container materials that are safe without harmful substances and have functions based on different uses has also increased day by day.
In view of this, many efforts have been made by food packaging container-related companies to produce food packaging containers that are advantageous in terms of convenience, safety and price.
As an example thereof, there has been proposed a technology relating to an environment-friendly heat-resistant material and a packaging container comprising the same (korean patent laid-open publication No. 10-1778629). Specifically, the above-identified issued patents disclose a packaging container comprising a heat-resistant material having a 2-layer structure comprising an ethylene vinyl alcohol (EVOH) gas barrier layer on at least one side of a Polyethylene terephthalate (PET) foam.
However, the ethylene vinyl alcohol has a disadvantage of being difficult to mold because of a large difference in melting point with polyethylene terephthalate, although it is excellent in barrier property. Specifically, a high-temperature heat treatment is required to improve the heat resistance of polyethylene terephthalate, but in this case, the ethylene vinyl alcohol is melted, and therefore, a gas barrier layer or the like cannot be formed on the entire area of the food packaging container, which causes a problem of a structural failure of the food packaging container.
Disclosure of Invention
The present invention provides a molded article comprising a first foamed sheet, a gas barrier layer and a second foamed sheet laminated in this order, and satisfying the following formula 1, wherein the first foamed sheet and the second foamed sheet are foamed polyester resin, the molded article has an average thickness of 1mm to 5mm, and an oxygen permeability of 20cc/m in accordance with ASTM D3985 under a temperature condition of 23 ℃ 2 Day or below, math figure 1: H/D is not less than 0.01, and in mathematical formula 1, a molded body having a container structure including a receiving portion and an opening is formed, wherein H represents the depth of the receiving portion and is 1cm to 10cm, and D represents the diameter of the opening.
The present invention also provides a packaging container comprising the molded article.
Further, the present invention provides a method for producing a molded article, comprising: disposing a sheet having a structure in which a first foamed sheet, a gas barrier layer, and a second foamed sheet are sequentially stacked between a female mold and a male mold of a molding device; and molding the molded article by applying pressure to the male mold, wherein the first foamed sheet and the second foamed sheet are foams of a polyester resin.
The molded article of the present invention comprises the first foamed sheet and the second foamed sheet on both sides of the gas barrier layer, respectively, so that the oxygen permeability and the water permeability can be minimized. Meanwhile, when the molded body is used for a food packaging container, food decay and the like due to oxygen and moisture can be prevented, and the food can be easily stored.
Drawings
FIG. 1 is a sectional view of a molded article of the present invention.
Fig. 2 is a view sequentially showing a method for producing a molded article of the present invention.
Description of the reference numerals:
1: sheet
10: shaped body
101: first foamed sheet
101': second foamed sheet
102: gas barrier layer
11: bottom part
12: wall part
13: flange
20: die set
21: concave mould
22: convex die
23: and (4) a pressure reducing hole.
Detailed Description
The present invention relates to a molded article including a gas barrier layer, a packaging container including the same, and a method for producing the molded article. In particular, in the molded article of the present invention, the first foamed sheet and the second foamed sheet are provided on both sides of the gas barrier layer, so that the oxygen permeability and the water permeability can be minimized. Meanwhile, when the molded body is used for a food packaging container, food decay and the like due to oxygen and moisture can be prevented, and the food can be easily stored.
Fig. 1 is a sectional view of the molded article of the present invention, and fig. 2 is a view sequentially showing a method for producing the molded article of the present invention. The molded article of the present invention will be described in detail below with reference to fig. 1 and 2.
The present invention provides a molded article 10 which is formed by laminating a first foamed sheet 101, a gas barrier layer 102 and a second foamed sheet 101 'in this order and satisfies the following formula 1, wherein the first foamed sheet 101 and the second foamed sheet 101' are foamed polyester resin, the molded article 10 has an average thickness of 1mm to 5mm, and an oxygen permeability of 20cc/m under a temperature condition of 23 ℃ based on ASTM D3985 2 Day or below, math figure 1: H/D is not less than 0.01, and is in the numberIn formula 1, a molded body having a container structure including a housing portion and an opening is formed, H represents the depth of the housing portion, and the depth is 1cm to 10cm, and D represents the diameter of the opening.
Specifically, in the molded article of the present invention, the oxygen permeability measured based on ASTM D3985 may be 0.1cc/m 2 Day to 20cc/m 2 Day. More specifically, when the oxygen permeability of a test piece (length. times. width. times. height: 40 mm. times.40 mm. times.3 mm) of the molded body prepared was measured for 30 minutes under the temperature condition of (23. + -.1). degree.C, the oxygen permeability of the molded body may be 0.1cc/m 2 Day to 20cc/m 2 Day, 0.1cc/m 2 Day to 15cc/m 2 Day, 0.1cc/m 2 Day to 13cc/m 2 Day, 0.1cc/m 2 Day to 10cc/m 2 Day, 0.1cc/m 2 Day to 7cc/m 2 Day, 0.1cc/m 2 Day to 5cc/m 2 Day or 0.1cc/m 2 Day to 3cc/m 2 Day.
As described above, the first foamed sheet 101 and the second foamed sheet 101 'of the polyester resin are formed on the outer layer of the cross section of the molded article 10, and the gas barrier layer 102 is formed between the first foamed sheet 101 and the second foamed sheet 101', so that the oxygen permeability as described above can be satisfied. That is, the molded article 10 of the present invention has an advantage that it has an oxygen permeability within the above range, and therefore has excellent oxygen blocking performance, and can prolong the shelf life of food.
Specifically, in the molded article 10 of the present invention, the first foamed sheet 101 and the second foamed sheet 101' are formed on both sides of the gas barrier layer 102, whereby the oxygen permeability can be controlled within the above range.
At the same time, the water vapor permeability according to ASTM F1249 is 50g/m at a temperature of 37 ℃ and a relative humidity of 100% 2 Day or less. For example, the water vapor permeability may be at 0.1g/m 2 Day to 50g/m 2 Day, 0.1g/m 2 Day to 40g/m 2 Day, 0.1g/m 2 Day to 30g/m 2 Day, 0.1g/m 2 Day to 20g/m 2 Day, 0.1g/m 2 Day to 10g/m 2 Day, 0.1g/m 2 Day to day7g/m 2 Day, 0.1g/m 2 Day to 5g/m 2 Day or 0.1g/m 2 Day to 3g/m 2 The range of days. Since the molded article 10 of the present invention has the above water vapor permeability, it can be widely used for products requiring gas barrier properties. For example, in the case of using as a food packaging container, the food can be prevented from rotting due to the reaction with water vapor, and therefore, the food can be stored easily.
The polyester resin may include recurring units derived from an acid component and a glycol component. Specifically, the polyester resin may be one or more selected from the group consisting of aromatic and aliphatic polyester resins synthesized from a dicarboxylic acid component and an ethylene glycol component or hydroxycarboxylic acid.
For example, the polyester resin may be one or more selected from the group consisting of Polyethylene Terephthalate (PET), Polybutylene Terephthalate (PBT), polylactic acid (PLA), Polyglycolic acid (PGA), Polyethylene adipate (PEA), Polyhydroxyalkanoate (PHA), Polytrimethylene Terephthalate (PTT), and Polyethylene naphthalate (PEN). As an example, Polyethylene Terephthalate (PET) may be used in the present invention.
Meanwhile, the gas barrier layer 102 may include one or more of ethylene vinyl alcohol (EVOH), polyvinylidene chloride (PVdC), and polyethylene terephthalate (PET).
Specifically, the barrier layer 102 may be formed using ethylene vinyl alcohol. In this case, gas generated from the food inside the packaging container can be discharged to the outside, and oxygen supply from the outside can be blocked.
The molded body 10 of the present invention is a multilayer structure, and the average thickness of the multilayer structure for forming the molded body 10 may be in the range of 1mm to 5 mm.
For example, the molded body 10 may have a 3-layer structure, in which case the average total thickness of the 3-layer structure may be 1.2mm to 4mm, 1.5mm to 3.5mm, 1.8mm to 3mm, or 2 mm. Also, the average thickness of the gas barrier layer 102 may be 0.01mm to 2mm, and the average thickness of the gas barrier layer 102 may be 0.05mm to 2mm, 0.1mm to 1.9mm, 0.2mm to 1.85mm, 0.3mm to 1.8mm, 0.5mm to 1.6mm, 0.7mm to 1.4mm, 0.9mm to 1.2mm, or 1 mm.
Meanwhile, the average thicknesses of the first foaming sheet 101 and the second foaming sheet 101 'may be 0.5mm to 1.5mm, respectively, and the average thicknesses of the first foaming sheet 101 and the second foaming sheet 101' may be 0.6mm to 1.3mm, 0.7mm to 1.2mm, 0.8mm to 1.0mm, and 0.9mm to 0.95mm, respectively. The molded article 10 of the present invention is composed of the foamed sheets 101 and 101' and the gas barrier layer 102 having the thickness in the above range, and therefore can satisfy the oxygen permeability and the water vapor permeability as described above, and can satisfy the lightweight property and the like while improving the compressive strength.
In one example, the melting points (T) of the first foamed sheet 101 and the second foamed sheet 101' are m ) May average from 240 ℃ to 260 ℃. Specifically, the melting points of the first foaming sheet 101 and the second foaming sheet 101' may be 242 ℃ to 257 ℃, 245 ℃ to 255 ℃, 247 ℃ to 253 ℃, or 248 ℃ to 251 ℃ on average. As an example, the melting point average of the first foamed sheet 101 and the second foamed sheet 101' each comprising a polyethylene terephthalate (polyethylene terephthalate) resin may be 248 ℃ to 251 ℃.
At the same time, the melting point (T) of the gas barrier layer 102 m ) May average from 150 ℃ to 190 ℃. Specifically, the melting point of the gas barrier layer 102 may be 150 ℃ to 190 ℃, 155 ℃ to 185 ℃, 160 ℃ to 180 ℃, 165 ℃ to 175 ℃, or 169 ℃ to 171 ℃ on average. For example, the melting point of the gas barrier layer made of ethylene-vinyl alcohol may be 170 ± 0.5 ℃.
On the other hand, since polyethylene terephthalate and ethylene vinyl alcohol have large difference in melting point, when a molded article having a 2-layer structure (foamed sheet/gas barrier layer) is molded, ethylene vinyl alcohol is peeled off or dissolved, and there is a problem that the barrier layer 102 and the like cannot be formed uniformly over the entire area of the molded article, but the problems that the gas barrier layer 102 is dissolved and disappears, and the gas barrier layer 101 and 101' are peeled off from the foamed sheets 101 and 101' can be solved by laminating the foamed sheets 101 and 101' on both sides of the gas barrier layer 102.
As an example, the molded article 10 of the present invention includes a bottom 11 and a wall 12, and the upper end of the wall 12 is open along the periphery of the bottom 11 and the bottom 11, and in the above formula 1, the H/D value may be 0.01 to 1.3, 0.05 to 1.2, 0.1 to 1.1, 0.3 to 1.0, 0.4 to 0.9, 0.5 to 0.8, 0.55 to 0.7, or 0.6 to 0.65. Also, in the above mathematical formula 1, the H value may be 1cm to 10 cm. For example, the diameter of the opening of the molded body 10 may be 10cm, and the depth of the housing portion may be 3 cm. The molded article 10 of the present invention may have a container shape, and the molded article 10 of the present invention may have a cylindrical container shape or a rectangular container shape.
On the other hand, in the molded article 10 of the present invention, the first foamed sheet 101 and the second foamed sheet 101' are formed on both surfaces of the gas barrier layer 102, respectively, so that the molded article 10 satisfying the following formula 2 can be provided.
|T 2 -T 1 | ≧ 10 ℃ (mathematic formula 2)
In the above mathematical formula 2, T 1 Is the outside surface temperature, T, of the molded body measured after the molded body is put in water of 100 ℃ under the condition of 1atm at the temperature of 20 ℃ and 1 minute is passed 2 The temperature of water inside the molded body was measured after 1 minute passed after 100 ℃ water was put in the molded body at a temperature of 20 ℃ under 1 atm.
The molded body 10 of the present invention includes the first foamed sheet 101 and the second foamed sheet 101', and thus has excellent thermal barrier properties. Specifically, the difference between the temperature of water inside the molded article and the temperature of the outer surface of the molded article may be 10 ℃ or more when 1 minute passes under the conditions of normal temperature (20 ℃) and 1 atmospheric pressure in a state where 100 ℃ water of 70% (v/v) is put inside the molded article. This represents that the molded article 10 of the present invention has excellent heat barrier properties, and specifically, the temperature difference is a temperature difference between the temperature of water contained inside the molded article 10 and the temperature of the outer surface of the molded article 10 at a time when one minute passes in a state where 70% (v/v) of 100 ℃ water is put in the prepared molded article.
As an example, when 70% (v/v) of 100 ℃ water is put into the molded article 10 of the present invention and the outside temperature of the molded article at the time when one minute passes is 40 ℃, the temperature of the water contained in the molded article 10 may be 95 ℃. The molded body 10 of the present invention can maintain a relatively high temperature difference between the temperature of the water contained in the molded body 10 and the outer surface of the molded body 10 under the above conditions, and thus has an excellent heat barrier property and an effect of effectively improving the heat retention of the food.
In another aspect, the first and second foamed sheets 101 and 101' of the present invention may respectively include 0.5 to 9 weight percent of calcium carbonate (CaCO) 3 )。
Specifically, as the above calcium carbonate (CaCO) 3 ) By including the inorganic ions as described above, the first foamed sheet 101 and the second foamed sheet 101' of the present invention exhibit uniform sheet surfaces and excellent thermoformability.
The thermal conductivity of the calcium carbonate may be 1.0 to 3.0kcal/mh ℃. Specifically, the thermal conductivity of the calcium carbonate may be 1.2kcal/mh ℃ to 2.5kcal/mh ℃, 1.5kcal/mh ℃ to 2.2kcal/mh ℃, or 1.8kcal/mh ℃ to 2.0kcal/mh ℃. More specifically, the thermal conductivity of the calcium carbonate can be 1.5kcal/mh ℃ to 2.5kcal/mh ℃ or 1.8kcal/mh ℃ to 2.3kcal/mh ℃. The first foamed sheet 101 and the second foamed sheet 101' comprising calcium carbonate as described above have excellent thermal conductivity, thus having a uniform surface, and have excellent thermoformability.
For example, the calcium carbonate may be contained in an amount of 0.5 to 9 weight percent. Specifically, the calcium carbonate may be present in an amount of 0.5 to 8 weight percent, 0.6 to 7 weight percent, 0.7 to 6 weight percent, 0.8 to 5 weight percent, 0.9 to 4 weight percent, 1.0 to 3.0 weight percent, 2 to 3.5 weight percent. For example, the calcium carbonate may be contained in an amount of 1.0% by weight or 3% by weight.
In one example, the density of the foamed sheets 101, 101' (KS M ISO 845) can be, on average, 300kg/M 3 To 700kg/m 3 . Specifically, the density of the foamed sheets 101, 101' may average 325kg/m 3 To 650kg/m 3 、350kg/m 3 To 600kg/m 3 、375kg/m 3 To 550kg/m 3 、400kg/m 3 To 500kg/m 3 Or 425kg/m 3 To 450kg/m 3 。
In another example, the foamed sheets 101, 101' of the present disclosure may have an elongation at high temperature of 325% to 375% at a temperature of 200 ℃ for 10 seconds. Specifically, the foamed sheet 101, 101' may have a high-temperature elongation of 330% to 360%, 345% to 370%, or 335% to 360% at a temperature of 200 ℃ for 10 seconds. More specifically, the foamed sheet 101, 101' may have an elongation at a high temperature of 345% to 355% at a temperature of 200 ℃ for 10 seconds.
The present invention includes the polyester and calcium carbonate as described above, and thus the foamed sheets 101 and 101' of the present invention can exhibit excellent processability.
The first foamed sheet 101 and the second foamed sheet 101 'of the molded article 10 of the present invention are foamed polyester resin, and the polyester resin of the first foamed sheet 101 and the second foamed sheet 101' may be Polyethylene Terephthalate (PET) resin. The invention uses the PET resin, thereby realizing environmental protection and easy repeated use.
When the elution specification was measured based on the specifications of the relevant instruments and container packages and raw materials thereof in food and drug safety, the total elution amount was 30ppm or less, antimony germanium, terephthalic acid, isophthalic acid, and acetaldehyde were not detected, and when the residual specification was measured, volatile substances were not detected.
Specifically, the molded article 10 of the present invention is prepared by using the polyester resin which is an environmentally friendly material as described above, and thus, the potential substances described in the standard and specification report on the packaging of instruments and containers issued in the korea food and drug safety department can be controlled within the allowable range.
The food packaging container 10 is prepared using the molded body 10 using the material as described above, so that an environmentally friendly food container can be provided.
As an example, the molded article 10 of the present invention may have Barrier (Barrier) properties, hydrophilization functions, or water-repellent functions, and the resin foam sheet of the present invention may further include one or more functional additives selected from the group consisting of surfactants, hydrophilizing agents, heat stabilizers, water-repellent agents, cell size enlarging agents, infrared attenuating agents, plasticizers, fire-retardant chemicals, pigments, elastic polymers, extrusion aids, antioxidants, air discharge preventing agents, and ultraviolet absorbers. Specifically, the resin foamed sheet of the present invention may include a thickener, a heat stabilizer, and a foaming agent.
The above thickener is not particularly limited, but pyromellitic dianhydride (PMDA) can be used in the present invention.
The heat stabilizer may be an organic phosphorus compound or an inorganic phosphorus compound. For example, the above-mentioned organic phosphorus compound or inorganic phosphorus compound may be phosphoric acid and organic esters thereof, phosphorous acid and organic esters thereof. For example, the heat stabilizer is commercially available, and the heat stabilizer may be phosphoric acid, alkyl phosphate, or aryl phosphate. Specifically, the heat stabilizer in the present invention may be triphenyl phosphate, but is not limited thereto and may be used without limitation in the conventional range as long as the heat stability of the above resin foamed sheet can be improved.
As an example of the above blowing agent, there is N 2 、CO 2 Physical blowing agents such as freon, butane, pentane, neopentane, hexane, isohexane, n-heptane, isoheptane and chloromethane, azodicarbonamide (azodicarbonamide) compounds, p '-oxybis (benzenesulfonylhydrazide) [ p, p' -oxy bis (benzenesulfonylhydrazide)]Chemical foaming agents such as N, N '-dinitrosopentamethylene tetramine (N, N' -dinitroso pentamethylene tetramine) compounds, and more specifically, CO can be used in the present invention 2 。
The present invention also provides a method for producing the molded article.
FIG. 2 is a view sequentially showing a method for producing a molded article of the present invention. Referring to fig. 2, the present invention provides a method for producing a molded article, comprising: a step of disposing a sheet 1 having a structure in which a first foamed sheet, a gas barrier layer, and a second foamed sheet are sequentially laminated between a female mold 21 and a male mold 22 of a molding device; and a step of molding the molded body 10 by applying pressure to the male mold 22, wherein the first foamed sheet and the second foamed sheet are foams of polyester resin.
On the other hand, although the method for producing the first foamed sheet and the second foamed sheet is not particularly limited, the first foamed sheet and the second foamed sheet can be produced by, for example, extrusion foaming of a polyester resin. Specifically, as the type of foaming method, there are roughly bead foaming or extrusion foaming. Generally, the bead foaming is a method in which resin beads are heated to achieve first foaming, subjected to appropriate aging treatment, filled in a plate-shaped or barrel-shaped mold, heated again, welded and molded by second foaming to prepare a product. In contrast, in the case of extrusion foaming, the resin is heated and melted, and the molten resin is continuously extruded and foamed, thereby simplifying the process steps, enabling mass production, and preventing cracks, particle damage, and the like from occurring between the beads at the time of bead foaming.
Secondly, the processing steps include: a step of disposing a sheet 1 having a structure in which a first foamed sheet, a gas barrier layer, and a second foamed sheet are sequentially laminated between a female mold 21 and a male mold 22 of a molded body molding device 20; and a step of molding the molded body 10 by applying pressure to the male mold 22.
Specifically, the sheet 1 disposed between the female die 21 and the male die 22 may be molded into the molded body 10 by thermoforming. The thermoforming may be vacuum forming, pressure-air forming, vacuum pressure-air forming combining vacuum forming and pressure-air forming, thermoforming using a male mold (plug) or vacuum and/or pressure-air forming after using the male mold 22, or the like.
Referring to fig. 2, part (a) of fig. 2 shows an arrangement step of arranging the sheet 1 between the female die 21 and the male die 22 of the molding apparatus before molding the sheet 1. Fig. 2 (b) is a diagram showing the stretching step and the thermal step, and as shown in fig. 2 (b), the sheet 1 is stretched by lowering the male mold 22, shaped into the cavity shape of the female mold 21 by vacuum suction from the female mold 21, and heated. Fig. 2 (c) shows that the sheet 1 being molded is shaped into the shape of the male mold 22 by pressurization of the male mold 22 and compressed air from the female mold 21, whereby the molded body 10 as a final molded article is molded. Next, after cooling, the molded body 10 is taken out by raising the male die 22.
In the molding step, the molded body 10 may be molded by heating the sheet to a surface temperature of 140 to 160 ℃ and setting the surface temperatures of the female mold 21 and the male mold 22 to 60 to 200 ℃.
On the other hand, in the molding step, the surface of the male mold 22 and the cavity surface of the female mold 21 may be different in temperature. Preferably, the surface temperature of the male mold 22 may be 250 to 280 ℃, 255 to 275 ℃, 260 to 270 ℃ or 265 ℃, respectively, and the cavity surface temperature of the female mold 21 may be 200 to 250 ℃, 210 to 240 ℃, 215 to 235 ℃, 220 to 230 ℃, or 225 ± 3 ℃.
For example, the surface temperature of the male mold 22 may be 265 ± 1 ℃ and the surface temperature of the female mold 21 may be 225 ℃, and preferably, the male mold 22 is brought into contact with the female mold 22 for 0.5 to 15 seconds. A decompression hole 23 for decompressing a cavity as an internal space may be formed at one side of the die 21.
Therefore, a container-shaped molded article in which the first foamed sheet of polyester resin, the gas barrier layer, and the second foamed sheet of polyester resin are laminated in this order, or a packaging container including the molded article can be produced by the above-described method for producing a molded article.
The present invention will be described in more detail below with reference to examples and experimental examples.
However, the following examples and experimental examples are only for illustrating the present invention, and the contents of the present invention are not limited to the following examples and experimental examples.
Preparation example 1
100 parts by weight of the PET resin was dried at a temperature of 130 c to remove moisture,100 parts by weight of the above PET resin from which water was removed, 1 part by weight of pyromellitic dianhydride (PMDA), and 1 part by weight of calcium carbonate (CaCO) were mixed in a first extruder 3 ) 0.1 parts by weight of Irganox (IRG 1010), and heated at a temperature of 280 ℃ to prepare a resin melt. Next, butane was mixed as a blowing agent in the first extruder, and the resin melt was fed into the second extruder and cooled at a temperature of 220 ℃. The cooled melt is passed through a Die (Die) and formed into a foamed sheet.
At this time, the density of the prepared polyester resin foamed sheet was 380kg/m 3 The thickness is 1 mm.
Example 1
On one side of the foamed sheet prepared in preparation example 1, an EVOH film of 0.05mm was laminated as a barrier layer, and the foamed sheet prepared in preparation example 1 was laminated on the above barrier layer. Then, the laminated sheet having a 3-layer structure was molded into a container shape, thereby preparing a molded body (H: depth of the housing portion, D: diameter of the opening) having an H/D of 0.3. The diameter of the opening of the molded article was 10 cm. On the other hand, in molding the molded article, the surface temperature of the male mold was 60 ℃ and the surface temperature of the female mold was 120 ℃.
Example 2
A molded body was produced in the same manner as in example 1, except that the barrier layer of the 2-layer film structure was composed of EVOH having a thickness of 0.02mm and PET having a thickness of 0.03 mm.
Example 3
A molded body was produced in the same manner as in example 1, except that the value of H/D was 0.5.
Comparative example 1
A2-layer structured sheet was prepared by laminating an EVOH film of 0.05mm on one side of a foamed sheet prepared in the same manner as in preparation example 1, except that the thickness was 2 mm. Then, a molded body (H: the depth of the housing portion, D: the diameter of the opening) having an H/D of 0.3 was prepared by molding the laminated 2-layer sheet into a container shape. The diameter of the opening of the molded article was 10 cm. On the other hand, the surface temperature of the male mold was 60 ℃ and the surface temperature of the female mold was 120 ℃.
Comparative example 2
A container having the same structure as in example 1 was molded using a PP multilayer sheet (PP/EVOH/PP) having an H/D of 0.3 while maintaining the mold temperature at 20 ℃ during molding.
In examples and comparative examples, molded articles were prepared according to the sheet type and molding conditions of the molded articles as shown in the following table 1.
TABLE 1
Experimental example 1 measurement of oxygen permeability
For the molded bodies prepared in examples and comparative examples, oxygen permeability was measured under conditions of a temperature of 23 ℃ and a relative humidity of 50%. On the other hand, in order to confirm whether or not the gas barrier layer is uniformly distributed in the inside of the molded body, test pieces of the molded body were randomly cut out and measured. And, the results thereof are shown in the following table 2.
Oxygen permeability test
-test method: ASTM D3985
-a test apparatus: OX-TRAN 702(MOCON corporation, USA)
-test temperature: 23 deg.C
-test time: 30 minutes
-measurement range: 0.1 to 2000cc/m 2 Day(s)
-specimen size: length × width × height: 40mm by 3mm
TABLE 2
Referring to Table 2, it is understood that the molded article of the present invention has a low oxygen permeability and can prevent most of the oxygen from permeating. This means that the gas barrier layer is uniformly distributed over the entire area of the shaped body. In contrast, the molded body of comparative example 1 had a high oxygen permeability. From this, it was judged that the gas barrier layer was damaged at the time of molding of the molded article. Further, comparative example 2, which is a non-foamed product, has a low oxygen permeability, but it can be confirmed from a thermal barrier property test described later that the thermal barrier property is not excellent.
In contrast, the molded body of comparative example 1 had a high oxygen permeability. From this, it was judged that the gas barrier layer was damaged at the time of molding of the molded article. Further, comparative example 2, which is a non-foamed product, has a low oxygen permeability, but it can be confirmed from a thermal barrier property test described later that the thermal barrier property is not excellent.
Experimental example 2 measurement of Water vapor permeability
For the molded bodies prepared in examples and comparative examples, the water vapor permeability was measured at a temperature of 37 ℃ and a relative humidity of 100% based on ASTM F1249. And, the results thereof are shown in the following table 3.
TABLE 3
As can be seen from Table 3, the molded articles of examples 1 to 3 each showed 8.5g/m 2 Day, 17g/m 2 Day and 18g/m 2 Lower results of days, etc. This means that the gas barrier layer is uniformly distributed over the entire area of the shaped body. Also, comparative example 1 shows 19g/m 2 Days, the values are higher than in the examples. From this, it was judged that the gas barrier layer was damaged at the time of molding the molded article of comparative example 1. Further, comparative example 2, which is a non-foamed product, has a low oxygen permeability, but it can be confirmed from a thermal barrier property test described later that the thermal barrier property is not excellent.
Experimental example 3 measurement of thermal Barrier Properties
In order to evaluate the heat-blocking property of the molded bodies of examples and comparative examples, the temperature of an arbitrary point inside the molded body and an arbitrary point outside the container was measured at the time when 2 minutes passed in a state where water of 100 ℃ was put in 70% (v/v) inside the molded body. The results are shown in table 4.
Mathematical formula 2
|T 2 -T 1 |≥10℃
In the above-mentioned numerical expression 2,
T 1 is the outside surface temperature of the molded body measured after water of 100 ℃ is put in the molded body and 1 minute passes under the condition of 1atm at a temperature of 20 ℃,
T 2 the temperature of water in the inside of the molded article was measured after 1 minute passed after 100 ℃ water was put in the molded article at a temperature of 20 ℃ and 1 atm.
TABLE 4
As is clear from table 4 above, the molded bodies of the examples had a temperature difference of 10 ℃ or more between the temperature of water contained in the molded bodies and the temperature of the surface of the molded bodies, and had excellent heat-barrier properties. In contrast, in the molded articles of comparative examples 1 and 2, | T 2 -T 1 I is 27 ℃ and 0 ℃ respectively, and the heat barrier property is poor. Accordingly, it is known that the molded body of the present invention includes the PET foam sheet to have excellent heat barrier property, thereby enabling outstanding heat retention characteristics and handling safety.
In particular, it is found that the gas barrier layer has excellent thermal barrier properties by including the first foam sheet and the second foam sheet on both sides thereof.
From the above, it is understood that the molded article of the present invention has low water vapor permeability and oxygen permeability and is excellent in heat barrier property.
Industrial applicability
The molded article of the present invention comprises the first foamed sheet and the second foamed sheet on both surfaces of the gas barrier layer, thereby minimizing the oxygen permeability and the water permeability, and when the molded article is used for a food packaging container, food decay and the like due to oxygen and moisture can be prevented, and the food can be easily stored.
Claims (11)
1. A molded article comprising a first foamed sheet, a gas barrier layer and a second foamed sheet laminated in this order, and satisfying the following numerical formula 1,
the first foamed sheet and the second foamed sheet are foamed products of polyester resin,
the molded article has an average thickness of 1mm to 5mm, the gas barrier layer has an average thickness of 0.01mm to 2mm, and the first foam sheet and the second foam sheet each have an average thickness of 0.5mm to 1.5mm,
the first foamed sheet and the second foamed sheet each contain 0.5 to 9.0% by weight of calcium carbonate,
an oxygen permeability of 20cc/m based on ASTM D3985 under a temperature condition of 23 DEG C 2 The number of days or less,
mathematical formula 1: H/D is more than or equal to 0.01,
in the case of the mathematical formula 1,
a molded body having a container structure including a housing portion and an opening portion,
h represents the depth of the containing part, and the depth is 1cm to 10cm,
d represents the diameter of the opening.
2. Shaped body according to claim 1, characterized in that the water vapor permeability according to ASTM F1249 is 50g/m at a temperature of 37 ℃ and a relative humidity of 100% 2 Day or less.
3. The molded body according to claim 1, wherein the gas barrier layer comprises one or more of ethylene-vinyl alcohol, polyvinylidene chloride, and polyethylene terephthalate.
4. Shaped body according to claim 1, characterized in that the melting point (T) of the gas barrier layer is m ) An average melting point (T) of 150 ℃ to 190 ℃ and the first foamed sheet and the second foamed sheet m ) The average is 240 ℃ to 260 ℃.
5. The molded article according to claim 1, wherein the polyester resin is a polyethylene terephthalate resin.
6. The molded body according to claim 1, wherein the following formula 2 is satisfied,
mathematical formula 2: i T 2 -T 1 |≥10℃
In the above-mentioned numerical expression 2,
T 1 the outer surface temperature of the molded article was measured after 1 minute of the molding in which water of 100 ℃ was put at a temperature of 20 ℃ and 1atm,
T 2 the temperature of water inside the molded body was measured after 1 minute passed after 100 ℃ water was put in the molded body at a temperature of 20 ℃ under 1 atm.
7. A packaging container comprising the molded body according to any one of claims 1 to 6.
8. A packaging container according to claim 7, characterized in that the packaging container is a food packaging container.
9. A method for producing a shaped body according to claim 1, comprising:
disposing a sheet having a structure in which a first foamed sheet, a gas barrier layer, and a second foamed sheet are sequentially stacked between a female mold and a male mold of a molding device; and
a step of applying pressure to the male mold to mold the molded body,
the first foamed sheet and the second foamed sheet are foamed products of polyester resin.
10. The method of producing a molded article according to claim 9, wherein in the molding step, the molded article is molded by heating to a sheet surface temperature of 140 ℃ to 160 ℃ and setting the surface temperatures of the female mold and the male mold to 60 ℃ to 200 ℃.
11. The method of producing a molded body according to claim 9, wherein a decompression hole for decompressing the internal space is formed at one side of the female mold.
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| KR1020180074664A KR102040237B1 (en) | 2018-06-28 | 2018-06-28 | A molded product having gas barrier layer, A packaging container comprising the same, and Method for preparing the molded product |
| KR10-2018-0074664 | 2018-06-28 | ||
| PCT/KR2018/016023 WO2020004744A1 (en) | 2018-06-28 | 2018-12-17 | Molded article including gas barrier layer, packing container including same, and method for preparing molded article |
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| KR (1) | KR102040237B1 (en) |
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| KR102313714B1 (en) * | 2019-11-26 | 2021-10-19 | 주식회사 휴비스 | Polyester foam sheet comprising inorganic particles with different average diameters |
| KR20210087584A (en) * | 2020-01-02 | 2021-07-13 | 주식회사 휴비스 | Polyester resin foam sheet having embossed surface and manufacturing method thereof |
| KR20210087149A (en) * | 2020-01-02 | 2021-07-12 | 주식회사 휴비스 | Polyester resin foam sheet having embossed surface and manufacturing method thereof |
| KR20210087163A (en) * | 2020-01-02 | 2021-07-12 | 주식회사 휴비스 | Polyester foam sheet and manufacturing method of the same |
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| CN112203835A (en) | 2021-01-08 |
| JP2021079703A (en) | 2021-05-27 |
| WO2020004744A1 (en) | 2020-01-02 |
| JP7110422B2 (en) | 2022-08-01 |
| KR102040237B1 (en) | 2019-11-06 |
| JP2020528835A (en) | 2020-10-01 |
| JP6838145B2 (en) | 2021-03-03 |
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