WO1995018011A1 - Conteneur thermoforme, partiellement expanse et son procede de fabrication - Google Patents

Conteneur thermoforme, partiellement expanse et son procede de fabrication Download PDF

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Publication number
WO1995018011A1
WO1995018011A1 PCT/JP1994/002248 JP9402248W WO9518011A1 WO 1995018011 A1 WO1995018011 A1 WO 1995018011A1 JP 9402248 W JP9402248 W JP 9402248W WO 9518011 A1 WO9518011 A1 WO 9518011A1
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WO
WIPO (PCT)
Prior art keywords
container
layer
foamed
foaming
laminated sheet
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP1994/002248
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English (en)
Japanese (ja)
Inventor
Ikuya Ishii
Ryuuji Moriwaki
Tetsurou Yasuike
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Idemitsu Petrochemical Co Ltd
Original Assignee
Idemitsu Petrochemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP34706593A external-priority patent/JP3342762B2/ja
Priority claimed from JP17775294A external-priority patent/JP3400553B2/ja
Application filed by Idemitsu Petrochemical Co Ltd filed Critical Idemitsu Petrochemical Co Ltd
Publication of WO1995018011A1 publication Critical patent/WO1995018011A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B29C51/14—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor using multilayered preforms or sheets
    • 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
    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B29C51/08—Deep drawing or matched-mould forming, i.e. using mechanical means only
    • 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
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
    • 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
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0012—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular thermal properties
    • B29K2995/0015—Insulating

Definitions

  • the present invention does not require any special manufacturing equipment, and it is possible to obtain not only foamed containers having a uniform thickness distribution and foaming ratio but also intentionally foamed containers having a nonuniform thickness distribution and foaming ratio. Learn how to do it.
  • the foamed container obtained by the method of the present invention can be suitably used in various fields including foods and pharmaceuticals. Background art
  • the conventional foaming container aims at uniform foaming, and the foaming ratio is intentionally changed, that is, a portion having a high foaming ratio and a low foaming ratio in the container.
  • the existence of the part was previously unknown.
  • the present invention solves such conventional drawbacks, eliminates the need for special manufacturing equipment, and moves the gas in the foam layer at the time of container molding, thereby intentionally increasing the thickness distribution and the like.
  • the purpose of the present invention is to provide a method capable of obtaining a foamed container having a non-uniform sheet density.
  • the present invention does not require special manufacturing equipment, and maintains a sheet foaming state, forms a secondary foam or partially foams, or partially foams a container at the time of molding.
  • the purpose of the present invention is to provide a method (third aspect of the present invention to be described later) that can perform any one of the methods described above to obtain a container having a uniform thickness distribution and foam. Disclosure of the invention
  • the present invention firstly provides a foam core layer and adjacent to both sides thereof.
  • a foamed container obtained by thermoforming a laminated sheet having at least a three-layer structure, wherein the foamed core layer is made of a thermoplastic resin. It comprises an inorganic filler and a foaming agent, and the thermoplastic resin and the inorganic filler are blended in a ratio of 99.9 to 50% by weight of the former and 0.1 to 50% by weight of the latter.
  • a foam having open cells, wherein the convex portions are formed only on the outer surface of the container, and the expansion ratio of the concave portions formed on the inner surface of the container is the foaming core of the laminated sheet before molding.
  • Another object of the present invention is to provide a partially foamed thermoformed container characterized by having a lower expansion ratio than the layer.
  • the foamed core layer is composed of a thermoplastic resin, an inorganic filler and a foaming agent, and the thermoplastic resin and the inorganic filler are mixed with each other.
  • a thermoplastic resin an inorganic filler and a foaming agent
  • thermoplastic resin and the inorganic filler are mixed with each other.
  • a continuous foam layer having open cells and an outer layer adjacent to both sides of the foam core layer is heated.
  • a laminated sheet having at least a three-layer structure as a non-breathable layer made of a plastic resin is used, and the laminated sheet is thermoformed using a mold having only female molds with irregularities.
  • the foamed core layer is composed of a thermoplastic resin, an inorganic filler and a foaming agent, and the thermoplastic resin and the inorganic filler are formed by the former method. It has open cells that are mixed at a ratio of 9 to 50% by weight and the latter at 0.1 to 50% by weight.
  • the container outer surface side of the laminated sheet is heated to a high temperature, the container inner surface side is cooled to a low temperature immediately before shaping at the time of forming the container, and
  • the surface temperature difference (X) between the outer surface and the inner surface of the container is 10. Molding at a temperature such that C ⁇ X ⁇ 70 ° C and maintaining the sheet foaming state, secondary foaming or partially foaming, or partial foaming
  • Another object of the present invention is to provide a method for producing a foamed container characterized by performing one of the following steps. BRIEF DESCRIPTION OF THE FIGURES
  • FIG. 1 is a perspective view showing the external shape of the cup-shaped containers obtained in Examples 1 to 7 and Comparative Examples 1 and 3 to 7.
  • FIG. 2 is a perspective view showing the external shape of the wrapped container obtained in Comparative Example 2.
  • FIG. 3 is a longitudinal sectional view of the mold A used in Examples 1 to 5 and Comparative Examples 1 and 3 to 5.
  • FIG. 4 is a cross-sectional view of the mold A used in Examples 1 to 5 and Comparative Examples 1 and 3 to 5, and is a cross-sectional view taken along the line II of FIG.
  • FIG. 5 shows the cross-sectional shape of the container obtained in Comparative Example 3.
  • FIG. 6 shows the cross-sectional shape of the container obtained in Comparative Example 4.
  • FIG. 7 shows the cross-sectional shape of the container obtained in Example 4.
  • FIG. 1 is a perspective view showing the external shape of the cup-shaped containers obtained in Examples 1 to 7 and Comparative Examples 1 and 3 to 7.
  • FIG. 2 is a perspective view showing the external shape of the wrapped container obtained in Compar
  • FIG. 8 shows Embodiments 1, 2, 3, This figure shows the cross-sectional shape of the container obtained in steps 6 and 7.
  • FIG. 9 shows a cross-sectional shape of the container obtained in Example 5.
  • FIG. 10 shows the cross-sectional shape of the container obtained in Comparative Example 5.
  • FIG. 11 shows the cross-sectional shape of the containers obtained in Comparative Examples 1 and 6.
  • FIG. 12 shows the cross-sectional shape of the container obtained in Comparative Example 2.
  • FIG. 13 shows the shape of the cup-shaped container obtained in Example 14;
  • FIG. 13 (a) is a perspective view, and
  • FIG. (B) is a cross-sectional view of the uneven part (grip part).
  • FIG. 14 shows the shape of the cup-shaped container obtained in Example 15;
  • FIG. 14 (a) is a perspective view and
  • FIG. 14 (b) is FIG. 15 which is a cross-sectional view of the uneven portion (grip portion) shows the shape of the cup-shaped container obtained in Example 16;
  • FIG. FIG. 15 (b) is a perspective view, and
  • FIG. 15 (b) is a cross-sectional view of an uneven portion (grip portion).
  • FIG. 16 shows the shape of the cup-shaped container obtained in Comparative Example 10;
  • FIG. 16 shows the shape of the cup-shaped container obtained in Comparative Example 10;
  • FIG. 16 (a) is a perspective view
  • FIG. 16 (b) Is a cross-sectional view of the uneven portion (grip portion).
  • reference numeral 1 indicates a rib
  • reference numeral 2 indicates a female mold
  • reference numeral 3 indicates a male mold
  • reference numeral 4 indicates a clamp.
  • the partially foamed thermoformed container of the present invention comprises a foamed core layer and both sides thereof.
  • the partially foamed thermoformed container of the present invention has an outer shape such as a cup shape, a cylindrical shape, a truncated cone shape, a rectangular tube shape, a truncated pyramid shape, a flat box shape, a flat dish shape, and has an uneven surface. It is a thing.
  • the foamed core layer in the laminated sheet which is a material for obtaining the partially foamed thermoformed container of the present invention, is a foam having open cells, comprising a thermoplastic resin and a foaming agent.
  • the foam has an open cell ratio of 30% or more and 100% or less.
  • the foam core layer constituting the laminated sheet used in the present invention is a continuous foam layer having air permeability.
  • the foam form of the foamed core layer is a continuous cell, and is characterized by having continuity.
  • the open cell ratio in this foamed core layer is usually at least 30%, at most 100%, preferably at least 60%, as described above.
  • the open cell ratio in the foamed core layer is less than 30%, the foamed core layer has poor continuity and a small amount of gas moves, so that a partial foamed container cannot be obtained.
  • the open cell ratio is measured as follows.
  • a foam layer is provided in the intermediate layer, and both outer layers are non-foamed skin layers.
  • the dry automatic density meter measures the volume of a sample by the gas displacement method. For this reason, when measuring a foam sheet with this measuring instrument, the replacement gas penetrates into the foam cell, and as a result, a value lower than the apparent volume is measured. . Using this, the difference between the apparent volume: V and the measured volume: V A
  • ⁇ is the expansion ratio.
  • V T X L X W
  • a laminated sheet used as a molding material for a foamed container has a foamed core layer and a non-foamed outer layer adjacent to both sides of the foamed core layer as described above. It has at least a three-layer structure.
  • the foamed core layer which is an intermediate layer, is composed of a thermoplastic resin, an inorganic filler, and a foaming agent, and is a continuous foamed layer having open cells as described above. ing.
  • thermoplastic resin is not particularly limited as long as it is used for molding a container.
  • Polyolefin resins, polyvinyl chloride resins, and polyamide resins are used.
  • resins, polyester resins, vinyl acetate resins, styrene resins, and acrylate resins are used.
  • polyester resins, vinyl acetate resins, styrene resins, and acrylate resins are used.
  • the most preferred being polyolefin resins.
  • polystyrene resin there is no particular limitation on the polyolefin resin, but in particular, ethylene or a homopolymer of propylene, or ethylene or propylene and other polymers And high-density, medium-density or low-density polyethylene, linear low-density polyethylene, and the like. , Ethylene-vinyl acetate copolymer, ethylene acrylate copolymer, atactic, syndiotactic or isotactic Topoxypropylene, ethylene-propylene block copolymer or random copolymer, polybutene, polymethylpentene, etc. These may be used alone or in combination of two or more. Can be used as a mixture.
  • the melt index (Ml) of these thermoplastic resins may be appropriately selected in consideration of the use of the molded article, etc., and is not particularly limited, but is usually 0.3. ⁇ 10 g Z About 10 minutes is required.
  • Ml melt index
  • the foamed container obtained by the method of the present invention is used in a food or pharmaceutical-related field, etc., there is no problem in hygiene as a thermoplastic resin. It is necessary to select and use one.
  • foaming agent in addition to water, ordinary chemical foaming agents, for example, inorganic salts such as sodium bicarbonate, ammonium bicarbonate, ammonium carbonate, and azo.
  • inorganic salts such as sodium bicarbonate, ammonium bicarbonate, ammonium carbonate, and azo.
  • Organic compounds such as drug, paratoluenesulfonyl hydrazide and citric acid, and combinations of two or more of these foaming agents are listed.
  • the amount of the foaming agent used is not particularly limited, but is usually used so that the foaming ratio (primary foaming ratio) of the foamed core layer is 20 times or less, particularly 10 times or less.
  • a sodium bicarbonate foaming agent having a decomposition temperature of about 160 ° C. is used.
  • the amount of the foaming agent varies depending on the molding temperature, the type of the resin, the type of the foaming agent, and the like. Usually, the total amount of the thermoplastic resin and the inorganic filler described later is 100 parts by weight. 0.1 to 20 parts by weight with respect to the weight. Furthermore, it is indispensable to mix an inorganic filler in the foamed core layer as the intermediate layer. By blending such an inorganic filler, the foam core layer can be made into a continuous foam layer having air permeability.
  • the inorganic filler is not particularly limited.
  • silica, diatomaceous earth, rhodium oxide, rhodium oxide, pumice, pumice balun Such as oxides, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, etc., calcium carbonate, magnesium carbonate Carbonates such as um, dolomite and dosonite; sulfates such as calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite; Sulphite tanolec, clay, mai force, asbestos, glass paste, glass beads, cane oleate, monmorillo Nitrate, bentonite, etc., and salts of carbon, such as carbon black, graphite, carbon hollow spheres, etc.
  • Powders such as molybdenum sulfide, zinc borate, barium metaborate, calcium borate, sodium borate, etc. Shaped, granular, and plate-like materials can also be used. Of these, talc and carbonated water are particularly preferred. These inorganic fillers may be used alone or in combination of two or more.
  • the mixing ratio of the thermoplastic resin and the inorganic filler in the foamed core layer is usually from 99.9 to 50% by weight of the thermoplastic resin, and from 0.1 to 50% by weight of the inorganic filler. Percentage, preferably the former The ratio of the latter is 0.5 to 35% by weight relative to 99.5 to 65% by weight. If the blending ratio of the inorganic filler is too small, it is not possible to form a permeable continuous foam layer, and it is not possible to obtain a sufficient communication rate of the foam core layer. On the other hand, if the mixing ratio of the inorganic filler is too large, the foam becomes coarse and the sheet becomes brittle, so that when the container is formed, the container is broken. This makes it difficult to form containers. Therefore, neither is preferred.
  • the outer layer (layer adjacent to both sides of the foamed core layer) constituting the laminated sheet used in the present invention is a non-foamed non-breathable layer made of a thermoplastic resin. It is.
  • the non-breathable means a material that does not substantially breathe instantaneously.
  • thermoplastic resin in the outer layer examples include those described in the description of the foaming core layer, and are usually used in the foaming core layer.
  • the same thermoplastic resin preferably a polyolefin resin
  • a different thermoplastic resin preferably a polyolefin resin
  • Refin resin may be used.
  • Particularly preferred are homopolymers of ethylene or propylene, or copolymers of ethylene or propylene with other olefins. You.
  • the laminate used in the present invention has at least a three-layer structure of the above-described foamed core layer and outer layers adjacent to both sides of the foamed core layer.
  • an ethylene vinyl layer is provided between the outer layer on one side and the foam core layer via an adhesive layer.
  • EVOH is a copolymer obtained by genating an ethylene vinyl acetate copolymer and having a content of 25 to 50 mol% of ethylene. Used.
  • the adhesive constituting the adhesive layer is not particularly limited as long as it is suitable for bonding the EVOH layer and the foamed core layer.
  • the adhesive may be an unsaturated carboxylic acid-modified polyester. Examples include propylene, ethylene-ethyl acrylate copolymer, and ethylene monovinyl acetate copolymer.
  • the inorganic filler is provided between the foamed core layer and the outer layer.
  • Those provided with a non-foamed layer containing a thermoplastic resin may also be used.
  • the inorganic filler used for the non-foamed layer containing the inorganic filler-containing thermoplastic resin the same ones as those used in the foamed core layer can be used, and particularly, Is preferred.
  • the inorganic filler used in this layer the same one as that used in the foam core layer or a different one may be used.
  • the ratio of the inorganic filler in this layer is usually from 0.1 to 50% by weight of the inorganic resin to 99.9 to 50% by weight of the thermoplastic resin.
  • thermoplastic resin used for the non-foamed thermoplastic resin-containing thermoplastic resin layer is the same as that described in the description of the foamed core layer. Also used in layers The same thermoplastic resin as described above may be used, or a different thermoplastic resin may be used. Especially preferred are polyolefin-based resins, especially single polymers of ethylene or propylene, or ethylene or propylene and other olefins. Is a copolymer of
  • a laminated sheet provided with a separation layer that can be separated at the interface on at least the outer surface of one of the outer layers can be used as the laminated sheet.
  • Such a separation layer is provided on at least one outer layer (outside) via a lower surface layer below (inside) and at an interface so as to be separable.
  • this release layer is located on the inner surface of the container.
  • the outer layer of one outer layer provided with a separation layer through the lower surface layer has a five-layer structure, and the outer layer of both outer layers has a seven-layer structure. It will be something.
  • This release layer is made of the same thermoplastic resin as described above, and contains no inorganic filler or foaming agent (a thermoplastic resin containing no inorganic filler). (Foamed layer).
  • thermoplastic resin used in the separation layer and the lower surface layer those described in the description of the foamed core layer are mentioned, and the same thermal resins as those used in the foamed core and the outer layer are used.
  • a plastic resin preferably a polyolefin resin
  • a different resin may be used.
  • thermoplastic resin that constitutes the release layer Resin in particular, polyethylene or polypropylene is preferred.
  • thermoplastic resin constituting the lower layer it is preferable to use a polyolefin-based resin.
  • a polypropylene resin and a polyethylene resin Preference is given to using a mixture.
  • the layers constituting the laminated sheet may be used, if necessary, with lubricants, coloring agents, antioxidants, ultraviolet absorbers, surfactants, flame retardants, etc. Additives such as plasticizers and antistatic agents may be added.
  • foam core layer outer layer, etc.
  • Additives such as plasticizers and antistatic agents may be added.
  • the amount of these additives is usually about 0.01 to 10 parts by weight based on 100 parts by weight of the resin component.
  • the laminated sheet used as the molding material of the foam container is basically composed of a foam core layer and at least an outer layer adjacent to both sides of the foam core layer.
  • Each of the three layers is composed of three layers, and various layers are laminated as necessary.
  • a method of lamination there is a method of forming each layer sheet separately, and then bonding each layer sheet by thermocompression bonding or sandwiching each layer with an adhesive, but using a respective extruder for each layer.
  • the method of co-extrusion using a common die is the most preferable in terms of efficiency and food hygiene. That is, the components of each layer are The mixture is melt-kneaded using a well-known Banbury mixer, single-screw / double-screw kneader, or the like, and the obtained pellets are co-extruded using a common die using an extruder for each layer.
  • the method is preferred.
  • Such a co-extrusion method is less likely to cause cracks and break the sheet during molding than the laminating method by thermocompression bonding, and the bonding is also small. Efficient and highly preferred for food hygiene.
  • the laminated sheet obtained in this way has a structure in which a foam core layer forming a permeable continuous foam layer is an RB layer, and the foam core layer (RB layer)
  • the non-breathable outer layer (non-foamed layer) adjacent to both sides is defined as an HH layer
  • the ethylene-vinyl alcohol copolymer layer is defined as an EVOH layer
  • the RB layer and the HH layer are defined as an EVOH layer.
  • the laminated sheet used in the present invention is not limited to those having these structures.
  • each layer of the laminated sheet varies depending on the use of the container, it is generally 0.2 to 4.5 mm for the RB layer and 0.1 for the HH layer. 11.5 mm, EV0H layer is about 0.01-0.1 mm, bottom layer is about 0.01-0.2 mm, and separation layer is about 0.01-0.2 mm. However, it is preferable that the total thickness of the laminated sheet is 0.5 to 6 mm.
  • the thickness of the outer layer be 50% or less of the total layer thickness, particularly 5 to 30%.
  • the thickness of the outer layer exceeds 50% of the total layer thickness, it becomes impossible to find properties as a foam, such as heat insulation and weight reduction.
  • the partially foamed thermoformed container of the present invention is a foamed container obtained by thermoforming the laminated sheet as described above, wherein the convex portion is formed only on the outer surface of the container.
  • the present invention is characterized in that the expansion ratio of the concave portion formed on the inner surface of the container is lower than the expansion ratio of the expanded core layer of the laminated sheet before molding.
  • the convex portion is formed only on the outer surface of the container, and a very small concave portion is formed on the inner surface of the container. .
  • the expansion ratio (N) of the convex portion formed on the outer surface of the container is n
  • the distance be in the range of 1.2 ⁇ k ⁇ 4.
  • the foaming ratio of the convex portion formed on the outer surface of the container is at least 1.2 times the foaming ratio of the foamed core layer of the laminated sheet before molding. If this value is less than 1.2 times, there is a significant difference in the heat insulation compared to a container that is not partially foamed. Not.
  • the expansion ratio of the convex portion formed on the outer surface of the container exceeds 4 times the expansion ratio of the expanded core layer of the laminated sheet before molding, the convex portion formed on the outer surface of the container is reduced. The air bubbles become very coarse, resulting in tearing of the outer surface of the container and deterioration of the container appearance.
  • an extremely small concave portion is formed on the inner surface of the container inside the portion where the convex portion is formed, and the expansion ratio of this concave portion is: It is lower than the expansion ratio of the foamed core layer of the laminated sheet before molding.
  • Such a partially foamed thermoformed container of the present invention can be manufactured, for example, as follows.
  • the foamed core layer is composed of a thermoplastic resin, an inorganic filler, and a foaming agent, and the thermoplastic resin and the inorganic filler are formed in the former 99.9.
  • a thermoplastic resin 0.1 to 50% by weight as a continuous foam layer
  • the outer layers adjacent to both sides of the foam core layer are made of a thermoplastic resin.
  • a laminated sheet having at least a three-layer structure as an air-impermeable layer is used, and the laminated sheet is thermoformed using a mold having only female molds with irregularities.
  • the present invention also provides a method for producing the first partially foamed thermoformed container of the present invention.
  • the foamed core layer is composed of a thermoplastic resin, an inorganic filler and a foaming agent, and the thermoplastic resin and the inorganic filler are composed of 99.9 to 50% by weight of the former and 0.1% by weight of the latter. ⁇ 50% by weight At least a three-layer structure in which a continuous foam layer formed by mixing the two layers together and an outer layer adjacent to both sides of the foam core layer is an air-impermeable layer made of a thermoplastic resin
  • the sheet is as described in the first part of the present invention.
  • the open cell ratio in the foamed core layer is usually 30% or more, 100% or less, preferably 60% or more, 100% or less, and more preferably 6% or less. 5% or more and 100% or less is also as described in the first aspect of the present invention. Further, the usage ratio of the foaming agent is as described in the first item of the present invention.
  • the laminated sheet is thermoformed using a mold provided with irregularities only in a fit mold.
  • thermoforming method of the foaming container examples include vacuum forming, vacuum pressure forming, and the like, and the preceding clamp plug vacuum forming is particularly preferable.
  • plug-assist vacuum forming plug-assist vacuum forming is performed while clamping the outer periphery of the container opening.
  • the molding conditions may be ordinary molding conditions, but it is necessary to thermally mold the laminated body using a metal mold having only female molds with irregularities.
  • the shape of the unevenness can be various shapes such as vertical stripes, horizontal stripes, meshes, hemispheres, and the like. No need. In addition, these irregularities should be provided not only on the part that is gripped by the hand of the container, but also on other parts, for example, the female mold part corresponding to the bottom of the container and the entire outer surface. 0
  • gas is moved from a narrow portion to a wide portion through a gas-permeable continuous foam layer, as described below. This is because we are trying to manufacture containers with uneven wall thickness distribution and sheet density.
  • the second aspect of the present invention is to form a raw sheet as it is by concentrating the air in the layer on a part of the container by utilizing the characteristics of the sheet having open cell properties.
  • a temperature difference is formed between the upper and lower portions of the sheet in a later-described embodiment. It is formed by the thermoforming method described in Japanese Patent Application No. 5-347065, which is characterized by.
  • the distance between the female mold and the male mold is smaller than the value obtained by dividing the sheet thickness by the expansion ratio of the container (surface area ⁇ inner opening area) in the area other than the convex part of the container.
  • the convex part is formed by using a female mold that is wider than the value obtained by dividing the sheet thickness by the expansion ratio of the container.
  • a container having a non-uniform thickness distribution and a non-uniform sheet density can be used without requiring special manufacturing equipment. It can be manufactured.
  • a foamed container partially having a high foaming portion and a low foaming portion can be obtained. This is not due to foaming, but to the movement of gas in the laminate (laminated sheet). Therefore, if the amount of gas held in the sheet volume required for molding is A and the amount of gas held in the molding container is B, the raw foam and the foam container , The relationship A ⁇ B holds. In other words, the amount of gas held in the molding container is equal to or less than the amount of gas held in the volume of the laminated sheet required for molding.
  • the foaming ratio of the portion formed in the concave portion of the female mold is higher than the foaming ratio of the laminated sheet (raw foam), and partially.
  • a foaming container having a high foaming portion and a low foaming portion can be obtained.
  • the highly foamed portion is formed not by the secondary foaming but by the gas movement in the laminated sheet, so that the foamed core layer and the foamed core layer are not formed by the secondary foaming.
  • a breathable continuous foam layer is used, and the outer layers adjacent on both sides are non-breathable layers made of a thermoplastic resin. Due to such gas movement in the laminated sheet, foaming is intentionally caused by the presence of a high foaming portion and a low foaming portion, and the thickness distribution and the sheet density are not uniform. container Has never been known before.
  • the foamed sheet in the laminated sheet is formed by performing thermoforming using the laminated sheet as described above and using a mold having only female dies with irregularities.
  • the gas in the layer is concentrated in the recesses of the female mold during thermoforming, and after molding, high and low expansion ratio parts can be formed in the container. is there.
  • the wall thickness distribution and foaming are non-uniform, and there are partially high foaming parts and low foaming parts. It is possible to obtain a foam container having excellent properties.
  • the first foamed container of the present invention obtained by the second of the present invention has an outer shape such as a cup shape, a cylindrical shape, a truncated cone shape, a square tube shape, a truncated pyramid shape, a flat box shape, a flat dish shape, or the like. It has a surface and has irregularities on its surface.
  • the outer surface of the container has irregularities, a foamed container having improved rigidity can be obtained.
  • the second aspect of the present invention it is possible to faithfully reproduce more detailed three-dimensional patterns and designs than can be obtained by embossing or the like on the outer surface of the foamed container. May be omitted It is possible.
  • the foamed core layer comprises a thermoplastic resin, an inorganic filler and a foaming agent, and the thermoplastic resin and the inorganic filler are formed by the former method.
  • a foamed container by using a laminated sheet having at least a three-layer structure in which the outer layer is a non-breathable layer made of a thermoplastic resin, and forming the laminated sheet, Immediately before shaping at the time of forming the container, the outer surface of the laminated sheet is heated to a high temperature, the inner surface of the container is cooled, and the surface temperature difference (X) between the outer surface of the container and the inner surface of the container is 10 °. Mold at a temperature such that C ⁇ X ⁇ 70 ° C to maintain the sheet foaming state, or secondary foaming or partially foaming. Either, or partially or to the secondary expansion, Ru Nodea also a manufacturing method for provision of the bubbling container, wherein the this Cormorant row the noise Zureka.
  • the laminated sheet used as the molding material of the foamed container is the same as that used in the second aspect of the present invention.
  • the outer surface side of the laminated sheet is heated to a high temperature just before shaping at the time of molding the container.
  • the container is molded at a temperature such that the inside surface of the container is at a low temperature and the surface temperature difference (X) between the outside surface of the container and the inside surface of the container is 10 ° C ⁇ X ⁇ 70 ° C.
  • X surface temperature difference
  • Examples of the method for forming the foam container include vacuum forming and vacuum pressure forming, but vacuum pressure forming is particularly preferable.
  • the molding conditions may be ordinary molding conditions, but immediately before shaping at the time of molding the container, the outer surface of the laminated sheet is heated to a high temperature, the inner surface of the container is cooled, and the outer surface of the container (the female mold side).
  • the surface temperature difference (X) is 10 ° C or less, foaming does not occur (because the inside surface is pulled to the outside surface and the foam becomes flattened down).
  • a container having a uniform thickness distribution and uniform foam can be manufactured.
  • a container having an irregular surface on the outer surface of the foamed container can be obtained.
  • the side wall and the bottom of the female mold and the cavity are made uneven, and such a mold is used.
  • the outer surface side of the container of the foamed sheet or laminated sheet is heated to a high temperature, and the inner surface side of the container is cooled to a constant temperature difference. Then, only the part of the outer surface of the container that hits the convex part is foamed. If there is no temperature difference between both sides of the foamed sheet or the laminated sheet, the inner part of the container may be formed into a shape along the outer irregularities or may not foam.
  • the high temperature side of the sheet (outer surface side of the container) is shaped according to the shape of the concave and convex cut in the female mold of the mold, while the low temperature side of the sheet is formed.
  • the side (the inner side of the container) is not formed along the uneven surface and is formed on a smooth surface.
  • one-stage foaming type Chemical foaming agent manufactured by Boehringer Gelnheim, trade name: Handrocell
  • two-stage foaming type chemical foaming agent manufactured by Dainichi Seika, product Name: Die blow
  • each of the above raw materials was pelletized and fed to each extruder (65 mm diameter extruder for the foam core layer and 65 mm diameter extruder for both outer layers). Co-extrusion using an ordinary T-die at an extrusion temperature of 160 to 200 ° C. The thickness of both outer layers is 0.5 mm, and the thickness of the foam core layer is 3.2 mm. Manufactured sheets. The foaming ratio of the foamed core layer of this laminated sheet was 3.2 times. The communication rate of the foamed core layer, that is, the open cell rate was 70%. The open cell rate was calculated by the above-described open cell rate measurement method based on the measurement value obtained using a dry automatic densitometer (manufactured by Shimadzu Corporation).
  • This three-layer laminated sheet is formed into a cup-shaped container by the thermoforming method according to Japanese Patent Application No. 5-347065, that is, a method of providing a heating temperature difference between the upper and lower sheets. Molded.
  • the method of the present invention is not limited to this thermoforming method.
  • the resulting container had a cap-like shape with an opening diameter (inner dimension) of 95.5 mm and a height of 35 mm having the appearance as shown in Fig. 1.
  • the length of rib 1 is 20 mm
  • the height of rib 1 is 2 mm
  • the width of rib 1 is 4 mm
  • the distance between ribs is 2 mm
  • the number of ribs is 50 It was a book, and the unfolding magnification was 2.45 times (surface area ⁇ inner opening area).
  • the cross-sectional shape of the container was as shown in FIG.
  • FIG. 4 is a cross-sectional view taken along the line I-I of FIG.
  • the female mold 2 was provided with an uneven shape, the length of the concave portion was 2 Omm, and the number of the concave portions was 50 (the length of the rib 1 and the Corresponding to the number).
  • reference numeral 3 is a male mold, and reference numeral 4 is a clamp.
  • Table 1 shows the results of the heat insulation when compared with the above.
  • One-stage foaming type chemical foaming agent manufactured by Behringer Ingelheim, product name: Cellulose Hand Cell
  • the raw material of the foamed core layer is made of polypropylene resin (polypropylene homopolymer, manufactured by Idemitsu Petrochemical, trade name: Idemitsu Polypropylene)
  • a cup-shaped container was obtained in exactly the same manner as in Example 1 except that the height of the rib 1 of the container was 1.5 mm. The results are shown in Table 1.
  • Example 5 As is evident from Table 1, the partial foamability and the appearance of the container were good. Insulation was slightly different from that of Comparative Example 2 but significant. Example 5
  • a cup-shaped container was obtained in the same manner as in Example 1 except that the height of the rib 1 of the container was 5 mm. The results are shown in Table 1.
  • Example 1 the cup was completely formed in the same manner as in Example 1 except that the container was not provided with any rib portion and was formed into a container having a container appearance as shown in FIG. A container was obtained. The results are shown in Table 1.
  • Example 1 A cup-shaped container in the same manner as in Example 1 except that the height of the rib 1 of the container was set to 0.1 mm in Example 1. I got The results are shown in Table 1.
  • Comparative Example 4 The container obtained in Comparative Example 3 would have a k of 1.2 due to a change in the uneven shape of the container. Comparative Example 4
  • a cup-shaped container was obtained in the same manner as in Example 1 except that the height of the rib 1 of the container was 0.5 mm. The results are shown in Table 1.
  • Comparative Example 5 The container obtained in Comparative Example 4 has a value of 1.2 due to a change in the uneven shape of the container. Comparative Example 5
  • a cup-shaped container was obtained in the same manner as in Example 1 except that the height of the rib 1 of the container was 5.5 mm. The results are shown in Table 1.
  • Example 7 In the same manner as in Example 1, except that the blending amounts of the polypropylene resin and the inorganic filler were changed to 90% by weight and 10% by weight, respectively. Table 1 shows the results of obtaining cup-shaped containers. As is evident from Table 1, the partial foaming property and the appearance of the container were good, and the heat insulating property was significantly different from the heat insulating property of Comparative Example 2.
  • Example 7
  • Example 1 In the same manner as in Example 1, except that the blending amounts of the polypropylene resin and the inorganic filler were changed to 80% by weight and 20% by weight, respectively. Table 1 shows the results of obtaining cup-shaped containers.
  • a cup-shaped container was obtained in the same manner as in Example 1 except that no inorganic filler was used in Example 1. The results are shown in Table 1.
  • Example 4 70% 3.2 times ⁇ 6 Figure 3.6 times 1.1 X kW riff ⁇ 3 ⁇ 4 0.5 band
  • inorganic 30 parts by weight of tark manufactured by Katsumitsuyama, average particle diameter: 10 m
  • calcium carbonate manufactured by Nitto Powder Chemical, average particle diameter: 1 / D1 or less
  • Titto Powder Chemical average particle diameter: 1 / D1 or less
  • anatase type (produced by Hara Sangyo), antioxidant (lin-based antioxidant, trade name: PEP —— 8, Asahi Denka)
  • Surfactant (trade name, manufactured by Toho Chemical) : A mixture of 0.5 parts by weight of T-solvent and 50 ppm of water was mixed using a high-speed mixing mixer (Hensil mixer manufactured by Kawada Seisakusho). Then, the mixture was charged into a bent type single-screw kneader and extruded at 210 ° C. to obtain a porous pellet having a void ratio of 50%.
  • thermoplastic containing inorganic filler 1.0% by weight of a chemical foaming agent (trade name: Hydrocell, manufactured by Dainichi Seika) was added to the porous pellet, and the resulting mixture was added to an intermediate layer (thermoplastic containing inorganic filler).
  • a chemical foaming agent trade name: Hydrocell, manufactured by Dainichi Seika
  • the outer layer thermoplastic resin non-foamed layer
  • pellets were obtained in the same manner as above.
  • the three-layer laminated sheet is formed by vacuum pressure forming method.
  • Table 2 shows the surface temperature of the laminated sheet on the outer surface side of the container (sculpture mold side) and the inner surface side of the container (male mold side) immediately before shaping.
  • the outer surface of the container (female mold side) just before shaping Table 2 shows the evaluation results of the surface temperature and formability of the laminated sheet on the inner surface side (male mold side) of the container.
  • a cup-shaped container was molded in the same manner as in Example 8, except that the container was changed to an opening diameter of 135 mm, a bottom diameter of 95 mm, and a height of 10 Omm. did.
  • Table 2 shows the evaluation results of the surface temperature and moldability of the laminated sheet on the outer surface side (female mold side) and inner surface side (male mold side) of the container immediately before shaping.
  • Example 10
  • an adhesive layer (a product made by Idemitsu Petrochemical: Idemitsu Polytax E—a layer made of an adhesive resin indicated by 100) is provided between one outer layer and the intermediate layer on one side. (Made by Kuraray, trade name: EVAL E) layer was co-extruded through the above to obtain a laminated sheet having the thickness shown in parentheses and having the following six-layer structure.
  • Example 1 Using this laminated sheet, a cup-shaped container was formed in the same manner as in Example 8, except that an EVOH layer was formed on the inner surface side of the container.
  • Table 2 shows the evaluation results of the surface temperature and moldability of the laminated sheets on the outer surface side (female mold side) and the inner surface side (male mold side) of the container immediately before shaping.
  • Example 1 1
  • Example 8 on the outer surface of one outer layer on one side, a separation layer capable of separating at the interface was provided via the lower surface layer, and as a component constituting the outer layer, a high-density polyethylene was used.
  • Len made by Idemitsu Petrochemical, trade name: 52 MB
  • Polypropylene made by Idemitsu Petrochemical, trade name E—100G
  • tal Mer by Katsumitsuyama, average particle diameter: 10 m
  • the same procedure as in Example 8 was carried out to obtain the following Thus, a laminated sheet having a five-layer structure was obtained. ⁇ Layer (0.1mm) Z Lower layer (0.1mm) Z Outer layer (0.2mm) Z Middle layer (1.2mm) Z layer (0.2mm) 0
  • Idemitsu Petrochemical's Polypropylene (trade name: E-20 OS) was used as a component of the separation layer, and a high-density polymer was used as a component of the lower surface layer.
  • Ethylene (manufactured by Idemitsu Petrochemical, trade name: 52 MB) 42 parts by weight
  • Polypropylene (manufactured by Idemitsu Petrochemical, trade name: E-100G) 2 & parts by weight Luc (manufactured by Katsumitsuyama, average particle size: 10 m)
  • a material consisting of 30 parts by weight was used.
  • a cup-shaped container was formed in the same manner as in Example 8 except that the laminated sheet was arranged so that the separation layer was on the inner surface side of the container.
  • Table 2 shows the evaluation results of the surface temperature and moldability of the laminated sheets on the outer surface side (female mold side) and the inner surface side (male mold side) of the container immediately before shaping.
  • Example 1 2
  • Example 8 between the outer layer and the intermediate layer, a polypropylene (made by Idemitsu Petrochemical Co., trade name: E—105 GM) 60 weight parts and a talc (made by Katsumitsuyama, Example 8 Except that an inorganic filler-containing thermoplastic resin layer (thickness: 2 mm) consisting of 40 parts by weight of each was provided to form a 5-layer laminated sheet.
  • a cup-shaped container was formed in the same manner as described above.
  • Table 2 shows the evaluation results of the surface temperature and moldability of the laminated sheet on the outer surface side of the container (female mold side) and the inner surface side of the container (male mold side) immediately before shaping.
  • Example 13 shows the evaluation results of the surface temperature and moldability of the laminated sheet on the outer surface side of the container (female mold side) and the inner surface side of the container (male mold side) immediately before shaping.
  • Example 8 The procedure was performed in the same manner as in Example 8 except that the shape of the container was a square tray having a mouth of 16 cm ⁇ 10 cm, a bottom of 13 cm ⁇ 7 cm, a height of 2 cm, and vacuum forming.
  • a foamed container was obtained in the same manner as in Example 8.
  • Table 2 shows the evaluation results of the surface temperature and moldability of the laminated sheets on the outer surface side (sculpture mold side) and the inner surface side (male mold side) of the container immediately before shaping. Comparative Examples 8 to 9
  • Example 8 except that the surface temperature of the laminated sheet on the outer surface side (female mold side) and the inner surface side (male mold side) of the container immediately before shaping was changed as shown in Table 2. Then, a cup-shaped container was formed in the same manner as in Example 8. ⁇ Outside of container just before shape (Female mold Table 2 shows the evaluation results of the formability, as well as the surface temperature of the laminated sheet on the inner side (male mold side) and the inner side of the container (male mold side). (Hereinafter, margin)
  • As an inorganic filler Katsumitsuyama, average particle size: 10 m
  • calcium carbonate Nito Powder Chemical, average particle size: 1 m or less
  • the blended components were mixed using a high-speed mixing mixer (Henschel mixer manufactured by Kawada Seisakusho), and then charged into a bent single-shaft k
  • thermoplastic resin foam layer 1.0% by weight of a chemical foaming agent (trade name: Hydrocell, manufactured by Dainichi Seika) was added to the porous pellet, and the resulting mixture was added to the intermediate layer (heat containing inorganic filler).
  • a chemical foaming agent trade name: Hydrocell, manufactured by Dainichi Seika
  • the outer layer thermoplastic resin non-foam layer
  • the polypropylene resin containing no inorganic filler (same as above)
  • pellets were obtained in the same manner as above.
  • This three-layer laminated sheet was formed by vacuum pressure forming method with an opening diameter of 135 mm, a bottom diameter of 135 mm, and a height of 105 mm. It was formed into a cup-shaped container with a convex shape in the area (gripping part) of the shape shown in Fig. 13.
  • the temperature of the laminated sheet on the outer surface side (female mold side) of the container immediately before shaping was 121 ° C, and the surface temperature of the laminated sheet on the inner surface side of the container (male mold side) was 98 ° C. It was made to be C, and it was molded using a specially shaped metal mold with irregularities as the female metal.
  • Table 3 shows the evaluation results of the maximum foaming ratio and the heat insulation (grip time).
  • the heat insulation indicates the time during which hot water at 95 ° C was poured into the sample container up to the 8th minute and held with bare hands. If this time is less than 30 seconds, it cannot be used practically, and if it is more than 60 seconds, it can be used practically.
  • Example 14 the shape of the mold to be used was changed, and as shown in FIG. 14, a cup-shaped container having an uneven surface on the entire side (opening diameter 70 mm, bottom (70 mm diameter, 6 O mm height) was molded.
  • Table 3 shows the evaluation results of the maximum foaming ratio and the heat insulation (grip time).
  • Example 14 the shape of the mold used was changed, and as shown in FIG. 15, a cup-shaped container having an unevenness only at the lower portion of the side of the container (open diameter: 135 mm, bottom diameter: It was molded to have a height of 135 mm, a height of 105 mm, and a height of 4 Omm below the side wall of the container, with a concave-convex shape as a gripping part).
  • Table 3 shows the evaluation results of the maximum foaming ratio and heat insulation (grip time). Comparative Example 10
  • Example 14 except that the surface temperature of the laminated sheet on the outer surface side (female mold side) and the inner surface side (male mold side) of the container immediately before shaping were both set to 121. Gap-shaped containers were formed in the same manner as in Example 14. The obtained cup-shaped container had an irregular inner surface as shown in Fig. 16. Table 3 shows the evaluation results of the maximum foaming ratio and the heat insulation (grip time). Table 3
  • the first partially foamed container of the present invention having a high-foamed portion and a low-foamed portion, not by secondary foaming but by gas transfer inside the laminate. Is obtained.
  • the thickness distribution and the foaming are non-uniform, the foam has a partially highly foamed portion, and
  • the first partially foamed container of the present invention having excellent design properties can be obtained.
  • the container obtained according to the second aspect of the present invention has a partially high foaming portion, so that it can be directly grasped by hand even when it contains high-temperature contents. It is possible. Further, according to the second aspect of the present invention, since the outer surface of the container has irregularities composed of a high foaming portion and a low foaming portion, it becomes a rib to obtain a foamed container having improved rigidity. Can be done.
  • the inside of the molded foam container is smooth with almost no irregularities, which is excellent in appearance as a container, and is excellent in covering food and medicine. It is possible to obtain a container in which almost no contents remain, and at least the portion of the outer surface of the container that is gripped by hand has irregularities.
  • the second aspect of the present invention it is possible to faithfully reproduce a more detailed three-dimensional pattern, pattern, etc. than can be obtained by embossing or the like on the outer surface of the foamed container. It is also possible to omit the printing.
  • the thickness of the container other than the foamed portion is thin. It becomes bad. Therefore, it has such characteristics that the whole container has a thin feeling, is not bulky, and has good thermal conductivity, and can be frozen and boiled even though it is an insulated container.
  • the third aspect of the present invention no special manufacturing equipment is required, and when the container is formed, the sheet is kept in a foamed state, is subjected to secondary foaming or partially foamed, or is partially foamed. It is possible to obtain a container with uniform wall thickness distribution and foaming by subjecting either secondary foaming or foaming. Further, the foamed container obtained by the third aspect of the present invention has excellent heat insulating properties. I In the third aspect of the present invention, thermoforming is easy.
  • the third aspect of the present invention there is no need for special manufacturing equipment as described above, and it is a simple equipment, which is excellent in design and accommodates high-temperature contents. Even so, a heat-insulating foam container that can be directly grasped by hand can be manufactured.
  • the foaming on the inner side of the molded foam container is suppressed, the unevenness is almost smooth and the container is excellent in appearance.
  • a container that contains little food or medicine, etc. and has at least a part of the outer surface of the container that is gripped by hand, with irregularities. can get.
  • the gripping portion is highly foamed, the container has high heat or low temperature contents, in combination with high heat insulation and a large surface area of the gripping portion. Can be grasped with bare hands.
  • the first partially foamed container of the present invention obtained by the second of the present invention can be suitably used in various fields including foods and pharmaceuticals. Furthermore, the first partially foamed container of the present invention obtained by the third of the present invention can also be suitably used in various fields including foods and pharmaceuticals.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)

Abstract

Un conteneur expansé est obtenu par thermoformage d'une feuille stratifiée présentant une structure à au moins trois couches composées d'une âme expansée et de deux couches externes non expansées de chaque côté de l'âme et adjacentes à celle-ci. L'âme expansée est composée d'une résine thermoplastique, d'une charge minérale et d'un agent d'expansion. 99,9 à 50 % en poids de la résine thermoplastique et 0,1 à 50 % de la charge minérale sont mélangés pour former un corps expansé à alvéoles ouverts. Des parties en saillie sont formées uniquement sur la surface externe du conteneur, le taux de cavités formées sur la surface interne du conteneur étant inférieur à celui de l'âme de la feuille stratifiée avant le formage. L'invention peut se présenter non seulement sous la forme d'un conteneur expansé, dont la répartition des épaisseurs de parois et le moussage sont uniformes, mais aussi sous la forme d'un conteneur partiellement expansé, dont la répartition des épaisseurs de parois et le moussage sont non uniformes, présentant des zones en partie fortement expansées et doté d'un excellent design. Ledit conteneur partiellement expansé est obtenu par introduction d'un gaz dans la couche expansée au moment du formage du conteneur et par moussage d'une partie du conteneur. Par conséquent, l'épaisseur de paroi du conteneur est faible dans les zones non expansées. Le conteneur semble ainsi présenter des parois peu épaisses dans sa totalité. Bien que le conteneur soit peu encombrant et isolé thermiquement, il présente une conductibilité thermique élevée et peut être réfrigéré ou réchauffé.
PCT/JP1994/002248 1993-12-27 1994-12-27 Conteneur thermoforme, partiellement expanse et son procede de fabrication Ceased WO1995018011A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP5/347065 1993-12-27
JP34706593A JP3342762B2 (ja) 1993-12-27 1993-12-27 発泡容器とその製造方法
JP17775294A JP3400553B2 (ja) 1994-07-07 1994-07-07 部分発泡熱成形容器とその製造方法
JP6/177752 1994-07-07

Publications (1)

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WO1995018011A1 true WO1995018011A1 (fr) 1995-07-06

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2423916B (en) * 2005-03-09 2009-02-11 Taylor Egbert H & Company Ltd Insulated waste container

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5278153A (en) * 1975-12-24 1977-07-01 Nihon Matai Co Ltd Production of heat insulation container
JPS61216836A (ja) * 1986-03-20 1986-09-26 Sekisui Plastics Co Ltd 皮付のフルモールド用発泡ブロー成形品の製造方法
JPH0554810B2 (fr) * 1988-06-30 1993-08-13 Sekisui Plastics

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5278153A (en) * 1975-12-24 1977-07-01 Nihon Matai Co Ltd Production of heat insulation container
JPS61216836A (ja) * 1986-03-20 1986-09-26 Sekisui Plastics Co Ltd 皮付のフルモールド用発泡ブロー成形品の製造方法
JPH0554810B2 (fr) * 1988-06-30 1993-08-13 Sekisui Plastics

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2423916B (en) * 2005-03-09 2009-02-11 Taylor Egbert H & Company Ltd Insulated waste container

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