WO2024090280A1 - Matériau en feuille multicouche et procédé de production associé - Google Patents

Matériau en feuille multicouche et procédé de production associé Download PDF

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Publication number
WO2024090280A1
WO2024090280A1 PCT/JP2023/037451 JP2023037451W WO2024090280A1 WO 2024090280 A1 WO2024090280 A1 WO 2024090280A1 JP 2023037451 W JP2023037451 W JP 2023037451W WO 2024090280 A1 WO2024090280 A1 WO 2024090280A1
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WIPO (PCT)
Prior art keywords
resin
sheet material
base resin
laminated sheet
filler particles
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PCT/JP2023/037451
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English (en)
Japanese (ja)
Inventor
恭一 豊村
豊 竹澤
知行 古川
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Dic株式会社
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Publication of WO2024090280A1 publication Critical patent/WO2024090280A1/fr

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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
    • 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
    • B29C44/12—Incorporating or moulding on preformed parts, e.g. inserts or reinforcements
    • 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
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • 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
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • B29C45/26—Moulds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material

Definitions

  • This disclosure relates to a laminated sheet material and a method for manufacturing the same.
  • Laminated resin sheets have a wide range of applications, such as exterior materials for various industrial products, interior materials for automobiles, sound-absorbing materials, heat-insulating materials, cushions, and even surface materials for applications that reproduce a specific texture, such as artificial skin.
  • laminated resin sheets with foam layers, such as foams or foam sheets are useful because they have excellent texture, sound-absorbing properties, heat-insulating properties, and flexibility.
  • Patent Document 1 JP Patent Publication 2022-105688 discloses a method for manufacturing a foam laminate sheet.
  • This method for manufacturing a foam laminate sheet includes a lamination step of laminating a plurality of foam sheets to form a laminate, and a thermocompression step of thermocompressing the laminate at a temperature equal to or higher than the softening point and equal to or lower than the melting point of the plurality of foam sheets constituting the laminate.
  • the foam sheet raw material when the foam sheet raw material is a foam sheet having a skin layer on both surfaces, it may include a step of dividing the foam sheet raw material into two foam sheets having a skin layer only on one surface, or a step of dividing the foam sheet raw material into two foam sheets having a skin layer only on one surface and one or more foam sheets having no skin layer.
  • a foam sheet is usually formed with a bubble-free skin layer on both surfaces of the sheet in the process of forming a composition that is a raw material for the foam into a sheet, but it has been pointed out that this skin layer is hard due to its high density, which leads to a decrease in cushioning properties and ability to follow fine irregularities. Due to this problem, it has been disclosed that in order to ensure cushioning properties and conformability to uneven surfaces, the skin layer may be divided and removed by splitting or other processes, and only the core portion without the skin layer may be used as the foam sheet.
  • Patent Document 2 JP Patent Publication 2021-053945 discloses a method and an apparatus for manufacturing a foamed resin molded product.
  • a cavity formed on the separation surface between a first mold and a second mold is filled with a foamed resin, and then the volume of the cavity is increased to foam the foamed resin, which is called a core-back method.
  • Patent Document 2 describes that the core-back method is known as a method for molding a foamed resin molded product by filling a mold with a resin layer containing a foaming agent, the mold having a variable cavity volume.
  • the foamed resin filled in the mold is cooled from the contact surface with the mold to form a skin layer, and then the volume of the cavity is expanded when the temperature of the foamed resin in the cavity reaches an appropriate temperature, thereby forming a core layer with a bubble structure inside the skin layer.
  • Patent Document 3 JP 2021-187039 A discloses a method for molding a foamed resin sheet. This method for molding a foamed resin sheet employs core-back molding, in which the mold is retracted after shaping to expand the mold space.
  • the foamed resin sheet in a molten state is sandwiched between a pair of dies, each of the dies is brought into contact with the foamed resin sheet, and after a predetermined time has passed, each of the dies is retracted while vacuum suction is applied.
  • the foamed resin sheet in a molten state is sandwiched between a pair of dies, each of the dies is brought into contact with the foamed resin sheet, and after the surface of the foamed resin sheet is hardened, each of the dies is retracted while vacuum suction is applied.
  • the foamed resin sheet in a molten state is sandwiched between a pair of dies, each of the dies is brought into contact with the foamed resin sheet, and after the core-back is not performed immediately, but after a predetermined time has passed. Therefore, after the dies are brought into contact with the foamed resin sheet, the temperature of the surface of the foamed resin sheet decreases with the passage of time, the surface hardens, and a so-called skin layer is formed. In this state, the foamed resin sheet and the dies are kept in close contact with each other by vacuum suction, and the bubbles of the foamed resin sheet are sufficiently expanded by the core-back, and the thickness is also sufficiently expanded.
  • a skin layer may be formed on both sides of the foam, etc.
  • a process of manufacturing and then laminating the foam, etc. is required, which reduces productivity.
  • it may be necessary to remove the skin layer from the foam, etc. which reduces productivity. Therefore, it is desired to provide a laminated sheet material that is highly flexible in the thickness direction and highly productive, and a manufacturing method thereof.
  • This disclosure has been made in consideration of the above-mentioned circumstances, and its purpose is to provide a laminated sheet material that is highly flexible in the thickness direction and highly productive, and a method for manufacturing the same.
  • the laminated sheet material comprises: A resin sheet material; A foam layer laminated on the resin sheet material; a skin layer laminated adjacent to the foam layer, The base resin of the skin layer and the foam layer contains a thermoplastic resin,
  • the foam layer is An internal space formed between the resin sheet and the skin layer;
  • a plurality of column portions extending from the skin layer to the resin sheet along a thickness direction, The area ratio of the cross section of the column portion in a cross section perpendicular to the thickness direction of the foamed layer is 10% or more and 60% or less.
  • the present disclosure provides a method for producing the laminated sheet material described above, A melting step of melting a base resin containing a thermoplastic resin; an impregnation step of impregnating the base resin with a supercritical fluid of carbon dioxide or nitrogen to obtain a foamable base resin; and a molding step of injecting the foamable base resin into a mold in which a resin sheet material has been set in advance, and molding the base resin by a core-back molding method.
  • a method for producing a laminated sheet material includes: A melting step of melting a base resin containing a thermoplastic resin; an impregnation step of impregnating the base resin with a supercritical fluid of carbon dioxide or nitrogen to obtain a foamable base resin; A molding step of injecting the foamable base resin into a mold in which a resin sheet material has been set in advance, and molding the foamable base resin by a core-back molding method, the base resin includes filler particles having a surface that is poorly compatible with the thermoplastic resin; The content of the filler particles in the base resin is 0.5% by mass or more and 30% by mass or less, The filler particles have an average particle size on a volume basis of 5 ⁇ m or more and 100 ⁇ m or less.
  • This disclosure makes it possible to provide a laminated sheet material that is highly flexible in the thickness direction and highly productive, as well as a method for manufacturing the same.
  • FIG. 2 is a cross-sectional view of the laminated sheet material according to the embodiment.
  • FIG. 2 is an explanatory diagram of an injection molding apparatus for implementing the manufacturing method according to the present embodiment.
  • FIG. 4 is an explanatory diagram of a dispersion state of filler particles in a base resin in a base layer.
  • FIG. 2 is an explanatory diagram of the structure of a filler particle.
  • FIG. 2 is a cross-sectional view illustrating a structure of a mold.
  • FIG. 11 is an explanatory view of a state in which the second mold is relatively separated from the first mold.
  • FIG. 13 is an explanatory diagram of a state in which a resin sheet material is set in a mold.
  • FIG. 2 is an explanatory diagram of the state immediately after a foamable base resin is supplied to a mold.
  • FIG. 2 is an explanatory diagram of a state in which a mold to which a foamable base resin has been supplied is in a core-back state.
  • 1 is an image of a cross section of a laminated sheet material observed with an optical microscope. This is an image of the cross section taken along the line XI-XI in FIG. 10 and observed with an optical microscope. This is an image obtained by performing mapping processing on the image shown in FIG.
  • FIG. 2 is an explanatory diagram (cross-sectional view) of the structure of a column portion in a foam layer.
  • FIG. 13 is an explanatory diagram (cross-sectional view) of a state in which a column portion of a foam layer is bent.
  • FIG. 1 shows a cross-sectional view of a laminated sheet material 100 according to this embodiment. First, an overview of the laminated sheet material 100 and its manufacturing method will be described.
  • the laminated sheet material 100 includes a resin sheet material 1, a foam layer 20 laminated on the resin sheet material 1, and a skin layer 4 laminated adjacent to the foam layer 20.
  • the base resin of the skin layer 4 and the foam layer 20 contains a thermoplastic resin.
  • the foam layer 20 has an internal space 21 formed between the resin sheet material 1 and the skin layer 4, and a plurality of column portions 22 extending from the skin layer 4 to the resin sheet material 1 along the thickness direction.
  • the area ratio of the column portions 22 in a cross section perpendicular to the thickness direction of the foam layer 20 is 10% or more and 60% or less.
  • the laminated sheet material 100 can be manufactured, for example, by the following manufacturing method. That is, the laminated sheet material 100 can be manufactured by a manufacturing method including a melting step of melting a base resin containing a thermoplastic resin, an impregnation step of impregnating the base resin with a supercritical fluid of carbon dioxide or nitrogen to form a foamable base resin, and a molding step of injecting the foamable base resin into a mold 7 in which a resin sheet material 1 has been set in advance, and molding by a core-back molding method.
  • FIG. 2 shows an example of an injection molding device 200 that realizes the manufacturing method according to this embodiment.
  • the laminated sheet material 100 and its manufacturing method are described in detail below.
  • the laminated sheet material 100 is used as a surface material for applications that reproduce a specific texture, such as exterior materials for various industrial products, interior materials for automobiles (exterior materials for the interior of automobiles), sound absorbing materials, heat insulating materials, cushions, and even artificial skin (exterior materials used in areas where it is desired to reproduce the texture of human skin).
  • the laminated sheet material 100 is used as an exterior material for an article.
  • the surface side (outer surface side) of the laminated sheet material 100 used as an exterior material may be simply referred to as the surface side or surface.
  • FIG. 1 shows a conceptual diagram illustrating the cross-sectional structure of a laminated sheet material 100.
  • the laminated sheet material 100 comprises a resin sheet material 1 and a base layer 2 on which a foam layer 20 and a skin layer 4 are laminated.
  • the resin sheet material 1, the foam layer 20, and the skin layer 4 are laminated in this order.
  • the resin sheet material 1 is a layer exposed on the surface side of the laminated sheet material 100.
  • the resin sheet material 1 is appropriately selected according to the design and feel required for the surface of the laminated sheet material 100.
  • the resin sheet material 1 is made of resin (for example, polyurethane), and is a synthetic leather with many air bubbles formed inside the sheet, a polyvinyl chloride sheet (so-called PVC leather), or the like.
  • resin sheet materials examples include "PARMIA (registered trademark)”, “REFLA (registered trademark)”, “ZUTTFIT (registered trademark)”, and “P-TOUCH (registered trademark)” manufactured by Toyo Cross Co., Ltd., "LOOMISH (registered trademark)”, “CHRONOS (registered trademark)”, “CARAVELL (registered trademark)” (synthetic leather), and “LE CARLE” manufactured by Kyowa Leather Co., Ltd., and “BEZANT (registered trademark)” manufactured by Komatsu Matere Co., Ltd.
  • the thickness direction of the laminated sheet material 100 (hereinafter sometimes simply referred to as the thickness direction) is the same as the thickness direction of the resin sheet material 1.
  • the substrate layer 2 is a layer of thermoplastic resin with the resin sheet material 1 supported on its surface side.
  • the substrate layer 2 is a layer that serves as a base or substrate for the resin sheet material 1.
  • the substrate layer 2 has a foam layer 20 disposed on the resin sheet material 1 side, and a skin layer 4 laminated on the foam layer 20 on the side opposite the resin sheet material 1 side.
  • thermoplastic resins that form the substrate layer 2 include polyvinyl chloride-based resins such as vinyl chloride; polyamide (nylon)-based resins such as nylon 6, nylon 66, nylon 11, and nylon 12; polyurethane-based resins; polyolefin-based resins such as polyethylenes such as low-density polyethylene and linear low-density polyethylene, polypropylene, and ethylene-vinyl acetate copolymers; fluororesins such as FEP, PFA, ETFE, and PTFE; polystyrene-based resins such as polystyrene, high-impact polystyrene, acrylonitrile-styrene copolymers, and ABS resins; cellulose-based resins such as cellulose acetate; and thermoplastic elastomers such as polyurethane-based thermoplastic elastomers, polyester-based thermoplastic elastomers, styrene-based
  • the base layer 2 contains at least one of these as the base resin in a total amount of 75% by weight or more and 100% by mass or less.
  • base resins polyolefin-based resins and thermoplastic elastomers are preferred from the viewpoint of superior flexibility in the thickness direction, and olefin-based thermoplastic elastomers are more preferred.
  • olefin-based thermoplastic elastomers include ethylene-based polymers, propylene-based copolymers, and butene-based copolymers.
  • More specific examples include copolymers of ethylene and an ⁇ -olefin having 3 to 20 carbon atoms, copolymers of ethylene and an ⁇ -olefin having 3 to 20 carbon atoms and a cyclic olefin, ethylene-based copolymers having various vinyl compounds as comonomers, such as styrene, vinyl acetate, (meth)acrylic acid, and (meth)acrylic acid esters, copolymers of propylene and an ⁇ -olefin having 4 to 20 carbon atoms, copolymers of propylene and an ⁇ -olefin having 4 to 20 carbon atoms and a cyclic olefin, and ethylene-based copolymers having various vinyl compounds as comonomers, such as styrene, vinyl acetate, (meth)acrylic acid, and (meth)acrylic acid esters.
  • the base resin preferably has a melt flow rate (hereinafter referred to as MFR) of 3.0 g/10 min or more and 8.0 g/10 min or less, measured in accordance with ASTM D1238 using a cylinder with an inner diameter of 9.550 mm and a standard die with a hole diameter of 2.095 mm and a hole length of 8.000 mm at a temperature of 190°C and a load of 2.16 kg.
  • MFR melt flow rate
  • the extrusion amount per unit time (MFR) measured using the above cylinder and die, with the base resin filled in the cylinder, at a temperature of 190°C, and the base resin extruded from the die at a load of 2.16 kg is preferably 3.0 g/10 min or more and 8.0 g/10 min or less.
  • the base resin of the base layer 2 may have base resin and filler particles P dispersed therein.
  • FIG. 3 shows a cross section of the base layer 2.
  • the content of the filler particles P in the base resin is, for example, 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and 30% by mass or less, preferably 20% by mass or less, and more preferably 10% by mass or less, relative to the total amount of the base resin and the filler particles P.
  • a gap Q is formed at least partially between the base resin and the filler particles P.
  • the maximum distance between the filler particles P and the base resin is 20% or more and 60% or less of the diameter of the filler particles P.
  • the formation of the gap Q may improve the insulation, heat storage, vibration damping, sound absorption, etc. of the laminated sheet material 100. If the compatibility between the base resin and the surface of the filler particles P is low, the gap Q is more likely to form.
  • the average particle diameter of the filler particles P on a volume basis is, for example, 5 ⁇ m or more and 500 ⁇ m or less.
  • the average particle diameter of the filler particles P may be a value measured by a laser diffraction particle size distribution measuring device.
  • filler particles P are resin beads, metal particles, and inorganic oxide particles.
  • metal particles are particles of metals such as iron, lead, copper, zinc, aluminum, nickel, and tin, or particles based on such metals.
  • iron (iron powder) or particles based on iron may be collectively referred to as iron particles hereinafter.
  • inorganic oxide particles are particles of titanium oxide, calcium carbonate, and silica. It is preferable that the filler particles P have a small specific heat. If the specific heat of the filler particles P is small, they are easily cooled in a short time and the gaps Q are easily formed.
  • the specific heat of the filler particles P is 1 kJ/(kg ⁇ K) or less, and even more preferable that it is 0.5 kJ/(kg ⁇ K) or less and 0.1 kJ/(kg ⁇ K) or more.
  • Iron particles are particularly preferable as filler particles P because they have a small specific heat, are excellent in the ability to form gaps Q, and can form a foamed layer in a short time.
  • the specific heat of iron is 0.435 kJ/(kg ⁇ K).
  • the filler particles P may be so-called coated particles that are coated with a coating material that has low compatibility with the base resin. That is, as shown in FIG. 4, the filler particles P may have a core particle P1 and a coating layer P2 formed of a coating material that covers at least a portion of the core particle P1, preferably the entire surface. Note that FIG. 4 shows a cross section of the filler particle P.
  • An example of a filler particle P as a coating particle is an iron particle such as ferrite that serves as a core particle P1, which is coated with a coating material that has low compatibility with the base resin (e.g., silicone-based resin, fluorine-based resin) to form a coating layer P2.
  • a coating material e.g., silicone-based resin, fluorine-based resin
  • the skin layer 4 is a layer of dense thermoplastic resin that contains almost no air bubbles. "Contains almost no air bubbles” means that there are no air bubbles or that there are only a very small number of air bubbles. "Contains a very small number of air bubbles” means that when the cross section is observed under an optical microscope (magnification 20x), the cross-sectional area of the air bubbles is 10% or less, preferably 5% or less, more preferably 1% or less, and even more preferably substantially 0% (not detectable). While the resin sheet material 1 is the front surface of the laminated sheet material 100, the skin layer 4 is the back surface of the laminated sheet material 100.
  • the foam layer 20 is a layer disposed between the resin sheet material 1 and the skin layer 4.
  • the resin sheet material 1 is laminated adjacent to one side of the foam layer 20.
  • the resin sheet material 1 is laminated adjacent to the side of the foam layer 20 opposite to the side facing the resin sheet material 1.
  • the foam layer 20 preferably has a thickness of 1 mm or more, preferably 2 mm or more, and 20 mm or less, preferably 10 mm or less.
  • the foam layer 20 may be a layer formed by laminating a first foam layer 31 arranged on the resin sheet material 1 side, a second foam layer 32 arranged on the skin layer 4 side, and an intermediate foam layer 30 arranged between the first foam layer 31 and the second foam layer 32.
  • the foam layer 20 may be a layer formed by laminating the first foam layer 31, the intermediate foam layer 30, and the second foam layer 32 in this order from the resin sheet material 1 side to the skin layer 4.
  • the foam layer 20 has a number of pillars 22 that extend from the skin layer 4 to the resin sheet material 1 along the thickness direction.
  • the pillars 22 are an internal structure of the foam layer 20 that extend along the thickness direction.
  • the pillars 22 traverse the intermediate foam layer 30 along the thickness direction, and the ends 22a, 22b are formed integrally with the first foam layer 31 and the second foam layer 32, respectively.
  • the intermediate foam layer 30 is a layer including an internal space 21 formed between the resin sheet material 1 and the skin layer 4.
  • the internal space 21 is a space formed between adjacent column sections 22. It is preferable that the thickness of the intermediate foam layer 30 in the thickness direction, i.e., the height of the column sections 22 in the thickness direction, is approximately 70% or more and 95% or less of the thickness of the foam layer 20.
  • the first foamed layer 31 and the second foamed layer 32 are sponge-like layers containing tiny air bubbles. As described above, the first foamed layer 31 and the second foamed layer 32 are formed integrally with the ends 22a and 22b of the column section 22, respectively. When viewed on a number basis, it is preferable that the air bubbles in the first foamed layer 31 and the second foamed layer 32 are 90% or less of 500 ⁇ m bubbles.
  • the cross-sectional area ratio of the column portion 22 in a cross section perpendicular to the thickness direction of the foam layer 20 is 10% or more and 60% or less. Note that the cross section perpendicular to the thickness direction of the foam layer 20 is a cross section at the middle position of the foam layer 20 in the thickness direction. In the case where the foam layer 20 includes an intermediate foam layer 30, it corresponds to a cross section at the middle position in the thickness direction of the intermediate foam layer 30.
  • thermoplastic resin layer that contains almost no air bubbles, such as the skin layer 4, or it is so underdeveloped that it is difficult to clearly distinguish it from the first foam layer 31.
  • the laminated sheet material 100 can be manufactured by a manufacturing method including a melting process, an impregnation process, and a molding process.
  • the laminated sheet material 100 is manufactured, for example, by an injection molding device 200 shown in FIG. 2.
  • the injection molding device 200 shown in Figure 2 includes an extruder 5 that performs a melting process for melting a base resin containing a thermoplastic resin, and an impregnation process for impregnating the base resin with a supercritical fluid of carbon dioxide or nitrogen to form a foamable base resin, and a mold 7 in which a resin sheet material 1 (see Figure 1) is set in advance and a molding process in which the foamable base resin is injected to form a laminated sheet material 100.
  • the mold 7 is connected to the downstream tip of the extruder 5.
  • the extruder 5 has a heat source (e.g., an electric heater) for melting the base resin including a thermoplastic resin, and is equipped with a cylinder 51 (barrel) that forms a processing space in which the base resin is impregnated with a supercritical fluid of carbon dioxide or nitrogen to form a foamable base resin, a screw 52 inserted into the cylinder 51 and extruding the resin toward the mold 7, a discharge port 53 provided at the downstream end of the cylinder 51 for supplying the foamable base resin to the mold 7, a supply port 54 provided upstream of the cylinder 51 for supplying the base resin to the processing space in the cylinder 51, a vent port 55 provided between the discharge port 53 and the supply port 54 in the cylinder 51, a hopper 61 that supplies the base resin to the supply port 54, and a supercritical gas supply device (gas cylinder 62 and pressure adjustment valve 63) that supplies the supercritical fluid from the vent port 55 into the cylinder 51.
  • a heat source e.g., an electric heater
  • raw materials (base resin and additives such as filler particles) fed into a hopper 61 are fed into the cylinder 51 through the feed port 54.
  • the base resin fed into the cylinder 51 is melted by heat supplied from the heat source of the cylinder 51 and extruded toward the mold 7 by the screw 52.
  • the base resin comes into contact with the supercritical fluid supplied from the vent port 55 and is impregnated with the supercritical fluid to become a foamable base resin (if the raw materials contain additives such as filler particles, it is called a foamable base resin kneaded product.
  • foamable base resin will be used to collectively refer to the case where the base resin is a foamable base resin kneaded product).
  • This foamable base resin is fed (injected) into the mold 7 in a molten state.
  • the mold 7 has a first mold 71 and a second mold 72 that form a molding space S (cavity) for molding the laminated sheet material 100.
  • a gate 79 that supplies the foamable base resin supplied from the discharge port 53 to the molding space S is formed in the first mold 71.
  • FIG. 5 shows a cross section of the mold 7.
  • the molding space S is formed when the first mold 71 and the second mold 72 are fitted together. As shown in the cross-sectional view of FIG. 6, the second mold 72 moves away from the first mold 71 relatively, so that the volume of the molding space S is expanded.
  • the laminated sheet material 100 is formed as follows:
  • the resin sheet material 1 is set in advance in the second mold 72.
  • the resin sheet material 1 is set so that its front side is in contact with the inner surface of the second mold 72.
  • the resin sheet material 1 is set so that it is perpendicular to the direction in which the second mold 72 moves relatively away from the first mold 71.
  • a molten foamable base resin 2A (which may contain additives such as filler particles) is supplied (injected) from the extruder 5 into the molding space S (see Figure 5), and the laminated sheet material 100 (see Figure 1) is core-back molded.
  • the second mold 72 slowly moves away from the first mold 71 relative to the first mold 71 (so-called core back), as shown in the cross-sectional view of FIG. 9.
  • the speed at which the second mold 72 moves away from the first mold 71 relatively is, for example, 0.2 mm/s to 0.6 mm/s.
  • a foam structure that will become the foam layer 20 is formed in the molten material 2A. This foam structure is produced when the supercritical fluid gas impregnated in the molten material 2A foams due to the reduced pressure in the molding space S as the second mold 72 moves away from the first mold 71 relatively.
  • the molten material 2A of the foamable base resin supplied into the molding space S is cooled by the first mold 71 and quickly cooled and solidified near the inner surface of the first mold 71. Therefore, a foam structure is not formed in the molten material 2A near the inner surface of the first mold 71.
  • the portion of the molten material 2A near the inner surface of the first mold 71 where a foam structure is not formed becomes the skin layer 4.
  • the molten material 2A of the foamable base resin supplied into the molding space S is kept warm by the resin sheet material 1 in the vicinity of the resin sheet material 1 and is prevented from being cooled by the second mold 72, so that the molten material 2A does not cool and solidify early.
  • a foam structure is formed in the molten material 2A in the vicinity of the resin sheet material 1. Therefore, a dense thermoplastic resin layer containing almost no air bubbles, such as the skin layer 4, is not formed between the resin sheet material 1 and the foam layer 20.
  • the base resin mixture in which the filler particles have been mixed or kneaded beforehand may be melted.
  • the filler particles may be mixed and dispersed in the base resin as a so-called master batch, in which the filler particles have been mixed in high concentration into the base resin beforehand.
  • the base resin and the master batch may be melted in a mixed state.
  • the filler particle content may be 0.5% by mass or more and 30% by mass or less.
  • FIG. 10 shows an example of an image of a cross section perpendicular to the surface (resin sheet material 1) of the laminated sheet material 100 produced by the above-mentioned production method.
  • the image shown in FIG. 10 was taken by observing this cross section with an optical microscope.
  • the structure of the cross section is similar to the structure described in the conceptual diagram shown in FIG. 1.
  • FIG. 11 shows a cross-sectional image taken along the line XI-XI of the laminated sheet material 100 shown in FIG. 10 (a cross-sectional view perpendicular to the thickness direction of the foamed layer 20, and an image of a cross-section of the central part of the foamed layer 20 in the thickness direction).
  • the image shown in FIG. 11 was obtained by observing the cross-section corresponding to the line XI-XI of the laminated sheet material 100 shown in FIG. 10 with an optical microscope.
  • the white areas are the pillars 22, and the rest is the internal space 21 (end 22b or second foamed layer 32).
  • the pillars 22 in FIG. 11 are highlighted by mapping using image processing.
  • the black and white shading in FIG. 11 is shown by filling in areas with a density of 50% or less with black.
  • the area of the black-filled region (the region with a density of 50% or less in the black and white shading of FIG. 11), i.e., the area ratio of the cross section of the column portion 22 in a cross section perpendicular to the thickness direction of the foam layer 20, is preferably 10% or more and 60% or less.
  • the laminated sheet material 100 As shown in Figs. 1 and 10, no skin layer is formed between the resin sheet material 1 and the foam layer 20. Therefore, the tactile sensation from the resin sheet material 1 side of the laminated sheet material 100 does not give the impression of a hard skin layer, but rather a natural softness. In other words, the laminated sheet material 100 has high flexibility in the thickness direction.
  • the manufacturing method of the laminated sheet material 100 described above does not require a step of removing a skin layer from the base layer 2 in order to make the laminated sheet material 100 highly flexible in the thickness direction. Therefore, the laminated sheet material 100 and its manufacturing method have high productivity.
  • the internal space 21 is likely to form a structure in which it communicates with the air bubbles in the first foamed layer 31 and the resin sheet material 1 via pores, etc.
  • the laminated sheet material 100 is compressed, the air G in the internal space 21 is likely to flow out from the internal space 21 to the outside via the first foamed layer 31 and the resin sheet material 1 (see FIG. 1).
  • the laminated sheet material 100 gives a tactile sensation due to the elastic force of the air spring of the internal space 21 immediately after touching the laminated sheet material 100, and a subsequent sinking tactile sensation as the air G escapes from the internal space 21.
  • a foam layer 20 including an internal space 21 and a column portion 22 is formed, so that the laminated sheet material 100 gives a slightly hard feel due to the resistance to the compressive force on the column portion 22 immediately after touching the laminated sheet material 100, followed by a melting-like feel at the moment when the column portion 22 bends in a direction intersecting the thickness direction (bending from the state of the column portion 22 shown in Figure 13 to the state of the column portion 22 shown in Figure 14), and then a soft elastic feel as the column portion 22 bends in a direction intersecting the thickness direction.
  • the above-mentioned tactile sensation provided by the laminated sheet material 100 can be adjusted by the thickness of the laminated sheet material 100, the foam layer 20, the intermediate foam layer 30 and each of the other layers, and the balance between the column portion 22 and the internal space 21 (for example, the cross-sectional area ratio of the column portion 22).
  • the thermal sensation (the sensation of warmth or coldness and the change in sensation over time) felt when touching the laminated sheet material 100 can be adjusted by adjusting the thermal insulation provided by the internal space 21 and the heat capacity of the filler particles P (see Figure 3) contained in the base resin.
  • the size of the gap Q (see FIG. 3) can be adjusted to adjust the timing at which the change in warmth caused by the heat capacity of the filler particles P is felt. Specifically, for example, if the filler particles P are of a large heat capacity such as iron, making the gap Q larger can delay the timing at which the warmth caused by heat entering and leaving the laminated sheet material 100 is felt.
  • the laminated sheet material 100 is excellent at adjusting the feel and warmth. Therefore, the laminated sheet material 100 is also suitable for applications such as expressing a comfortable feel or reproducing the feel of human skin (for example, as a material for artificial skin).
  • the laminated sheet material 100 when used as a material for artificial skin, when a magnetic material such as ferrite is used as the filler particles P, the laminated sheet material 100 can be heated by, for example, electromagnetic induction heating, to give the sensation of body heat.
  • the insulating properties of the internal space 21 and the heat storage properties of the filler particles P can make the laminated sheet material 100 give the sensation of warmth similar to that of human skin.
  • the laminated sheet material according to this embodiment will be described based on examples.
  • the laminated sheet described below was manufactured using an apparatus configuration similar to the injection molding apparatus described above.
  • Example 1 and 2 The laminated sheet materials according to Examples 1 and 2 were produced as follows.
  • an olefin-based thermoplastic elastomer manufactured by Dow Chemical Company an example of an ethylene- ⁇ -olefin-based copolymer, product name: Engage 8200
  • the filler particles soft ferrite manufactured by Powder Tech Co., Ltd. (product name: EF96, average particle size: 35 ⁇ m) was used.
  • the MFR of "Engage 8200" is 5.0 g/10 min (190° C., load 2.16 kg), and the density is 0.870 g/cm 3 .
  • the synthetic leather shown in Table 1 was placed as a resin sheet material in a mold with a cavity for forming the laminated sheet material, so that it was in contact with the surface of the mold.
  • the mold was a channel type (one gate).
  • a supercritical gas supplying device (TREXEL, model: T-100J) was used to supply the filler gas shown in Table 1 in a supercritical state to the molten material and impregnate the base resin to produce a foamable base resin kneaded material.
  • TREXEL supercritical gas supplying device
  • Example 1 carbon dioxide (CO 2 ) was used as the filler gas
  • Example 2 carbon dioxide (N 2 ) was used as the filler gas.
  • the amount of the filling gas (supercritical gas) impregnated into the base resin was 2% by mass relative to the base resin.
  • This foamable base resin mixture was then injected into a mold.
  • the initial temperature of the mold (the temperature before the foamable base resin mixture was injected) was 20°C.
  • the back pressure when injecting the foamable base resin mixture into the mold was 10 MPa, and the holding pressure was also 10 MPa.
  • the injection holding pressure time was 0.3 seconds.
  • the initial thickness of the cavity in the mold was set to 2.5 mm
  • the release distance in the core back was 4 mm
  • the release time (the time it takes to open the mold by the release distance) was 10 seconds.
  • Comparative Example 1 The laminated sheet material according to Comparative Example 1 differs from Example 1 in that no master batch was used as a raw material and no filler particles were contained in the expandable base resin kneaded product, but was otherwise manufactured in the same manner as Example 1.
  • the thickness (wall thickness) of the laminated sheet material according to Comparative Example 1 was 7.5 mm.
  • a cross section perpendicular to the surface was observed for each laminate sheet material.
  • a foam layer was observed that had multiple pillars extending from the skin layer to the resin sheet and an internal space formed between these pillars, which was an internal space formed between the resin sheet and the skin layer.
  • a honeycomb structure was formed in the region from the skin layer to the resin sheet, with fine, independent bubbles (approximately 500 ⁇ m in diameter or less).
  • the laminated sheet material according to the embodiment in which the pillar portion was observed was observed at a cross section perpendicular to the thickness direction of the foamed layer, at the cross section of the central part in the thickness direction of the foamed layer. That is, the foamed layer of each embodiment was cut at the central part in the thickness direction, and the exposed cut surface was photographed at a magnification of 20 times with an optical microscope (Microscope VHX-7000 manufactured by Keyence Corporation). The image of the cut surface was processed to divide the brightness (hereinafter referred to as "luminance") of the photographed image into 256 gradations from 0 to 255, and the occurrence frequency of each luminance was calculated, and a luminance value histogram of this image was obtained.
  • luminance brightness
  • the image was binarized in an automatic area measurement mode using 127 as the luminance threshold value, and the area ratio of the cross section of the pillar portion (resin) was obtained. Then, the area ratio of the cross section of the pillar portion 22 in this cross section was measured, and the area ratio of the cross section of the laminated sheet of Example 1 was 21%. Also, the area ratio of the cross section of the laminated sheet of Example 2 was 37%.
  • the hardness of the surface side (resin sheet material side) of each laminate sheet was measured. Hardness was measured using an automatic constant pressure loader (GS-610, manufactured by Tecrock Corporation) and A hardness was measured in accordance with JIS K 6253 (2012). The load during hardness measurement was 500 g and the load drop rate was 9 mm/s.
  • the hardness of the laminate sheets of Examples 1, 2 and Comparative Example 1 was 27.8, 27.7 and 46.3, respectively. Compared to the laminate sheet of Comparative Example 1, the laminate sheets of Examples 1 and 2 were more flexible in the thickness direction and achieved a softer feel. The laminate sheets of Examples 1 and 2 did not give the impression of a hard skin layer and gave a natural softness. More specifically, the feel of the laminated sheets of Examples 1 and 2 was a slightly hard feel immediately after touching the laminated sheet material from the resin sheet material side, followed by a slightly hard feel that crumbled as if it was melting, and then a soft, elastic feel.
  • This disclosure is applicable to laminated sheet materials and their manufacturing methods.
  • Resin sheet material 100 Laminated sheet material 2: Base layer 20: Foam layer 200: Injection molding device 21: Internal space 22: Column portion 22a: End portion 22b: End portion 2A: Melt 30: Intermediate foam layer 31: First foam layer 32: Second foam layer 4: Skin layer 5: Extruder 51: Cylinder 52: Screw 53: Discharge port 54: Supply port 55: Vent port 61: Hopper 62: Gas cylinder 63: Pressure regulating valve 7: Mold 71: First mold 72: Second mold 79: Gate G: Air P: Filler particle P1: Core particle P2: Coating layer Q: Gap S: Molding space

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne : un matériau en feuille multicouche présentant une flexibilité élevée dans le sens de l'épaisseur, tout en ayant une productivité élevée ; ainsi qu'un procédé de production dudit matériau en feuille multicouche. Ce matériau en feuille multicouche est pourvu d'un matériau en feuille de résine, d'une couche de mousse superposée sur le matériau en feuille de résine, et d'une couche de peau superposée de sorte à être adjacente à la couche de mousse ; la couche de peau et la couche de mousse comprennent une résine de matériau de base qui contient une résine thermoplastique ; la couche de mousse comprend un espace interne formé entre le matériau en feuille de résine et la couche de peau, et une pluralité de parties colonnes qui s'étendent de la couche de peau au matériau en feuille de résine dans le sens de l'épaisseur ; et le rapport de surface des coupes transversales des parties colonnes dans une coupe transversale de la couche de mousse - la coupe transversale étant perpendiculaire au sens de l'épaisseur - est compris entre 10 et 60 %.
PCT/JP2023/037451 2022-10-25 2023-10-16 Matériau en feuille multicouche et procédé de production associé WO2024090280A1 (fr)

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CN112745623A (zh) * 2019-10-31 2021-05-04 中国石油化工股份有限公司 用于制备聚丙烯塑木复合材料的组合物及其制得的复合材料和应用
CN113789035A (zh) * 2021-09-06 2021-12-14 北京工商大学 一种取向的pbt微纳孔泡沫材料及其制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04140199A (ja) * 1990-09-30 1992-05-14 Achilles Corp シャープな凹凸模様を有する装飾シート
JP2007106021A (ja) * 2005-10-14 2007-04-26 Hayashi Telempu Co Ltd 樹脂発泡成形体およびその製造方法
JP2007160736A (ja) * 2005-12-14 2007-06-28 Mazda Motor Corp 表皮材積層発泡樹脂成形品の成形方法及び成形装置
JP2007223104A (ja) * 2006-02-22 2007-09-06 Mitsuboshi Kaseihin Kk 自動車用内装部品及びその製造方法
JP2012000909A (ja) * 2010-06-18 2012-01-05 Kaneka Corp 熱可塑性エラストマー発泡成形体
JP2012020544A (ja) * 2010-07-16 2012-02-02 Sekisui Chem Co Ltd 射出発泡成形品
US20150038607A1 (en) * 2013-08-02 2015-02-05 Nike, Inc. Method and thermoplastic foamed article
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JP2019171871A (ja) * 2018-03-28 2019-10-10 国立大学法人京都大学 発泡樹脂成形品の製造方法、該方法に使用される熱可塑性樹脂組成物および発泡樹脂成形品
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CN113789035A (zh) * 2021-09-06 2021-12-14 北京工商大学 一种取向的pbt微纳孔泡沫材料及其制备方法

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