WO2001015882A1 - Procede de production pour mousse de resine thermoplastique, moule de moulage prevu a cet effet et mousse de resine thermoplastique - Google Patents
Procede de production pour mousse de resine thermoplastique, moule de moulage prevu a cet effet et mousse de resine thermoplastique Download PDFInfo
- Publication number
- WO2001015882A1 WO2001015882A1 PCT/JP2000/005776 JP0005776W WO0115882A1 WO 2001015882 A1 WO2001015882 A1 WO 2001015882A1 JP 0005776 W JP0005776 W JP 0005776W WO 0115882 A1 WO0115882 A1 WO 0115882A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cavity
- thermoplastic resin
- foam
- resin foam
- expansion
- Prior art date
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Classifications
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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
- B29C44/34—Auxiliary operations
- B29C44/3442—Mixing, kneading or conveying the foamable material
- B29C44/3446—Feeding the blowing agent
- B29C44/3453—Feeding the blowing agent to solid plastic material
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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
- B29C44/08—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 using several expanding or moulding steps
- B29C44/083—Increasing the size of the cavity after a first part has foamed, e.g. substituting one mould part with another
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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
- B29C44/34—Auxiliary operations
- B29C44/58—Moulds
- B29C44/586—Moulds with a cavity increasing in size during foaming
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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
- B29C44/34—Auxiliary operations
- B29C44/3442—Mixing, kneading or conveying the foamable material
- B29C44/3446—Feeding the blowing agent
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249961—With gradual property change within a component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249987—With nonvoid component of specified composition
- Y10T428/249988—Of about the same composition as, and adjacent to, the void-containing component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249987—With nonvoid component of specified composition
- Y10T428/249988—Of about the same composition as, and adjacent to, the void-containing component
- Y10T428/249989—Integrally formed skin
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249987—With nonvoid component of specified composition
- Y10T428/249991—Synthetic resin or natural rubbers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249987—With nonvoid component of specified composition
- Y10T428/249991—Synthetic resin or natural rubbers
- Y10T428/249992—Linear or thermoplastic
Definitions
- thermoplastic resin foam Description Manufacturing method for thermoplastic resin foam, mold for molding the same, and thermoplastic resin foam
- the present invention relates to a thermoplastic resin for producing a thermoplastic resin foam by filling a mold cavity with a melt of a thermoplastic resin containing a foaming agent, and then expanding the cavity to foam the thermoplastic resin.
- the present invention relates to a method for producing a foam, and a mold for molding a thermoplastic resin foam used in the method.
- the present invention also relates to a lightweight thermoplastic resin foam having high compression rigidity and bending rigidity in the thickness direction.
- the thickness of a non-foaming skin layer is controlled. It is known how to change the expansion speed.
- the cavity is enlarged at the speed VI from the time when the filling is completed to the time T1, and then from the time T1 to the time T2. In between increases the cavities at a slow speed V3.
- thermoplastic resin foam As a molding method using a mold for molding thermoplastic resin foam, which expands the cavity of the mold, after filling the cavity with molten thermoplastic resin containing a foaming agent, the cavity is rapidly measured.
- a method of obtaining a foam molded article by forcibly enlarging the product is described in Japanese Patent Publication No. 51-84224 and Japanese Patent Application Laid-Open No. Hei 6-198668.
- the cavity is made smaller than the final shape, a thermoplastic resin containing a foaming agent is filled into the cavity, and the cavity is then expanded to the size of the final product, and the foam is expanded.
- the conventional method for producing a thermoplastic resin foam has a problem that it is difficult to obtain a foam having a high expansion ratio, for example, having a heat expansion of 5 times or more.
- Another problem is that only a fixed cell diameter can be obtained, and the diameter of the cell is as large as several mm or more. If the conditions are inappropriate, only hollow molded products can be obtained.
- the present invention has been made in view of the above-described problems of the prior art, and has as its object to solve the above problems, to obtain a high-magnification foam, and to obtain a cell having a desired diameter. It is intended to provide a method for producing a thermoplastic resin foam capable of producing a thermoplastic resin foam having a desired shape having particularly fine cells, and a mold for molding a thermoplastic resin foam used in the method. And to.
- Japanese Unexamined Patent Publication No. Hei 10-230528 discloses that a supercritical carbon dioxide or nitrogen is used as a foaming agent, and that an unfoamed portion having a good surface appearance and an integrated unfoamed portion is provided on the surface layer.
- a method for producing a foam having fine cells having closed cells having a uniform average cell density is described.
- Japanese Patent Application Laid-Open No. 08-108440 discloses that the cell structure has (a) a ratio of the size in the direction perpendicular to the surface of the foam plate to the size in the direction parallel to the foam plate of 2.5 to 2.5. (B) The percentage of cells whose size in the direction parallel to the plane of the foam plate is 500 m or less is 70% or more.
- a polyolefin resin foam plate is described in which the ratio of the compressive strength in the direction perpendicular to the surface of the foam plate to the compressive strength in the direction parallel to the surface of the foam plate is 2 or more, and the expansion ratio is 5 to 20 times. I have.
- this polyolefin resin foam plate a mixture of polyolefin resin, a chemical foaming agent, and a cross-linking agent is pressurized by a mold having opposed parallel inner surfaces, and heated to a temperature higher than the decomposition temperature of the chemical foaming agent. Then, the distance between the molding dies is increased, and the polyolefin resin is manufactured by a method of expanding only in a direction perpendicular to the inner surface when pressurized. In this method, the cell structure was flattened to achieve both low density and high compression rigidity.
- the manufacturing method of Japanese Patent Application Laid-Open No. H10-230528 is an injection molding method, the obtained foam has a fine and uniform independent cell structure, although it has a shape adaptability. Therefore, it has poor compressive strength and poor shock absorption against large impact force, and it is necessary to increase the density in order to obtain high physical properties, so that the weight of the foam molded product is heavy, the insulation performance is low, etc. There was a problem.
- the foam molded article of Japanese Patent Application Laid-Open No. H08-108440 has a weak bending strength because it has a single-layer structure of only a foam layer, and has a small deformation limit because of an independent cell. Due to the manufacturing method described above, there is also a problem that only a plate-shaped molded product can be obtained. In addition to the cost increase due to the use of the chemical foaming agent, unreacted and decomposed products of the chemical foaming agent remain in the foam, resulting in discoloration of the foam, generation of odor, Food hygiene problems o
- another object of the present invention is to provide a thermoplastic resin having high compression rigidity and bending rigidity in the thickness direction, light weight, excellent heat insulation and shock absorption, and having no residual chemical foaming agent. To provide a foam. Disclosure of the invention
- thermoplastic resin foam according to the first invention is a method for producing a thermoplastic resin melt containing a foaming agent in a mold cavity.
- the method of producing a thermoplastic resin foam by expanding the resin after filling and expanding the same, the filling of the resin after completion of filling the molten resin containing the blowing agent into the container is completed.
- the feature is to extend the tee to the final cavity expansion range.
- thermoplastic resin foam In the method for producing a thermoplastic resin foam according to the second invention, after filling a melt of a thermoplastic resin containing a foaming agent into a mold cavity, the resin is foamed by expanding the cavity.
- the method for producing a thermoplastic resin foam by heating after the filling of the molten resin containing the blowing agent into the cavity is completed, the cavity is maintained in the shape at the time of filling, and the average temperature of the molten resin in the cavity is reduced.
- the method for producing a thermoplastic resin foam according to the third invention is an embodiment of the first method for producing a thermoplastic resin foam, and comprises the steps of: (a) providing a molten resin containing a foaming agent into a cavity; It is characterized by including a step of keeping the time cavity in the shape at the time of filling, and a step of expanding the cavity to a final cavity expansion width after a predetermined time.
- the method for producing a thermoplastic resin foam according to the fourth invention is one mode of the second method for producing a thermoplastic resin foam, and comprises a method for producing a thermoplastic resin foam after a predetermined time after completion of filling of a molten resin containing a foaming agent.
- the first cavity enlargement process to enlarge the cavity to a predetermined amount less than the final cavity enlargement range, and the second stage to enlarge the cavity to the final enlargement range after stopping the cavity enlargement for a predetermined period of time It is characterized by including a step of expanding the abundance.
- the method for producing a thermoplastic resin foam according to the fifth invention is characterized in that, in the method for producing a thermoplastic resin foam according to the first or third invention, the expansion rate of the cavities in the step of expanding the cavities to the final expansion width is reduced. 2 to 5 mm / sec, and in the method for producing a thermoplastic resin foam according to the second or fourth invention, the expansion rate of the cavity in the first cavity expansion step is 2 S mm Z seconds. It is a characteristic.
- the method for producing a thermoplastic resin foam according to the sixth invention is the method for producing a thermoplastic resin foam according to the second, fourth or fifth invention, wherein the expansion rate of the cavities in the second cavity expansion step is 5 or more. 11 O mm Z seconds.
- the method for producing a thermoplastic resin foam according to the seventh invention is directed to the method for producing a thermoplastic resin foam according to any one of the first to sixth inventions, wherein the blowing agent does not react with an inert gas, that is, the resin. It is a characteristic gas.
- the forward direction refers to the direction in which the moving piece moves toward the gate portion of the cavity such that it reduces the cavity, and therefore, (51) in FIG. 4 (b) Direction.
- the retreat direction refers to the direction in which the moving piece moves away from the gate portion of the cavity so as to enlarge the cavity, and therefore refers to the direction (52) in Fig. 4 (b).
- thermoplastic resin foam molding die for producing a thermoplastic resin foam by expanding the resin by enlarging the viscosity
- a movable piece that can move back and forth in the thickness direction of the cavity (31) is provided on the movable die.
- a peripheral cavity space (32) is formed between the peripheral surface (33) and the cavity body space (34) between the front end surface of the moving piece and the cavity facing surface (35). It is characterized by having a shape that forms
- the peripheral cavity space (32) may be an integral cylindrical shape, and its cross-sectional shape may be a polygon such as a square or a circle.
- the movable piece (221a) provided on the movable die (22a) forms a bottomed cylindrical cavity (31) having a concave cross section in the advance / retreat direction when it is most advanced.
- the bottomed cylindrical cavity (31) is a peripheral cavity space (32) between the outer peripheral surface of the movable piece (221a) and the peripheral cavity (33), and the front end face of the movable piece (221a). And a cavity body space (34) between the cavity and the facing surface (35).
- the mold for molding a thermoplastic resin foam according to the ninth invention is the mold for molding a thermoplastic resin foam according to the eighth invention, wherein the length (t5) of the peripheral cavity space (32) in the reciprocation direction is ca. It is characterized in that it is larger than the width (t3) of the body body space (34) in the forward and backward directions.
- the length (t5) of the peripheral cavity space (32) of the bottomed cylindrical cavity (31) having a concave cross section in the retreating direction is (t5) of the cavity main body space (34). It is preferable that the width is larger than the width (t3).
- thermoplastic resin foam molding die according to the tenth aspect of the present invention is the thermoplastic resin foam molding die according to the eighth or ninth aspect of the present invention, wherein the length of the peripheral cavity space (32) in the forward and backward directions is different from that of the eighth or ninth aspect.
- T5 is characterized by being 50% to 70% of the final cavity enlargement width (t6).
- the length (t5) of the peripheral cavity space (32) of the bottomed cylindrical cavity (31) having a concave cross section in the forward and backward directions is:
- the final cavity width (t6) shown in FIG. 4 (c) is preferably 50 to 70%, more preferably 60 to 65%.
- the peripheral portion of the obtained thermoplastic resin foam does not follow the mold shape, and has a desired shape. May not be obtained. If the above-mentioned length (t5) is larger than 70% of the final cavity enlargement width (t6), the obtained thermoplastic resin foam may be wrinkled, which may impair the appearance of the product.
- the mold for molding a thermoplastic resin foam according to the eleventh aspect of the present invention is the mold for molding a thermoplastic resin foam according to the eighth, ninth or tenth aspect of the present invention, wherein the width (t4) of the peripheral cavity (32) is provided. Is 2 to 4 times the width (t3) of the cavity body space (34).
- the width (t4) of the peripheral cavity space (32) is 2 to 4 times, preferably 2.7 to 3.5 times the width (t3) of the cavity body space (34). It is.
- the width (t4) of the peripheral cavity space (32) is smaller than twice the width (t3) of the cavity main body space (34), the peripheral portion of the obtained thermoplastic resin foam will have a gold content. There is a possibility that the desired shape cannot be obtained without following the mold shape. If the width (t4) of the peripheral cavity (32) is larger than four times the width (t3) of the cavity body space (34), the thermoplastic resin foam will be deformed if cooling is insufficient and the desired shape is obtained. May not be obtained. Insufficient cooling can drastically reduce productivity. In addition, foaming of the thermoplastic resin in the peripheral cavity (32) may be insufficient.
- thermoplastic resin used in the present invention is particularly limited.
- polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-propylene-gen copolymer, ethylene-vinyl acetate copolymer, polybutene Olefin resin such as chlorinated polystyrene, polystyrene, styrene-butadiene-styrene copolymer, styrene-isoprene-styrene resin, polymethyl acrylate
- Acrylic resins such as ethylene-ethylene acrylate copolymer, chlorinated resins such as polyvinyl chloride, fluorinated resins such as polyfluorinated styrene, 6-nylon, 6 6—Nylon, 12—Polyamide resin such as Nylon, Polyethylene phthalate, Polyester resin such as Polyethylene phthalate, ABS resin, Polycarbonate , Polyacetal, polyphenylene sulfide, polyetheretherketone
- those having a melt tension or an elongational viscosity suitable for foaming are preferred.
- polyethylene, polypropylene, polystyrene, ABS resin, polyvinyl chloride, etc. are preferably used. Is done.
- polyethylene, polypropylene and the like a finely crosslinked resin having an adjusted extensional viscosity characteristic is preferable.
- the “melting point” is defined as a temperature at which a resin changes from a fluid state to a non-fluid state.
- the melting point is determined by the resin as follows. Crystalline resins such as polyethylene, polypropylene, polyacetyl, and polybutylene terephthalate are available from JIS.
- the melting temperature T pm measured by K 7 121 be the melting point.
- the melting point is the glass transition temperature Tmg measured according to JISK7121.
- vinyl chloride is a crystalline resin
- its melting temperature T pm is close to its thermal decomposition temperature, and molding is performed at a melting temperature T pm or less.
- the melting point of the crystalline resin in which the molding is performed at a melting temperature of T pm or less has a melting point of [T pm ⁇ 30 ° C.].
- amorphous resin molded at a glass transition temperature of T mg or lower has a melting point of [glass transition temperature T mg—30 ° C].
- the “average temperature of the resin” is defined as the average value of the temperature in the thickness direction of the filling resin layer in the mold cavity.
- the temperature in the thickness direction of the filled resin layer is not particularly limited, but is preferably the temperature at the center of the mold gate portion and the tip of the resin layer, that is, at the center of the layer thickness. is there.
- Examples of the method of determining the temperature of the molten resin filled in the mold include a method of installing an infrared temperature sensor in the mold to measure the temperature of the filled resin layer, and a method of determining the temperature of the filled resin by CAE injection flow analysis. A method of calculating the temperature of the fat layer by calculation and the like can be mentioned.
- keeping the cavity at the time of filling and “stopping the expansion of the cavity” mean a state where the moving piece is substantially stopped, and the moving speed of the moving piece is 0.1 I. mm Z seconds or less.
- the speed of expansion of the moving piece is preferably 0 mmsec.
- the foaming agent is not particularly limited, and organic and inorganic thermal decomposition type chemical foaming agents or physical foaming agents can be used.
- chemical foaming agents azo compounds, hydrazide compounds, nitroso compounds, semihydrorubazide compounds, hydrazo compounds, tetrazole compounds, ester compounds, bicarbonates, charcoal
- azodicarbonamide ADCA
- isoptyronitrile AZDN
- benzenesulfonylhydrazo (0BSH)
- dinitropentamethylentramine DPT
- azobisisoptyronitrile AIBN
- P-toluenesulfonhydrazide TSH
- potassium azodicarboxylate Ba-AC
- non-reactive gases such as carbon dioxide, nitrogen, argon, neon, helium, and oxygen. These may be used alone or in combination of two or more.
- the method of enlarging the mold cavity is not particularly limited, but as shown in Figs. 2 and 3, the hydraulic mechanism of the injection molding machine or the external hydraulic device and hydraulic screws Examples include a method in which the moving piece of the mold is moved in the direction in which the cavity is enlarged, and a method in which the cavity is enlarged by using the mold opening mechanism of the injection molding machine as shown in FIGS.
- the “primary cavity expansion width” in the second, fourth and fifth inventions is not particularly limited as long as it is equal to or smaller than the final cavity expansion width (t6).
- the width is preferably 3.0 times or less of the width (t3), particularly 6.5 mm or less. If this first-order cavity enlargement is too large, the cell membrane may be broken and many small cells may merge into one large cell.
- the “first-order cavity expansion speed” in the second, fourth, and fifth inventions, and the “enlargement speed up to the final cavity expansion” in the first, third, and fifth inventions are preferably 0. ⁇ / Per second, more preferably 2-5 mm Z seconds. If the cavity expansion rate is too slow, only foam with large cells can be obtained. If the enlargement speed is too fast, the mold and resin surface separate once, The cavities in the process When the movement is stopped, the resin surface is re-transferred to the mold surface, which may cause a problem that the appearance of the molded product surface deteriorates.
- the holding time from immediately after the completion of the resin filling to the start of the cavity expansion is determined by the resin temperature at the time of filling, the mold temperature, and the like, but is preferably 2 to 20 seconds. More preferably, it is 2 to 15 seconds. If the holding time is too long, the skin layer covering the surface of the resin becomes thick and the thickness of the substantial foam layer becomes thin, so that only a foam having a low expansion ratio may be obtained.
- the holding time from immediately after the completion of the filling of the resin to the start of the expansion of the primary cavity is preferably 0.1 to 11 seconds, more preferably 0.5 to 5 seconds.
- the stop time of the cavity expansion between the first cavity expansion process and the second cavity expansion process is preferably 0.5-30 seconds, more preferably 3-20 seconds. If the stop time is too short, the cell membrane may be broken and the cells may coalesce into one large cell, as in the case of the large amount of cavity expansion in the first cavity expansion process. There is. If the stop time is too long, the cooling of the resin proceeds and the elongation tension of the resin becomes larger than the foaming pressure.Therefore, the foam does not foam to the desired expansion amount or the surface differs from the mold shape. Irregularities may occur.
- the “second-order cavity expansion rate” in the second, fourth and sixth inventions is preferably 0. ⁇ ⁇ sec, more preferably 5 lOmmZsec. If the expansion speed of the cavity is too slow, the cooling of the resin proceeds during the expansion of the cavity, and the elongation tension of the resin becomes larger than the foaming pressure. Irregularities different from the mold shape on the surface
- a first invention is directed to a thermoplastic resin foam in which a foamed inner layer portion and two surface layer portions sandwiching the foamed inner layer portion are molded into a body.
- the surface layer has a thickness of 0.1 to 3.0 mm and has a non-foamed structure or a foamed structure having a cell diameter of 10 m or less, preferably 5 ⁇ m or less.
- the average cell diameter of the cells in the direction parallel to the surface is 6.0 mm or less, the cells communicating in the direction perpendicular to the surface is 70% or more, and the average density of the molded foam
- the present invention provides a thermoplastic resin foam characterized by having a foamed structure of 0.2 Og / cm 3 or less.
- Direction perpendicular to the surface refers to the direction perpendicular to the surface of the sandwich-like foam, that is, the thickness direction of the foam
- direction parallel to the surface refers to the direction perpendicular to the surface of the foam. It refers to the direction parallel to, that is, the direction perpendicular to the thickness direction.
- the cell wall of the foamed inner layer has a rib structure in the thickness direction.
- the cell shape in the cross section in the direction parallel to the plane is not particularly limited, but a honeycomb shape is preferable for improving the compressive strength. With such a foamed structure, it is possible to achieve both high rigidity against compression in the thickness direction and low density by using continuous cells.
- a tensile force acts on the surface layer (al) on the front side, and a compressive force acts on the surface layer (a2) on the back side.
- a foam inner layer (b) the foam has a two-layer surface layer (a) with high rigidity.
- each surface layer is 0.1 to 3.0 mm, and preferably 0.3 to 1.2 mm from the viewpoint of improving bending strength and foam molding. If the thickness of the surface layer portion is too thin, the rigidity of the surface layer portion itself becomes low, so that it is difficult to obtain a desired bending strength. If it is intended to obtain a molded product having a surface layer thickness of 3.0 mm or more, it is difficult to increase the expansion ratio of the inner layer of the foam, so that the average density of the foam increases. In order to obtain a foam having a high average density, the foam does not foam to a desired amount of expansion of the cavity or irregularities different from the mold shape are generated on the surface.
- the average cell diameter in the direction parallel to the surface should be 6.0 mm or less in order to secure the compressive strength in the direction perpendicular to the surface, but if the contact area of the compressed material is small, for example,
- the thickness is preferably 4.0 mm or less.
- the cell diameter is 6.0 mm or more, or if the contact area of the compact is small, the number of ribs contributing to the improvement of the compressive strength is reduced, so that sufficient compressive strength cannot be obtained.
- Average cell diameter refers to an average value of cell diameters in a direction parallel to the surface measured at a cross section parallel to the surface at the center in the thickness direction of the foam inner layer portion of the foam. The measurement is performed with a magnifying microscope. The measurement range is 5 mm square when the average cell diameter is 100 / zm or less, and 15 mm square when the average cell diameter exceeds 100 // m and l mm or less. If the average cell diameter exceeds l mm, it shall be 50 mm square, and the average value of any 30 cells in each range shall be calculated.
- the percentage of cells communicating in the direction perpendicular to the plane should be 70% or more. If it is less than 70%, the compressive strength in the direction perpendicular to the surface decreases.
- the continuous cell ratio of 70% or more means that the value obtained by measuring the continuity of the cells by the air pycnometer method (ASTM D 2856) is 70% or more. However, in this measurement, the apparent density was measured with the surface layer and the foamed inner layer integrated, and the measurement of the actual volume of the sample by the air pycnometer method separated the surface layer and the foamed inner layer. Perform in the state.
- a thirteenth invention provides a foam in which the thermoplastic resin of the first invention is a polypropylene resin
- the compressive strength in the direction perpendicular to the surface is 1. OMPa or more, the compressive modulus in the direction perpendicular to the surface is 0.025 GPa or more, the bending strength is 1. OMPa or more, and
- An object of the present invention is to provide a polypropylene resin foam characterized in that the average density of the molded foam is 0.20 gcm 3 or less.
- the polypropylene resin is not particularly limited, and is generally a homopolymer, a random copolymer, a block copolymer, a general polypropylene, a metal-containing polypropylene, or a polypropylene having a long-chain branch. It also includes those obtained by graphene polymerization of pyrene and other components, and these may be used alone or in combination of two or more.
- the compressive strength was measured at a compression speed of a thickness X 0.1 mmZ in the thickness direction of the sample using a test piece consisting of only the foamed inner layer portion with the surface layer removed.
- the fourteenth invention is directed to a thermoplastic resin foam in which a foamed inner layer and a two-layer surface layer sandwiching the foamed inner layer are molded into a body.
- the surface layer has a thickness of 0.1 mm to 3.0 mm and has a non-foamed structure or a foamed structure with a cell diameter of 10 zm or less, preferably 5 ⁇ or less.
- the average cell diameter of cells in the direction parallel to the plane is 4.0 mm or less, and the flattening ratio, that is, the ratio of the cell diameter in the vertical direction to the cell diameter in the direction parallel to the plane (the former Z)
- Thermoplastic resin foam characterized by having a foam structure in which cells having 2 to 6 are 65% or more and the average density of the molded foam is 0.12 g Z cm 3 or less It provides the body.
- this foam has the flat cell structure as described above, the cell wall in the thickness direction is thick and the cell wall in the plane direction is thin.
- the thick cell wall in the thickness direction has high rigidity against compression in the thickness direction, and the thin cell wall in the surface direction allows for a large cell volume, enabling high rigidity and high magnification foaming to be realized simultaneously. . Insulation is high due to the independent cell structure.
- the foamed inner layer when the average cell diameter in the direction parallel to the cell surface exceeds 4. 0 mm, if the aspect ratio exceeds 6, or the average density of the foam is 0. 1 2 g Z cm 3 If it does, the foam will have poor thermal insulation. When the flatness is lower than 2.0, or when the flatness is 2 to 6 is lower than 65%, sufficient compressive strength cannot be obtained.
- the fifteenth invention is directed to a thermoplastic resin foam in which a foamed inner layer portion and two surface layer portions sandwiching the foamed inner layer portion are molded into a body.
- Thermal conductivity is less than 0.070 WZmK
- compressive strength in the direction perpendicular to the surface is 0.25 MPa or more
- compressive modulus in the direction perpendicular to the surface is 0.004 GPa or more
- the bending strength is 1.
- any one of the first to fifteenth aspects when a chemical foaming agent is used as the foaming agent, a residue of the chemical foaming agent substantially exists in the obtained foam.
- the present invention provides a polypropylene resin foam characterized in that it is not.
- residue refers to both unreacted and decomposed products of chemical blowing agents.
- the decomposition product of the chemical blowing agent is, for example, in the case of azodicarbonamide (ADCA), HDCA, perazole, sialic acid, isocyanuric acid, shamride, ammonium cyanate, urea and the like.
- substantially no residue of the chemical foaming agent means that the residue is 50 ppm or less when a component analysis of the foam is performed by IR.
- thermoplastic resin foam according to the 12th to 16th inventions can be produced, for example, by the method according to the 2nd or 4th invention.
- FIG. 1 is a schematic view showing an example of an injection molding apparatus used in a method for producing a thermoplastic resin foam according to the present invention.
- FIG. 2 is a horizontal sectional view showing a state before the mold cavity is enlarged.
- FIG. 3 is a horizontal cross-sectional view showing a state after the cavities of the mold shown in FIG. 2 have been enlarged.
- FIG. 4 is a horizontal sectional view showing a mold for molding a thermoplastic resin foam according to the present invention.
- FIG. 5 is a horizontal sectional view showing another cavity enlarging means.
- FIG. 6 is a horizontal sectional view showing a state after the cavities are enlarged by the cavities enlarging means shown in FIG.
- FIG. 7 is a graph showing the relationship between the cavity expansion speed and time in the method for producing a thermoplastic resin foam according to the present invention.
- FIG. 8 is a side view showing the obtained foam.
- FIG. 9 is an explanatory diagram of the force generated when the thermoplastic resin foam of the present invention is bent.
- FIG. 10 is a photograph showing a cross section of the thermoplastic resin foam obtained in Example 7.
- FIG. 11 is a photograph showing a cross section of the thermoplastic resin foam obtained in Example 8.
- Fig. 12 is a graph showing the relationship between the cavity expansion rate and time in a conventional method for producing a thermoplastic resin foam.
- FIG. 13 is a horizontal sectional view showing a conventional mold for molding a thermoplastic resin foam.
- FIG. 1 is a schematic view showing an example of an injection molding apparatus.
- (1) is an injection molding machine
- (11) is a cylinder for plasticizing and kneading the resin of the molding machine (1)
- (12) is near the rear end of the cylinder (11).
- (13) is a hopper provided on the pressure-resistant chamber (12)
- (14) is a carbon dioxide gas cylinder used as a foaming agent.
- (141) is a pressure regulating valve provided in the line (142), and (121), (122), (123) and (124) are valves.
- (2) is an injection mold composed of a fixed mold (21) and a movable mold (22).
- Polypropylene (HMS-PP manufactured by Monte U-JPO; melting point: 127) is charged into the hopper (13) as a thermoplastic resin, the valve (122) is opened, and the resin is pressurized. One (12) was fed. After that, the valves (122), (123) and (124) are closed, and carbon dioxide gas whose pressure is adjusted to 5.5 MPa by the pressure adjusting valve (141) is passed through the valve (121) to the pressure-resistant chamber (121). 12).
- the pressure of the carbon dioxide gas was kept at 5.5 MPa and the temperature was kept at 45 ° C for 2 hours, and the carbon dioxide gas was dissolved in the thermoplastic resin.
- thermoplastic resin As a method of dissolving an inert gas under high pressure in a thermoplastic resin, there are a method of dissolving an inert gas in a molten thermoplastic resin and a method of dissolving an inert gas in a solid thermoplastic resin. However, either method may be adopted or both may be used in combination. Examples of a method of dissolving an inert gas under high pressure in a molten thermoplastic resin include a method in which the inert gas is mixed into the resin in a cylinder through a vent provided in the middle of the injection cylinder (11). Can be In this case, pressure sealing is performed with a molten thermoplastic resin.
- Examples of the method for dissolving an inert gas under high pressure in a solid-state thermoplastic resin include the following methods.
- thermoplastic resin in a pellet or powder state in advance inside a high-pressure container or the like
- the inert gas may be supplied from the gas cylinder (14) directly to the injection cylinder (11), or may be supplied under pressure using a plunger pump (not shown).
- thermoplastic resin was supplied from the pressure-resistant chamber (12) to the cylinder (11) set at 190 ° C via the valve (124). After that, the thermoplastic resin accumulated in the measuring section near the front end of the cylinder (11) is passed through the runner section (5) and the gate section (4) as shown in Fig. Injected into Viti (3).
- the movable mold (22) includes a moving piece (221) that can move forward and backward in the thickness direction of the cavity, and a wedge piece (222) that can move up and down.
- the hydraulic cylinder (223) connected to the hydraulic device (224) moves up and down. Then, as shown in FIG. 2, when the wedge piece (222) descends, the cavity (3) is reduced, and as shown in FIG. 3, when the wedge piece (222) rises, the cavity (3) becomes smaller. Is expanded.
- FIG. 4 shows an example of the mold according to the present invention.
- an initial cavity (31) is provided between the fixed mold (21a) and the movable mold (22a), and the movable piece (221a) of the movable mold (22a) is provided.
- the end is provided in the cavity (31) so as to be able to advance and retreat in the thickness direction ((51) or (52)) of the cavity.
- the initial cavity (31) has a bottomed cylindrical shape with a concave cross section in the forward and backward directions. Accordingly, as shown in FIG. 4 (b), when the molten resin is filled in the initial cavity (31), the bottom having a concave section in the advancing and retreating direction comprising the main body (41) and the cylindrical peripheral part (42).
- a cylindrical filling resin layer (40) is formed.
- the central part of the filling resin layer (40) foams following the retreat of the moving piece (221a).
- a foam (4) having a desired shape is formed.
- the cylindrical peripheral portion (42) of the filled resin layer (40) is maintained at a high temperature.
- the expansion of the cavities (31) makes it easier to manufacture foam (4).
- FIGS. 5 and 6 are explanatory views showing another example of the means for enlarging the cavity (3).
- the wedge pieces (222), the hydraulic device (224), and the hydraulic cylinder (223) as in the case of the cavity (3) shown in FIGS. )
- the opening and closing device for the mold (2b) instead of the wedge pieces (222), the hydraulic device (224), and the hydraulic cylinder (223) as in the case of the cavity (3) shown in FIGS.
- Fig. 4 shows a state in which the moving piece (221b) advances with the movable mounting plate (15) and the cavity (3) is reduced.
- Fig. 5 shows a state in which the moving piece (221b) is moved to the movable mounting plate (15). It retreats along with 15) and shows that the cavity (3) is expanded.
- FIG. 7 shows the relationship between the speed of expansion of the cavity and the time in the method for producing a thermoplastic resin foam according to the present invention.
- the first cavity expansion process that is, during the time from the beginning to T1
- the cavity expansion speed V1 and at the time T1
- the expansion of the cavity is stopped.
- the cavity enlargement process that is, the cavity is enlarged at the cavity enlargement speed V2 from time T2 to time T3.
- the holding time is 2 seconds, 9 seconds, and 22 seconds, respectively.
- the wedge piece (222) is raised by the hydraulic cylinder (223), the moving piece (221a) is retracted 12 mm, and the cavity ( 31) was expanded to include the final cavities.
- the cavity expansion speed of cavity (31) was S mmZ seconds.
- the average temperature of the molten resin when the moving piece (221a) is retracted is controlled by filling the resin into the initial cavity (31) and then maintaining the cavity in the shape at the time of filling for a predetermined time. did.
- the temperature at the time of cavity enlargement of 190 ° C. in Table 1 described below is a temperature under the condition that the time for keeping the cavity in the shape at the time of filling is 0 second.
- thermoplastic resin foam was cooled in the cavity (31) for 240 seconds, the mold (2) was opened, and the foam (4) was taken out.
- Table 1 shows the observation results of the obtained foam.
- the cell size was fine when the average temperature of the resin at the time of expanding the cavities was 120 ° C and 150 ° C. .
- the average temperature of the resin at the time of enlargement of the resin exceeds the range of [melting point + 30 ° C], such as 180 ° C and 190 ° C, the cell size may be large.
- large cavities were observed inside the thermoplastic foam.
- the average temperature of the resin at the time of enlargement was 150 ° C. and 180 ° C., the smoothness was excellent.
- thermoplastic resin foam does not expand to the desired shape, and a smooth foam can be obtained. Did not. Further, even at the average temperature of the resin of 190 ° C. when the cavity was enlarged, the thermoplastic resin foam did not expand to a desired shape, and a smooth foam could not be obtained.
- the initial cavity (31) where the width (t3) of the cavity body space (34) is 3 mm is filled with the molten polypropylene resin, and then the cavity (31) is removed.
- the shape at the time of filling was maintained for 0.5 seconds, and when the average temperature of the resin reached 185 ° C, the wedge piece (222) was raised by the hydraulic cylinder (223), and the moving piece (221a) was moved. It was retracted (4 mm) to the middle position.
- the expansion speed of the cavity (31) in the first cavity expansion process was 5 mmZ seconds and 0 s .
- thermoplastic resin foam was cooled for 360 seconds, the mold (2) was opened, and the foam (4) was taken out.
- Table 2 shows the observation results of the obtained foam.
- the average temperature of the resin at the start of the first cavity expansion step was within the range of [melting point to melting point + 60 ° C].
- the temperature at the center of the resin in the thickness direction at the start of the second cavity enlargement step was 170 ° C., 150 ° C., and 120 ° C.
- the cell size was fine.
- the expansion of the cavity was not stopped between the first and second cavity expansion processes, and the temperature in the center of the resin in the thickness direction at the start of the second cavity expansion process did not increase.
- the temperature was 190 ° C., a cavity was formed in the center of the obtained thermoplastic resin foam molded article, and cells in the portion below the cavity were coarse.
- the thermoplastic resin foam did not expand to a desired shape, and a smooth foam could not be obtained.
- the moving piece (221a) is removed when the average temperature of the resin filled in the initial cavity (31) reaches 195, 180, and 125 ° C. Except for the retraction, the same operation as in the first cavity enlargement step of Example 2 was performed.
- Table 3 shows the observation results of the obtained foam.
- the average temperature of the resin was 180 ° C. and 125 when the primary cavity was expanded. In the case of C, the cell size was fine.
- the average temperature of the resin when expanding the cavity is 195 ° C [melting point + 60 ° C. Under conditions exceeding the range of [C], the cell size was coarse and a hollow portion was observed at the center.
- the average temperature of the resin at the time of the first cavity enlargement was 195 ° C and 180 ° C, the smoothness was excellent.
- the average temperature of the resin at the time of the primary cavity expansion falls below the above range, such as 125 ° C, the thermoplastic resin foam will have the desired shape. Did not expand, and a smooth foam could not be obtained.
- Table 4 shows the observation results of the obtained foam.
- the movement of the cavity is stopped until the temperature in the center of the resin in the thickness direction reaches 160 ° C, and the enlargement speed of the cavity (31) is increased to 1, 10 and ZO. Except for mmZ seconds, the same operation as in the second cavity enlarging process of Example 2 was performed.
- Table 5 shows the observation results of the obtained foam.
- the cell size was fine when the secondary cavity expansion rate was 1 OmmZ seconds.
- the appearance was excellent when the second cavity expansion speed was 1, 10 mmZ seconds. Furthermore, when the secondary cavity expansion speed was 10 or 20 mmZ seconds, a foam molded article having excellent smoothness was obtained.
- the width (t3) of the cavity body space (34) in the reciprocation direction shown in Fig. 4 (a) is 3 mm
- the width (t4) of the peripheral cavity space (32) is shown.
- the initial cavity (31) having the length (t5) of the cavity (32) in the forward and backward directions of 0, 5, and 15 mm the molten material of the thermoplastic resin is filled, and the initial cavity (31) is filled.
- the same operation as in the first cavity enlargement step of Example 2 was performed except that the moving piece (221a) was retracted when the average temperature of the resin charged in the parentheses reached 180 ° C.
- Table 6 shows the thickness (t7) at the left side of the foam (4), the thickness (t2) from the gate portion to the lower center, and the thickness (t8) at the right side.
- the wedge piece (222) is raised again by the hydraulic cylinder (223), and the moving piece (221a) is retracted to the final cavity expansion width of 2 O mm.
- the expansion speed of the cavity (31) was 15 mm, sec.
- the thermoplastic resin foam was cooled in the cavity (31) for 120 seconds, the mold (2) was opened, and the foam (4) was taken out. .
- thermoplastic resin foam has an inner foam layer (b) and two surface layers (a) sandwiching it. ) And are integrally formed.
- the holding time before starting the primary cavity expansion is set to 2 seconds, and the cavity expansion speed in the primary cavity expansion process is increased.
- a foam was obtained by performing the same operation as in Example 7 except that the length was 3 mm, second.
- the retention time before starting the primary cavity expansion is 2 seconds
- the cavity expansion speed in the primary cavity expansion process is 3 mmZ seconds
- the primary cavity expansion is performed.
- the holding time until the first cavity expansion is started is set to 11 seconds, and the cavity expansion in the first cavity expansion process is performed.
- the large speed is set to l O mmZ seconds, and the first cavity enlargement process and the The suspension time of the cavity expansion during the secondary cavity enlargement process is set to 3 seconds, and the moving piece (221a) is retracted to the final cavity enlargement width of 30 mm in the secondary cavity enlargement process, and the cavity ( A foam was obtained in the same manner as in Example 7, except that the enlargement speed in (31) was 5 mm / sec.
- thermoplastic resin foam has an inner foam layer (b) and two surface layers (a) sandwiching it. ) And are integrally formed.
- the holding time until the first cavity expansion is started is 7 seconds, and the cavity expansion speed in the first cavity expansion process is increased.
- the length of time for stopping the expansion of the cavity between the first and second cavity enlargement steps is set to 1 second, and the moving piece (221a ) was retracted to the final cavity expansion width of 17 mm, and the same operation as in Example 7 was performed, except that the expansion speed of the cavity (31) was 5 mm, second, to obtain a foam.
- the holding time until the first cavity expansion is started is set to 10 seconds, and the cavity expansion in the first cavity expansion process is performed.
- the speed is set to 1 O mm Z second, and the first cavity enlargement process and
- the stop time of the expansion of the cavity during the secondary cavity enlargement process is set to 0.5 seconds, and the moving piece (221a) is retracted to the final cavity enlargement width of 17 mm in the secondary cavity enlargement process. Then, the same operation as in Example 7 was performed except that the expansion speed of the cavity (31) was set to ⁇ sec, to obtain a foam.
- the present invention has the following effects.
- thermoplastic resin foam According to the method for producing a thermoplastic resin foam according to the first and third inventions, it is possible to produce a foam having a uniform and fine cell diameter.
- thermoplastic resin foam according to the second and fourth inventions it is possible to produce a foam having a high magnification and a uniform cell diameter.
- thermoplastic resin foam according to the fifth invention it is possible to produce a foam having a good dimensional accuracy, a smooth and excellent appearance, and a uniform and fine cell diameter.
- thermoplastic resin foam According to the method for producing a thermoplastic resin foam according to the sixth aspect of the invention, it is possible to produce a foam having good dimensional accuracy, smoothness and excellent appearance, high magnification, and a uniform and fine cell diameter.
- thermoplastic resin foam according to the seventh aspect of the invention, since the foaming power is high and the resin can be uniformly dissolved in the resin, a high-quality foam with stable quality can be produced.
- thermoplastic resin foam molding die it is possible to produce a foam having a desired shape even in the peripheral portion.
- the resin temperature in the peripheral portion can be maintained at a higher temperature than the resin temperature in the moving piece portion. It is possible to manufacture foam with high magnification and uniform and various cell diameters because it is possible to stably produce foam and to be able to change the expansion timing of the moving mold in various ways. Is possible.
- thermoplastic resin foams according to the first and second inventions have extremely high compression and bending stiffness, are lightweight, and have excellent heat insulating properties.
- thermoplastic resin foams according to the fourteenth and fifteenth inventions are excellent in lightness and heat insulation, and have compression and bending stiffness.
- thermoplastic resin foam according to the sixteenth aspect of the present invention has no residual chemical foaming agent, and is applicable to food applications.
- the thermoplastic resin is polypropylene, it has excellent recyclability, and is used for food containers, heat insulating building materials, housing building materials, and automotive parts. Preferred applications are possible. Industrial applicability
- the present invention provides a thermoplastic resin foam of a desired shape having a high magnification and a cell having a desired diameter, particularly having fine cell cells. Further, the present invention provides a thermoplastic resin foam having extremely high compression and flexural rigidity, light weight, and excellent heat insulation.
Landscapes
- Injection Moulding Of Plastics Or The Like (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2000635519 DE60035519T2 (de) | 1999-08-30 | 2000-08-25 | Verfahren zur herstellung eines thermoplastischen schaumes und schaeumwerkzeug dafuer |
EP00955050A EP1226918B1 (en) | 1999-08-30 | 2000-08-25 | Production method for thermoplastic resin foam and molding mold therefor |
CA 2383270 CA2383270C (en) | 1999-08-30 | 2000-08-25 | Process for producing foamed body of thermoplastic resin, mold for forming same and foamed body of thermoplastic resin |
US10/069,717 US7195815B1 (en) | 1999-08-30 | 2000-08-25 | Process for producing foamed body of thermoplastic resin, mold for forming same and foamed body of thermoplastic resin |
US11/075,737 US7833445B2 (en) | 1999-08-30 | 2005-03-10 | Process for producing foamed body of thermoplastic resin |
US11/075,810 US20050181085A1 (en) | 1999-08-30 | 2005-03-10 | Process for producing foamed body of thermoplastic resin, mold for forming same and foamed body of thermoplastic resin |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
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JP24378699 | 1999-08-30 | ||
JP11/243786 | 1999-08-30 | ||
JP11/266031 | 1999-09-20 | ||
JP26603199A JP3320690B2 (ja) | 1999-09-20 | 1999-09-20 | 熱可塑性樹脂多孔体 |
JP2000/89142 | 2000-03-28 | ||
JP2000089142 | 2000-03-28 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
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US11/075,810 Division US20050181085A1 (en) | 1999-08-30 | 2005-03-10 | Process for producing foamed body of thermoplastic resin, mold for forming same and foamed body of thermoplastic resin |
US11/075,737 Division US7833445B2 (en) | 1999-08-30 | 2005-03-10 | Process for producing foamed body of thermoplastic resin |
Publications (2)
Publication Number | Publication Date |
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WO2001015882A1 true WO2001015882A1 (fr) | 2001-03-08 |
WO2001015882A8 WO2001015882A8 (fr) | 2002-04-11 |
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PCT/JP2000/005776 WO2001015882A1 (fr) | 1999-08-30 | 2000-08-25 | Procede de production pour mousse de resine thermoplastique, moule de moulage prevu a cet effet et mousse de resine thermoplastique |
Country Status (6)
Country | Link |
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US (3) | US7195815B1 (ja) |
EP (1) | EP1226918B1 (ja) |
CA (1) | CA2383270C (ja) |
DE (1) | DE60035519T2 (ja) |
ES (1) | ES2290049T3 (ja) |
WO (1) | WO2001015882A1 (ja) |
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- 2000-08-25 EP EP00955050A patent/EP1226918B1/en not_active Expired - Lifetime
- 2000-08-25 ES ES00955050T patent/ES2290049T3/es not_active Expired - Lifetime
- 2000-08-25 US US10/069,717 patent/US7195815B1/en not_active Expired - Fee Related
- 2000-08-25 CA CA 2383270 patent/CA2383270C/en not_active Expired - Fee Related
- 2000-08-25 WO PCT/JP2000/005776 patent/WO2001015882A1/ja active IP Right Grant
- 2000-08-25 DE DE2000635519 patent/DE60035519T2/de not_active Expired - Lifetime
-
2005
- 2005-03-10 US US11/075,810 patent/US20050181085A1/en not_active Abandoned
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2001088235A (ja) * | 1999-09-20 | 2001-04-03 | Sekisui Chem Co Ltd | 熱可塑性樹脂多孔体 |
CN100430201C (zh) * | 2003-07-24 | 2008-11-05 | 日东电工株式会社 | 生产聚合物泡沫体的方法及聚合物泡沫体 |
EP3881998A1 (en) * | 2020-03-20 | 2021-09-22 | King Steel Machinery Co., Ltd. | Molding method for operating molding device |
US11780129B2 (en) | 2020-03-20 | 2023-10-10 | King Steel Machinery Co., Ltd. | Molding method for operating molding device |
Also Published As
Publication number | Publication date |
---|---|
CA2383270A1 (en) | 2001-03-08 |
EP1226918A1 (en) | 2002-07-31 |
US7195815B1 (en) | 2007-03-27 |
ES2290049T3 (es) | 2008-02-16 |
DE60035519D1 (de) | 2007-08-23 |
WO2001015882A8 (fr) | 2002-04-11 |
US20050179158A1 (en) | 2005-08-18 |
US20050181085A1 (en) | 2005-08-18 |
US7833445B2 (en) | 2010-11-16 |
EP1226918B1 (en) | 2007-07-11 |
EP1226918A4 (en) | 2002-10-16 |
DE60035519T2 (de) | 2008-03-13 |
CA2383270C (en) | 2011-01-04 |
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