WO2011062141A1 - 樹脂発泡シート - Google Patents

樹脂発泡シート Download PDF

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Publication number
WO2011062141A1
WO2011062141A1 PCT/JP2010/070294 JP2010070294W WO2011062141A1 WO 2011062141 A1 WO2011062141 A1 WO 2011062141A1 JP 2010070294 W JP2010070294 W JP 2010070294W WO 2011062141 A1 WO2011062141 A1 WO 2011062141A1
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Prior art keywords
resin
foam sheet
polypropylene
resin composition
foamed
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PCT/JP2010/070294
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English (en)
French (fr)
Japanese (ja)
Inventor
正義 岩田
俊信 古木
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積水化成品工業株式会社
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Priority to CN201080051896.6A priority Critical patent/CN102612534B/zh
Publication of WO2011062141A1 publication Critical patent/WO2011062141A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/025—Polyolefin
    • 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
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/02—Cellular or porous
    • B32B2305/022—Foam
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/03—Extrusion of the foamable blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2389/00—Characterised by the use of proteins; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L89/00—Compositions of proteins; Compositions of derivatives thereof

Definitions

  • the present invention relates to a resin foam sheet formed by extruding and foaming a polypropylene resin composition with an extruder.
  • a resin foam sheet obtained by foaming a resin composition into a sheet has been widely used in applications where lightness and buffering properties are required.
  • the resin foam sheet formed with the polypropylene resin composition which has a polypropylene resin as a main component is widely used since it is comparatively cheap.
  • Such a foamed resin sheet is usually produced continuously by extruding and foaming a polypropylene resin composition, and not only a foamed resin layer single layer but also a non-foamed resin layer called a film layer on the surface.
  • This resin foam sheet is used as a glass sheet buffer sheet in the form of a sheet, and is also used as a raw material for producing a foam molded product having a three-dimensional structure such as a foam tray by a sheet molding method.
  • Patent Document 1 a polypropylene resin composition and a high melt tension polypropylene resin (hereinafter referred to as “HMS-PP”). It is described that a resin foam sheet having excellent moldability can be obtained by containing 50% by mass or more.
  • the resin foam sheet is molded into a foam tray or the like, the resin foam sheet is heated and softened, and vacuum molding is performed by adsorbing to a mold in which the tray shape is formed by negative pressure (evacuation).
  • a molding method called pressure air molding in which a resin foam sheet is pressed against a molding die with positive pressure is widely adopted.
  • the resin foam sheet is not in a uniform condition as a whole because it is performed to form irregularities on the resin foam sheet while gripping the periphery of the resin foam sheet, For example, if the thickness of the resin foam sheet is uneven, thin parts that are easily stretched due to stress are preferentially stretched. Depending on the case, appearance defects may occur in the molded product.
  • the present invention has been made in view of the above-described problems, and is intended to suppress fringes by an approach other than adjustment of extrusion conditions, and as a result, can be easily manufactured so that no fringes are seen.
  • the object is to provide a resin foam sheet.
  • the present inventors have found that the composition of the polypropylene resin composition to be used can be set to a predetermined value, and the present invention has been completed. It came to let you.
  • the present invention relating to a resin foam sheet is a resin foam sheet formed by extruding and foaming a polypropylene resin composition having a polypropylene resin component as a main component with an extruder.
  • the high melt tension polypropylene resin is contained so that the proportion of the polymer component contained is 20% by mass or more and less than 50% by mass.
  • the high melt tension polypropylene resin in the polymer component is set to a predetermined ratio, it is possible to make it difficult for the resulting resin foam sheet to have stripes when extruded and foamed by an extruder. Therefore, a margin is given to the extrusion conditions, and a high-quality resin foam sheet can be easily obtained. As a result, a homogeneous foamed resin sheet can be provided.
  • a general sheet forming method such as vacuum forming or pressure forming, there is a risk of causing an appearance defect or the like in the obtained molded product. Low resin foam sheet can be provided.
  • Sectional drawing which shows the structure of the resin foam sheet which concerns on this embodiment. Schematic which shows the structure of the manufacturing apparatus of the resin foam sheet which concerns on this embodiment. Sectional drawing which shows the structure of a confluence
  • the resin foam sheet 1 in this embodiment includes a non-foamed resin layer (surface layers 11 and 12) constituting the respective surfaces of the upper surface side and the lower surface side, and a foamed resin layer formed therebetween. 20 and a three-layer laminated structure. That is, the resin foam sheet 1 of this embodiment has non-foamed resin layers (surface layers 11 and 12) on both sides of the foamed resin layer 20.
  • the surface layers 11 and 12 are both formed in a non-foamed state by a polypropylene resin composition containing a polypropylene resin as a main component.
  • the upper surface layer 11 hereinafter also referred to as “first surface layer 11” and the lower surface layer 12 (hereinafter referred to as “second surface layer 12”) in FIG. ")
  • the foamed resin layer 20 is formed by extruding and foaming a polypropylene resin composition mainly composed of a polypropylene resin by a method described later.
  • the surface layers 11 and 12 are formed by coextruding a polypropylene resin composition for forming each of the surface layers 11 and 12 together with the polypropylene resin component for forming the foamed resin layer 20 by a method described later. It is.
  • the polypropylene resin composition used for forming the surface layers 11 and 12 and the foamed resin layer 20 is usually a composition suitable for each, those having different compositions are used.
  • the polypropylene-based resin composition used for forming the foamed resin layer 20 has a ratio of high melt tension polypropylene resin (HMS-PP) to the polymer component contained in a range from 20% by mass to less than 50% by mass. It is important that
  • HMS-PP molecules that have been cut or crosslinked by irradiation of active energy rays such as electron beams to form free-end long chain branches in the molecule, or free-end long chains in the molecule by chemical crosslinking are used. What formed the branch and formed high melt tension may be used. Moreover, what gave high melt tension by introduce
  • polypropylene resins other than HMS-PP examples include homopolypropylene resins (PP) consisting essentially of propylene components.
  • the polypropylene resin is HMS-PP or not can be determined not only by the difference in molecular structure as described above but also by its melt tension.
  • the high melt tension polypropylene resin is one having a melt mass flow rate (MFR) of 0.5 g / 10 min or more and 10 g / 10 min or less and a melt tension of 5 cN or more and 50 cN or less. Intended. This MFR was measured at a test temperature of 230 ° C. and a load of 21.18 N (2.16 kgf) in accordance with method A of JIS K7210 (1999). It can be measured as follows.
  • a polypropylene resin as a sample is accommodated in a cylinder with an inner diameter of 15 mm arranged in the vertical direction and heated at a temperature of 230 ° C. for 5 minutes to be melted.
  • a capillary die diameter: 2.095 mm, die length: 8 mm, inflow angle :
  • the measurement can be performed by extruding the molten resin from 90 degrees (conical).
  • the extruded string-like material can be measured by winding it around a tension detection pulley disposed below the capillary and then winding it using a winding roll.
  • the initial speed at the beginning of the take-up is 4 mm / s
  • the subsequent acceleration is 12 mm / s 2
  • the take-up speed is gradually increased.
  • the maximum tension until this “breaking speed” is observed can be measured as “melt tension”.
  • melt tension value measured by the above measurement does not reach the above value.
  • HMS-PP which defines the content in the polypropylene resin composition.
  • block copolymer and block PP mean that the melt tension value of a block copolymer having an olefin block and a polypropylene block does not reach the above value unless otherwise specified.
  • HMS-PP showing the melt tension value examples include those commercially available from Borealis under the trade names “WB130HMS”, “WB135HMS”, and “WB140HMS”.
  • a specific example of HMS-PP is commercially available from Basell under the trade name “Pro-fax F814”.
  • those commercially available from Nippon Polypro as trade names “FB3312”, “FB5100”, “FB7200”, and “FB9100” are also specific examples of HMS-PP.
  • the use of the product name “WB135HMS” manufactured by Borealis, in which free end long chain branches are formed in the molecule by chemical crosslinking improves the foaming degree when the foamed resin layer 20 is formed by extrusion foaming. This is preferable because it can be easily achieved.
  • the HMS-PP is contained in the polymer component contained in the polypropylene resin composition in a proportion of 20% by mass or more and less than 50% by mass. This is because, when the ratio is 50% by mass or more, the polypropylene-based resin composition is likely to generate stripes when extruded and foamed to produce a resin foam sheet.
  • the lower limit of HMS-PP is set to 20% by mass.
  • the content of HMS-PP is less than this, it becomes difficult to foam the polypropylene resin composition in a good state. This is because the selection range of the extrusion conditions for obtaining good products may be rather narrowed.
  • the content of HMS-PP in all polymer components is preferably 25% by mass or more and less than 50% by mass, and more preferably 30% by mass or more and 45% by mass or less.
  • the total amount of all the polypropylene resins including HMS-PP in the total polymer components of the polypropylene resin composition used for forming the foamed resin layer 20 is usually 80% by mass or more. Preferably, it is 90 mass% or more.
  • a polymer having a high compatibility with the polypropylene resin is suitable for use as a polymer component.
  • polyethylene resin ethylene-ethyl acrylate copolymer resin, ethylene-acetic acid
  • polyolefin resins such as vinyl copolymer resins, polybutene resins, and poly-4-methylpentene-1 resins
  • TPO polyolefin-based thermoplastic elastomers
  • the polypropylene resin composition used for forming the foamed resin layer 20 usually contains a component for foaming in addition to the polymer component as described above.
  • the foaming component include a gas component that is in a gaseous state at the extrusion temperature, a nucleating agent that serves as a nucleus when bubbles are formed by the gas component, and a gas that is thermally decomposed at the extrusion temperature. And thermal decomposition type foaming agent.
  • gas component examples include aliphatic hydrocarbons such as propane, butane, and pentane, nitrogen, carbon dioxide, and water. These gas components may be used alone or in combination.
  • nucleating agent examples include talc, mica, silica, diatomaceous earth, aluminum oxide, titanium oxide, zinc oxide, magnesium oxide, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, potassium carbonate, calcium carbonate, magnesium carbonate, and sulfuric acid.
  • examples include inorganic compound particles such as potassium, barium sulfate, and glass beads, and organic compound particles such as polytetrafluoroethylene.
  • This nucleating agent can be contained in the foamed resin layer forming material by, for example, a masterbatch method, and the nucleating agent is in any proportion within the range of 5% by mass or more and 50% by mass or less. By using the master batch dispersed in the matrix resin, it is possible to increase the effect exhibited with respect to the use amount of the nucleating agent.
  • thermal decomposition type foaming agent examples include azodicarbonamide, sodium hydrogen carbonate, a mixture of sodium hydrogen carbonate and citric acid, and the like.
  • the effect of the heat decomposable foaming agent is also improved by dispersing it in a matrix resin so as to be in any proportion within the range of 10% by mass or more and 50% by mass or less, and forming a master batch. be able to.
  • the polypropylene resin composition used for forming the foamed resin layer 20 can contain various additives in the same manner as the resin composition used for forming a general resin product, for example, an antioxidant. , An anti-aging agent, a processing aid and the like can be appropriately contained.
  • the resin foam sheet 1 according to the present embodiment is molded into a foam tray that is widely used as a buffer material for glass plates in the form of a sheet or as a display container for meat, fresh fish, and the like. In many cases, such as cases, it is required to suppress charging due to static electricity. Therefore, it is preferable to contain a nonionic antistatic agent in the polypropylene resin composition for forming the surface layers 11 and 12.
  • nonionic antistatic agent examples include alcohol antistatic agents, ether antistatic agents, ester antistatic agents, and ester / ether antistatic agents. Furthermore, examples of the nonionic antistatic agent include nitrogen-containing antistatic agents such as amine-based antistatic agents and amide-based antistatic agents. This nonionic antistatic agent is usually added to the polypropylene resin composition at a ratio of 0.5 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the polymer component contained in the polypropylene resin composition. Contained.
  • the alcohol-based antistatic agent examples include polyalkylene oxides such as polyethylene glycol (or polyethylene oxide) and poly (ethylene oxide) -poly (propylene oxide) block copolymers.
  • the degree of polymerization of the alkylene oxide is usually 1 or more and 300 or less (for example, 5 or more and 200 or less), preferably 10 or more and 150 or less (for example, 10 or more, 100). The following). More preferably, it is about 15 or more and 50 or less.
  • ether-based antistatic agent examples include polyoxyethylene alkyl ethers such as polyoxyethylene octyl ether, polyoxyethylene lauryl ether and polyoxyethylene cetyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether and the like. And polyoxyethylene alkylphenyl ether.
  • ester antistatic agent examples include many esters such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin, (poly) glycerin, pentaerythritol, sorbitan, sorbitol, sucrose, and esters of polyhydric alcohols and fatty acids.
  • esters such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin, (poly) glycerin, pentaerythritol, sorbitan, sorbitol, sucrose, and esters of polyhydric alcohols and fatty acids.
  • esters such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin, (poly) glycerin, pentaerythritol, sorbitan, sorbitol, sucrose, and esters of polyhydric alcohols and fatty acids.
  • examples thereof include glycerol
  • ester / ether antistatic agent examples include polyoxyethylene glycerin fatty acid esters such as polyoxyethylene glycerin stearate and polyoxyethylene glycerin oleate; polyoxyethylene sorbitan such as polyoxyethylene sorbitan stearate Fatty acid ester; Polyoxyethylene polyhydric alcohol fatty acid ester such as polyoxyethylene sucrose fatty acid ester. Examples thereof include polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil.
  • nitrogen-containing antistatic agent examples include polyoxyethylene alkylamines having an alkyl structure of 6 to 24 carbon atoms in the molecule, such as polyoxyethylene laurylamine; polyoxyethylene stearamide, etc.
  • fatty acids include saturated fatty acids (for example, saturated fatty acids having 6 to 24 carbon atoms such as capric acid, lauric acid, myristic acid, palmitic acid and stearic acid; unsaturated fatty acids such as oleic acid.
  • anionic antistatic agent in addition to this nonionic antistatic agent, anionic antistatic agent, cationic antistatic agent, amphoteric antistatic agent and polymer antistatic agent may be used in combination.
  • the agent include alkyl sulfonates, examples of the cationic low molecular weight antistatic agent include tetraalkylammonium salts, and examples of the amphoteric low molecular weight antistatic agent include alkyl betaine.
  • polymer antistatic agent examples include ionomers such as polyethylene oxide, polypropylene oxide, polyethylene glycol, polyester amide, and polyether ester amide, quaternary ammonium salts thereof, and polyether-polyolefin block copolymers ( And a copolymer of an olefin block and a hydrophilic block, such as a block copolymer of a polyether block and a polyolefin block).
  • ionomers such as polyethylene oxide, polypropylene oxide, polyethylene glycol, polyester amide, and polyether ester amide, quaternary ammonium salts thereof, and polyether-polyolefin block copolymers ( And a copolymer of an olefin block and a hydrophilic block, such as a block copolymer of a polyether block and a polyolefin block).
  • the polypropylene resin composition for forming the surface layers 11 and 12 preferably contains, together with the nonionic antistatic agent, a component that promotes bleedout of the nonionic antistatic agent.
  • a resin that is either ethylene- ⁇ -olefin copolymer or low-density polyethylene resin and has a crystallinity of 20% to 55% is particularly effective.
  • These ethylene- ⁇ -olefin copolymers and low-density polyethylene resins may be included singly or in combination in the polypropylene resin composition for forming the surface layers 11 and 12. . It is also possible to use one or more ethylene- ⁇ -olefin copolymers and one or more low-density polyethylene resins as a component for promoting bleedout of the nonionic antistatic agent.
  • the total amount of these is preferably 20% by mass or more, and 25% by mass or more in the polymer component of the polypropylene resin composition. More preferably.
  • the upper limit is usually about 40% by mass, and the total amount of these is preferably 35% by mass or less.
  • the degree of crystallinity in this ethylene- ⁇ -olefin copolymer or low-density polyethylene resin can be measured by JIS K7121: 1987 “Method for measuring transition temperature of plastic”. Specifically, using a differential scanning calorimeter (DSC) device “DSC6220 type” manufactured by SII Nanotechnology, about 7 mg of a sample is filled in a measurement container, and a nitrogen gas flow rate of 30 ml / min is 10 ° C./min. While the temperature rises (cools) at the rate of temperature rise (cooling), the point where the DSC curve leaves the baseline is the starting point of melting (crystallization), and the point where the DSC curve returns to the baseline again is the end point.
  • DSC differential scanning calorimeter
  • Crystallinity (%) (Heat of crystallization (mJ) / Heat of fusion of complete crystal (mJ)) ⁇ 100 (However, the complete crystal melting heat (theoretical value) is 285.7 mJ / mg.)
  • the polymer component of the polypropylene resin composition may be composed only of the HMS-PP and a component for accelerating the bleed-out of the nonionic antistatic agent.
  • Polypropylene resins other than the HMS-PP described as the forming material, and olefin resins and TPO having high affinity with the polypropylene resin can be added as appropriate.
  • this polypropylene-type resin composition comprises the surface of the resin foam sheet 1, it can contain the various additives for exhibiting the function with which this surface is equipped as needed. For example, it is possible to prevent the deterioration of the resin foam sheet 1 and the foam tray by containing a weathering agent and an anti-aging agent, or to improve slipperiness by containing a slip agent. Alternatively, it is possible to improve the appearance by coloring by adding a pigment.
  • the 1st surface layer 11 and the 2nd surface layer 12 do not necessarily need to make each thickness common, and the 1st surface layer 11 and the 2nd surface layer 12 are the same.
  • the blending content of the polypropylene resin composition used for forming the two surface layers 12 may be varied. For example, it is possible to add a pigment only to the side corresponding to the outside of the foaming tray, and to color the side corresponding to the inside of the foaming tray. Further, the nonionic antistatic agent or the like can be contained only on the side corresponding to the outer side of the foaming tray and not on the side corresponding to the inner side.
  • each layer of the first surface layer 11, the second surface layer 12, and the foamed resin layer 20 in the resin foam sheet 1 is not particularly limited, but the first surface layer 11 and the second surface layer are not limited.
  • the layer 12 usually has any thickness within the range of 50 ⁇ m to 150 ⁇ m.
  • the foamed resin layer 20 is usually formed to have any thickness within the range of 0.5 mm to 5.0 mm, and the density (apparent density) is 0.15 g / cm 3 to 0.6 g. / Cm 3 or less.
  • Such a resin foam sheet 1 can be manufactured by carrying out extrusion foaming of the polypropylene resin composition using an extruder generally used for manufacturing a resin foam sheet.
  • FIG. 2 is a schematic configuration diagram according to the apparatus for manufacturing a resin foam sheet
  • FIG. 3 is a cross-sectional view showing an internal state of the confluence mold (symbol XH) shown in FIG.
  • FIG. 4 shows a state in which the polypropylene-based resin composition is extruded and foamed, and shows a state indicated by a broken line A in FIG.
  • the resin foam sheet manufacturing apparatus shown in FIG. 2 includes two series of extruders: a first extruder 70 that is a tandem extruder and a second extruder 80 that is a single extruder. . Further, a merge mold XH into which the resin composition melt-kneaded in these extruders is merged, and an annular discharge hole for discharging the resin composition merged in the merge mold XH into a cylindrical shape A circular die CD is provided.
  • this manufacturing apparatus includes a cooling device CL for air-cooling the resin foam sheet discharged in a cylindrical shape from the circular die CD, and expanding the diameter of the cylindrical resin foam sheet into a cylindrical shape having a predetermined size. And a slitting device that cuts the resin foam sheet after passing through the mandrel MD along the extrusion direction and divides it into two sheets (not shown in FIG. 2: only the state of dividing vertically) And a take-up roller 92 for taking up the slit resin foam sheet 1 after passing the plurality of rollers 91.
  • a cooling device CL for air-cooling the resin foam sheet discharged in a cylindrical shape from the circular die CD, and expanding the diameter of the cylindrical resin foam sheet into a cylindrical shape having a predetermined size.
  • a slitting device that cuts the resin foam sheet after passing through the mandrel MD along the extrusion direction and divides it into two sheets (not shown in FIG. 2: only the state of dividing vertically)
  • a take-up roller 92 for taking
  • the first extruder 70 is for forming the foamed resin layer 20, and the upstream extruder (hereinafter also referred to as “upstream extruder 70 a”) is for forming the foamed resin layer 20.
  • upstream extruder 70 a the upstream extruder
  • a hopper 71 for introducing the polypropylene resin composition and a gas introduction part 72 for supplying gas components such as hydrocarbons into the cylinder are provided.
  • a polypropylene resin composition containing the gas component hereinafter also referred to as “foamable resin composition”
  • Extruder hereinafter also referred to as “downstream extruder 70b” is provided.
  • the second extruder 80 is for forming the first surface layer 11 and the second surface layer 12, and is a polypropylene-based resin composition (hereinafter referred to as a surface layer) for forming the surface layer in a non-foamed state.
  • the "non-foamable resin composition” is introduced from the hopper 81, and the non-foamable resin composition is melted and kneaded inside the cylinder and discharged to the joining mold XH.
  • the confluence mold XH includes a first resin flow path W1 that passes through the center from the right side to the left side of the front view of FIG. 3, and the first resin flow path.
  • a third resin flow path W3 for allowing the resin to flow into the first resin flow path W1 is formed.
  • the second resin flow path W2 is formed so that the resin composition can flow into the resin flow path W1 from an annular slit S1 opened in a wall surface forming the resin flow path W1.
  • the resin flow path W3 is connected to a tube P having an open end at the center of the first resin flow path W1, so that the resin composition can flow into the center of the first resin flow path W1. Is formed.
  • the first resin flow path W1 is connected to the first extruder 70 on the upstream side, and is connected to the circular die CD on the downstream side.
  • the second resin flow path W2 and the third resin flow path W3 is connected to the second extruder 80 via the distribution pipe D so that the non-foamable resin composition can flow from the second extruder 80.
  • the merge mold XH of the present embodiment is a circle having a triple structure of non-foamable resin composition / foamable resin composition / non-foamable resin composition on the downstream side of the first resin flow path W1.
  • a flow of columnar resin is formed, and these resins are provided so as to be supplied toward the circular die CD.
  • the circular die CD is fed in triple from the converging mold XH (“non-foamed resin composition” / “foamable resin composition” / “non-foamed resin composition”) from the center toward the outside.
  • the columnar resin composition flow is changed to a cylindrical flow so as to be co-extruded from the annular discharge hole.
  • a polypropylene resin composition used for forming the foamed resin layer 20 is introduced from the hopper 71 of the first extruder 70, and the surface of the second extruder 80 is There is a method in which a polypropylene resin composition for forming the layers 11 and 12 is charged, melt kneading at a temperature equal to or higher than the melting temperature of the resin is carried out in each extruder, and then co-extruded from the circular die CD.
  • Each resin composition may be introduced into the hopper after the individual components are brought into a homogeneous mixed state in advance, or may be separately introduced from the hopper and mixed in the extruder.
  • the gas component is press-fitted from the gas introduction part 72 provided in the upstream extruder 70a.
  • Mixing with molten resin is performed.
  • Co-extrusion from the circular die CD is performed by adjusting the foamable resin composition melt-kneaded by the upstream extruder 70a in the first extruder 70 to a temperature suitable for extrusion foaming by the downstream extruder 70b.
  • the non-foamable resin composition is adjusted to a temperature suitable for the formation of the first and second surface layers 11 and 12, and sent to the confluence mold XH. This can be implemented by previously forming a laminated structure of molten resin in the confluence mold XH.
  • the respective resin compositions merged in the merge mold XH are co-extruded from the annular discharge hole of the circular die CD, and the foamed resin layer 20 and the surface layers 11 and 12 are formed by the respective polypropylene resin compositions.
  • a cylindrical foam having a laminated structure with Thereafter, the foam is stretched in the circumferential direction along the outer peripheral surface of the mandrel MD larger in diameter than the discharge hole of the circular die CD and cooled, and the cooled foam is moved up and down with a cutting tool (not shown).
  • the belt-shaped resin foam sheet 1 is divided into two, and each is wound around a roll 92.
  • the polypropylene resin composition for forming the foamed resin layer 20 contains HMS-PP, it is extruded in a favorable foamed state.
  • the cylindrical foam causes an increase in thickness with an increase in the degree of foaming immediately after being discharged, and expands the apparent volume.
  • the foam does not expand in volume only in the thickness direction, but also expands in the circumferential direction. Further, the cylindrical foam is moved in the direction of the mandrel MD by the pulling force by the roll 92, and the diameter is gradually increased so as to approach the outer diameter of the mandrel MD along with the movement.
  • the foam FB between the mandrel MD and the circular die has a portion FT (hereinafter also referred to as “tensile portion FT”) where the pulling force by the roll 92 is applied along the inclination of the side surface of the truncated cone shape.
  • the slack portion FE moves between the circular die CD and the mandrel MD through the inner side than the side surface.
  • slack portions FE are formed in the foam FB, and in the vicinity of the circular die CD, slack portions FE and tension portions FT are alternately formed in the circumferential direction. Become.
  • the volume expansion of the foam FB usually converges at a location slightly away from the circular die CD, and a circumferential tension is applied to the slack portion FE as the diameter increases, so that the location close to the mandrel MD In general, no slack is observed. However, during this time, until the slack portion FE is eliminated, there is a difference in the stretching applied to the slack portion FE and the tension portion FT and how the cooling air strikes (cooling conditions), and the sheet thickness, density, etc. A difference is caused, and a striped pattern is formed on the resin foam sheet after passing through the mandrel MD due to the presence of the slack part FE and the tension part FT.
  • the polypropylene resin composition in the present embodiment has a mild foaming behavior because the upper limit is set for the content of HMS-PP, and the volume expansion after being extruded from the circular die CD is gentle. It becomes. Therefore, large slack is hardly generated in the foam FB, the stretching applied to the foam FB is substantially uniformly applied to the whole, and the cooling condition is also substantially uniform, so that the stripes are suppressed. As described above, when the content of HMS-PP is less than the lower limit, it is difficult to obtain a good foamed state.
  • the speed at which the diameter of the foam FB is increased can be improved by increasing the take-up speed (the length of the resin foam sheet wound around the roll 92 per unit time), this also suppresses the fringes. Although it can be achieved to some extent, the volume expansion occurs instantaneously, so that the effect of suppressing fringes is small as compared with adjusting the content of HMS-PP in the polypropylene resin composition. In addition, if the take-up speed is increased too much, a large tension is generated in the foam FB. Therefore, it is a simpler method to suppress fringes depending on the content of HMS-PP in the polypropylene resin composition. I can say that.
  • the take-up speed is usually 2 m / min or more and 10 m / min or less, although it depends on the type and thickness of the resin foam sheet to be produced.
  • the ratio (d2 / d1) between the diameter of the circular die CD (d1: the diameter of the intermediate circle between the inner circle and the outer circle of the discharge port) and the outer shape (d2) of the mandrel MD is increased.
  • This ratio (d2 / d1) is usually 1.9 or more and 3.2 or less, and the slit clearance of the circular die CD is usually selected from the range of 0.3 mm or more and 1.5 mm or less. .
  • the volume expansion behavior can be controlled to some extent by adjusting the foaming agent, if the amount of the foaming agent is excessively reduced, naturally the resin foam sheet may not exhibit a good foaming state. . From this point of view, it can be said that the method of suppressing fringes by the content of HMS-PP is a simple method.
  • the foaming agent for example, butane (n-butane, i-butane, or a mixture thereof) is used as the foaming agent
  • the ratio relative to 100 parts by mass of the polymer component is usually 1 part by mass or more.
  • the amount is 6 parts by mass or less.
  • the resin foam sheet produced in this way has a uniform thickness and foamed state. Further, in the surface layers 11 and 12, an ethylene- ⁇ -olefin copolymer having a crystallinity of 20% to 55% or a low density polyethylene resin having a crystallinity of 20% to 55% is a nonionic charge. Since it is contained together with the inhibitor, the nonionic antistatic agent can be quickly bleed out to the surface. As a result, at room temperature, for example, the surface resistivity is reduced to 1 ⁇ 10 13 ⁇ / ⁇ or less, and the antistatic performance can be exhibited. Therefore, the resin foam sheet can be used in a short period of time after the production without providing a curing period until the desired antistatic performance is exhibited, or even if it is provided. The inventory period of the sheet can be shortened.
  • the thick part is first brought into contact with the mold and bleeded out to this part.
  • the antistatic agent is easily moved to a portion not in strong contact with the mold.
  • the sheet molding method since the resin foam sheet is in a heated state, the mobility of the antistatic agent is also improved, and if the thickness of the resin foam sheet is uneven, the surface of the molded product There is a possibility of forming a portion where the antistatic agent is concentrated and a portion where the antistatic property has been lost. That is, it can be said that the resin foam sheet of the present embodiment can be used particularly suitably when the surface layers 11 and 12 are brought into contact with a mold and a molded product is produced by a sheet molding method.
  • Example 1 For the production of the resin foam sheet, equipment of the same kind as the apparatus configuration as shown in FIG. 2 was used. That is, the non-foamable resin composition is supplied from the second extruder 80 through the branch pipe D at two locations upstream and downstream of the resin flow path W1 into which the foamable resin composition flows from the first extruder 70.
  • the first and second extruders were connected to the merging die XH so as to flow in, and the circular die CD was connected to the downstream side of the merging die XH to perform co-extrusion.
  • a single screw extruder (upstream extruder) having a diameter of 90 mm and a single screw having a diameter of 115 mm connected to the single screw extruder.
  • a tandem type extruder composed of a shaft extruder (downstream extruder) was prepared.
  • HMS-PP commercially available from Borealis under the trade name “WB135”
  • block PP commercially available from Japan Polypro as trade name “BC6C”
  • trade name “Q-100F” trade name “Q-100F” from Sun Allomer.
  • a baking soda-citric acid-based foaming agent (Daiichi Seika) becomes 0.5 parts by mass.
  • This foamable resin composition was supplied to an extruder on the downstream side, the temperature of the foamable resin composition was lowered, and supplied to a confluence mold XH connected to the tip of the extruder at a discharge rate of 120 kg / hour.
  • a single-screw extruder having a diameter of 65 mm was prepared as a second extruder for melting and mixing the surface layer forming material.
  • a nonionic antistatic agent (trade name “TS-” manufactured by Kao Corporation), which is 2.0 parts by mass when the polymer component contained in a proportion of 30% by mass and the total amount of these polymer components is 100 parts by mass. 2B ") for forming the surface layer was supplied to the hopper of the second extruder and heated and melted at a temperature of 200 ° C.
  • the molten (non-foamable) polypropylene-based resin composition is bisected by a distribution pipe having a branch flow path, a tubular body opened at the center of the resin flow path of the confluence mold, From both the slits opened in the outer periphery of the resin flow path, the total amount is 15 kg / hour, each is discharged in an amount of 15 kg / hour, and after being laminated and joined to the inner layer side and the outer layer side of the foamable resin composition, merge Non-foamed on both the inner and outer sides via a foamed resin layer by co-extrusion from a circular die (caliber 140 mm, slit gap 1.0 mm) connected to the die tip in a cylindrical shape with a resin discharge rate of 135 kg / hour A cylindrical foam having a surface layer laminated thereon was formed.
  • a circular die caliber 140 mm, slit gap 1.0 mm
  • the cylindrical foam produced by extrusion foaming is expanded on a cooling mandrel having a diameter: 414 mm ⁇ length: 500 mm, and the outer surface is cooled by blowing air from an air ring.
  • Two strips of foamed resin foam sheets were produced by cutting with a cutter at two points that were symmetrical in the circumferential direction (opened 180 degrees).
  • the surface resistivity of the obtained resin foam sheet of Example 1 was measured based on JIS K 6911-1995.
  • the pretreatment time was 24 hours. Specifically, after a flat square test piece having a side of 10 cm is left in an atmosphere of a temperature of 22 ° C. and a humidity of 60% for 24 hours, a test apparatus (manufactured by Advantest Corporation) under an environment of a temperature of 22 ° C. and a humidity of 60% is used. Using a digital ultra-high resistance / microammeter R8340 and a resiliency chamber R12702A), an electrode is crimped to a test piece with a load of about 30 N, a voltage of 500 V is applied, and a resistance value after one minute has elapsed.
  • ⁇ s ⁇ (D + d) / (D ⁇ d) ⁇ Rs
  • ⁇ s Surface resistivity ( ⁇ / ⁇ )
  • D Inner diameter (cm) of the annular electrode on the surface (7 cm for the resiliency chamber R12702A)
  • d outer diameter (cm) of inner circle of surface electrode (5 cm for resiliency chamber R12702A)
  • Rs Surface resistance ( ⁇ )
  • a foam tray was prepared by a sheet molding method, but the appearance was beautiful and the mechanical strength was excellent.
  • Example 2 In the polypropylene resin composition for forming the surface layer, instead of the ethylene- ⁇ -olefin copolymer (KS240T) manufactured by Nippon Polyethylene, the crystallinity of 50 commercially available from Nippon Polyethylene under the trade name “LD400” A resin foam sheet was produced in the same manner as in Example 1 except that% low-density polyethylene (PE) resin was used, and a foam tray was produced.
  • PE low-density polyethylene
  • Example 3 In the polypropylene-based resin composition for forming the surface layer, instead of the ethylene- ⁇ -olefin copolymer (KS240T) manufactured by Nippon Polyethylene Co., Ltd., a commercial crystallinity of 53% as a trade name “LF441B” from Nippon Polyethylene Co., Ltd. A resin foam sheet was produced in the same manner as in Example 1 except that the low-density polyethylene (PE) resin was used, and a foam tray was produced. When the surface resistivity of the resin foam sheet of Example 3 was measured in the same manner as in Example 1, it was found that the resin foam sheet had a surface resistivity of 6.5 ⁇ 10 12 ⁇ / ⁇ . Further, no noticeable stripes were observed, and the foamed tray formed by the resin foamed sheet had a beautiful appearance and excellent mechanical strength.
  • PE low-density polyethylene
  • Example 4 In the polypropylene resin composition for forming the surface layer, instead of the ethylene- ⁇ -olefin copolymer (KS240T) manufactured by Nippon Polyethylene Co., Ltd., commercially available from Sumitomo Chemical Co., Ltd. under the trade name “Eriksen VL-100” A resin foam sheet was produced in the same manner as in Example 1 except that an ultra-low density polyethylene (PE) resin having a crystallinity of 36% was used, and a foam tray was produced. When the surface resistivity of the resin foam sheet of Example 4 was measured in the same manner as in Example 1, it was found that the resin foam sheet had a surface resistivity of 4.0 ⁇ 10 12 ⁇ / ⁇ . Further, no noticeable stripes were observed, and the foamed tray formed by the resin foamed sheet had a beautiful appearance and excellent mechanical strength.
  • PE ultra-low density polyethylene
  • Example 5 The proportion of HMS-PP (WB135) in the polypropylene resin composition for forming the foamed resin layer was changed to 25 mass% instead of 39 mass%, and the proportion of block PP (BC6C) was changed to 55 mass% instead.
  • a resin foam sheet was produced in the same manner as in Example 1 except that the content was 69% by mass to produce a foam tray.
  • the resin foam sheet of Example 5 was measured for surface resistivity in the same manner as in Example 1. As a result, it was found that the resin foam sheet had a surface resistivity of 3.5 ⁇ 10 12 ⁇ / ⁇ . Further, no noticeable stripes were observed, and the foamed tray formed by the resin foamed sheet had a beautiful appearance and excellent mechanical strength.
  • Example 6 In the polypropylene resin composition for forming the surface layer, a resin foam sheet was produced in the same manner as in Example 1 except that the polymer component was changed to 100% by mass of HMS-PP (WB135) to produce a foam tray.
  • the surface resistivity of the resin foam sheet of this Example 6 was measured in the same manner as in Example 1, it showed a surface resistivity of 4.5 ⁇ 10 13 ⁇ / ⁇ .
  • no noticeable stripes were observed on the resin foam sheet itself, and the foam tray formed from the resin foam sheet had a beautiful appearance and excellent mechanical strength.
  • Example 7 A resin foam sheet was produced in the same manner as in Example 1 except that the nonionic antistatic agent was not contained in the polypropylene resin composition for forming the surface layer, and a foam tray was produced.
  • the surface resistivity of the resin foam sheet of Example 7 was measured in the same manner as in Example 1, it showed a surface resistivity of 6.5 ⁇ 10 15 ⁇ / ⁇ .
  • no noticeable stripes were observed on the resin foam sheet itself, and the foam tray formed from the resin foam sheet had a beautiful appearance and excellent mechanical strength.
  • Example 8 A resin foam sheet was produced in the same manner as in Example 5 except that a nonionic antistatic agent was not included in the polypropylene resin composition for forming the surface layer, and a foam tray was produced.
  • a nonionic antistatic agent was not included in the polypropylene resin composition for forming the surface layer
  • a foam tray was produced.
  • the surface resistivity of the resin foam sheet of Example 8 was measured in the same manner as in Example 1, it exhibited a surface resistivity of 6.5 ⁇ 10 15 ⁇ / ⁇ .
  • no noticeable stripes were observed on the resin foam sheet itself, and the foam tray formed from the resin foam sheet had a beautiful appearance and excellent mechanical strength.
  • Comparative Example 1 The ratio of HMS-PP (WB135) in the polypropylene resin composition for forming the foamed resin layer was changed to 18% by mass instead of 39% by mass, and instead the ratio of block PP (BC6C) was changed to 55% by mass.
  • a resin foam sheet was produced in the same manner as in Example 1 except that the content was 76% by mass, and a foam tray was produced.
  • the resin foam sheet of Comparative Example 1 was measured for surface resistivity in the same manner as in Example 1, and was found to have a surface resistivity of 3.5 ⁇ 10 12 ⁇ / ⁇ .
  • the foamed resin sheet is not foamed to have a sufficient thickness, and no noticeable stripes were observed, but the foamed tray formed by the resin foamed sheet has mechanical strength in each example. It was inferior to.
  • Comparative Example 2 The proportion of HMS-PP (WB135) in the polypropylene resin composition for forming the foamed resin layer was changed to 50 mass% instead of 39 mass%, and the proportion of block PP (BC6C) was changed to 55 mass% instead.
  • a resin foam sheet was produced in the same manner as in Example 1 except that the content was 44% by mass to produce a foam tray.
  • the surface resistivity of the resin foam sheet of Comparative Example 2 was measured in the same manner as in Example 1, it was found to have a surface resistivity of 3.5 ⁇ 10 12 ⁇ / ⁇ .
  • the resin foam sheet is conspicuous, and the foam tray formed by the resin foam sheet has a perforation defect, making it difficult to obtain a foam tray having a good appearance.
  • a resin foam sheet suitable for a forming material of a foam molded product having a three-dimensional structure can be provided.
  • Resin foam sheet 11 First surface layer (non-foamed resin layer) 12: Second surface layer (non-foamed resin layer) 20: Foamed resin layer

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
PCT/JP2010/070294 2009-11-18 2010-11-15 樹脂発泡シート WO2011062141A1 (ja)

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JP5572364B2 (ja) * 2009-11-18 2014-08-13 積水化成品工業株式会社 樹脂発泡シート
JP5707048B2 (ja) * 2010-03-29 2015-04-22 積水化成品工業株式会社 樹脂発泡シート及び樹脂発泡シートの製造方法
JP7288323B2 (ja) * 2019-03-25 2023-06-07 積水化成品工業株式会社 包装用シート
JP2020163614A (ja) * 2019-03-28 2020-10-08 積水化成品工業株式会社 生分解性樹脂発泡シートの製造方法
CN113068898A (zh) * 2020-01-06 2021-07-06 广东昂斯新材料技术有限公司 一种带注射条纹路的热塑性聚氨酯发泡鞋底及其制备工艺
JP7385488B2 (ja) * 2020-02-13 2023-11-22 日立造船株式会社 繊維含有シートの製造方法
JP7628788B2 (ja) * 2020-09-17 2025-02-12 リスパック株式会社 熱成形用発泡樹脂積層シート、成形品、及び容器
JPWO2022065393A1 (enrdf_load_stackoverflow) * 2020-09-28 2022-03-31
US12227605B2 (en) 2021-05-12 2025-02-18 Borealis Ag High melt strength polypropylene
KR102532725B1 (ko) * 2021-10-05 2023-05-18 주식회사 애니켐 탄소중립 친환경 발포시트 및 그로부터 얻어지는 물품
JP2023082445A (ja) * 2021-12-02 2023-06-14 積水化成品工業株式会社 再生樹脂組成物、発泡体及びその製造方法
CN114274635B (zh) * 2021-12-29 2024-03-29 台山市大源新材料科技有限公司 一种树脂发泡片材及其生产工艺

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