WO2018079261A1 - Composition de résine à base de polypropylène pour moulage de mousse, corps moulé en mousse à base de polypropylène, corps moulé en mousse multicouche à base de polypropylène, et procédé de production de corps moulé en mousse à base de polypropylène - Google Patents

Composition de résine à base de polypropylène pour moulage de mousse, corps moulé en mousse à base de polypropylène, corps moulé en mousse multicouche à base de polypropylène, et procédé de production de corps moulé en mousse à base de polypropylène Download PDF

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WO2018079261A1
WO2018079261A1 PCT/JP2017/036833 JP2017036833W WO2018079261A1 WO 2018079261 A1 WO2018079261 A1 WO 2018079261A1 JP 2017036833 W JP2017036833 W JP 2017036833W WO 2018079261 A1 WO2018079261 A1 WO 2018079261A1
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Prior art keywords
polypropylene
molded article
foam
inorganic filler
resin composition
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PCT/JP2017/036833
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English (en)
Japanese (ja)
Inventor
智也 又吉
孝行 渡辺
江里口　真男
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三井化学東セロ株式会社
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Priority to JP2018547537A priority Critical patent/JP6790110B2/ja
Publication of WO2018079261A1 publication Critical patent/WO2018079261A1/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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • 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
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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

Definitions

  • the present invention relates to a polypropylene resin composition for foam molding, a polypropylene foam molded article, a polypropylene multilayer foam molded article, and a method for producing a polypropylene foam molded article.
  • Wooden boards such as hardboards and medium density fiberboards are used as, for example, building materials, furniture, partitioning materials, heat insulating materials, packing materials and the like because they are lightweight and have excellent mechanical properties.
  • Patent Document 1 Japanese Patent Laid-Open No. 2014-151599
  • Patent Document 2 Japanese Patent Laid-Open No. 2010-643066
  • Patent Document 1 includes a wood board formed by adhering a wood chip or wood fiber with an adhesive, and containing a parenchyma-removed bamboo fiber obtained by removing parenchyma cells from bamboo fiber obtained by crushing bamboo. The characteristic wood board is described.
  • Patent Document 2 discloses a wood board obtained by hot pressing a wood material together with an adhesive.
  • the wood board is made of a fine powder of sodium sulfite having an average particle size of 40 ⁇ m or more and 180 ⁇ m or less.
  • a wood board characterized by containing 0.1 to 30% by weight based on the dry weight is described.
  • the present inventors examined using a polypropylene foam sheet containing a polypropylene resin and an inorganic filler as an alternative to the wooden board.
  • the polypropylene foam sheet containing the polypropylene resin and the inorganic filler may have uneven appearance such as color unevenness and vertical stripes (flow pattern) on the surface, which may deteriorate the appearance. .
  • the present invention has been made in view of the above circumstances, and has an excellent appearance and can be used as a substitute for a wooden board.
  • a resin composition is provided.
  • the present inventors diligently studied to realize a polypropylene-based foam molded product and a polypropylene-based multilayer foamed molded product that have an excellent appearance and can be used as a substitute for a wooden board.
  • the present inventors have a resin composition in which an inorganic filler having a moisture content of a specific value or less is blended with a polypropylene resin, has an excellent appearance, and can be used as a substitute for a wooden board. It has been found that a polypropylene-based foam molded body and a polypropylene-based multilayer foam molded body can be realized.
  • the following polypropylene molding resin composition for foam molding, a polypropylene foam molding, a polypropylene multilayer foam molding, and a method for producing a polypropylene foam molding are provided.
  • a polypropylene resin composition for foam molding according to the above [1] A polypropylene resin composition for foam molding, wherein the inorganic filler contains talc.
  • a polypropylene-based resin composition for foam molding having a mass% or less.
  • the polypropylene resin composition for foam molding according to any one of the above [1] to [4] In accordance with ASTM D1238, the polypropylene resin composition for foam molding, wherein the melt flow rate of the polypropylene resin measured at 230 ° C. and a load of 2.16 kg is from 0.5 g / 10 min to 20 g / 10 min. .
  • a polypropylene resin composition for foam molding wherein the polypropylene resin has a Z average molecular weight (Mz) / weight average molecular weight (Mw) of 7 to 20 as measured by gel permeation chromatography (GPC).
  • Mz Z average molecular weight
  • Mw weight average molecular weight
  • GPC gel permeation chromatography
  • a polypropylene-based foam-molded article comprising the foam-molded polypropylene-based resin composition according to any one of [1] to [6].
  • polypropylene foam molded body used as an alternative to wood boards.
  • a polypropylene foam layer composed of the polypropylene foam molded article according to any one of the above [7] to [13];
  • a first non-foaming resin layer provided on one surface of the polypropylene-based foam layer and containing a thermoplastic resin and an inorganic filler;
  • a second non-foaming resin layer provided on the other surface of the polypropylene-based foam layer and containing a thermoplastic resin and an inorganic filler;
  • a polypropylene-based multilayer foamed molded article A polypropylene-based multilayer foamed molded article.
  • the ratio of the thickness of the first non-foamable resin layer to the thickness of the entire polypropylene-based multilayer foamed molded article is 0.01 or more and 0.5 or less
  • a polypropylene-based multilayer foamed molded article, wherein a ratio of the thickness of the second non-foamable resin layer to the thickness of the entire polypropylene-based multilayer foamed molded article is 0.01 or more and 0.5 or less.
  • a polypropylene-based multilayer foamed molded article wherein the inorganic filler in the first non-foamable resin layer and the second non-foamable resin layer includes one or more selected from talc, mica, and silica, respectively.
  • the first non-foamable resin layer and the second non-foamable resin layer have the same composition and have the same thickness, and are a polypropylene-based multilayer foamed molded article.
  • a production method for producing a polypropylene-based foamed molded article comprising a polypropylene-based resin and an inorganic filler,
  • the inorganic filler contains at least one selected from talc and silica, Adjusting the moisture content of the inorganic filler to 0.10% by mass or less based on the whole inorganic filler by heating the inorganic filler;
  • the manufacturing method of the polypropylene-type foaming molding containing this.
  • the polypropylene resin composition for foam molding according to this embodiment includes a polypropylene resin and an inorganic filler. And the said inorganic filler contains at least 1 type selected from a talc and a silica, and the moisture content of the said inorganic filler is 0.10 mass% or less with respect to the said whole inorganic filler.
  • the water content of the inorganic filler according to this embodiment is preferably 0.08% by mass or less, more preferably 0.07% by mass or less, still more preferably 0.06% by mass or less, particularly with respect to the entire inorganic filler. Preferably it is 0.05 mass% or less.
  • the minimum of the moisture content rate of the inorganic filler which concerns on this embodiment is not specifically limited, For example, it is 0.001 mass% or more with respect to the whole inorganic filler.
  • the moisture content of the inorganic filler can be calculated, for example, by quantifying the moisture generated by heating the inorganic filler in a nitrogen stream and by the Karl Fischer coulometric titration method.
  • the present inventors examined using a polypropylene foam sheet containing a polypropylene resin and an inorganic filler as an alternative to the wooden board.
  • the polypropylene foam sheet containing the polypropylene resin and the inorganic filler may have uneven appearance such as color unevenness and vertical stripes (flow pattern) on the surface, which may deteriorate the appearance. .
  • the present inventors have intensively studied to realize a polypropylene-based foam molded product and a polypropylene-based multilayer foamed molded product that are excellent in appearance and can be used as a substitute for a wooden board.
  • the present inventors have a resin composition in which an inorganic filler having a moisture content of a specific value or less is blended with a polypropylene resin, has an excellent appearance, and can be used as a substitute for a wooden board. It has been found that a polypropylene-based foam molded body and a polypropylene-based multilayer foam molded body can be realized.
  • an inorganic filler having a moisture content of not more than the above upper limit when used, the occurrence of unevenness such as gloss unevenness, color unevenness and vertical stripes (flow pattern) on the surface is suppressed, and the uniformity of the foamed cells is further improved. Therefore, it is possible to obtain a polypropylene-based foam molded article having an excellent appearance.
  • the inorganic filler having a moisture content of not more than the above upper limit value is, for example, obtained by heating the inorganic filler at 80 to 150 ° C. for about 0.5 to 48 hours using a dehumidifying dryer or a vacuum dryer. It can be obtained by removing moisture adsorbed inside.
  • the polypropylene resin composition for foam molding according to the present embodiment by containing at least one selected from talc and silica as the inorganic filler, for example, compared with the case where calcium carbonate is used as the inorganic filler, etc.
  • talc and silica as the inorganic filler
  • by containing at least one selected from talc and silica as the inorganic filler for example, compared with the case where glass fiber is used as the inorganic filler, etc.
  • the appearance of the polypropylene-based foamed molded product can be improved.
  • the polypropylene resin composition for foam molding according to the present embodiment uses a polypropylene resin that is a plastic, the resulting polypropylene foam molded article has excellent water resistance compared to a wooden board and is wet with water. Excellent mechanical properties can be maintained even when left in a humid environment for a long time.
  • the polypropylene-based foam-molded article composed of the foam-molded polypropylene-based resin composition according to the present embodiment is unlikely to be chipped like a wood board and is excellent in handleability.
  • the total content of the polypropylene resin and the inorganic filler in the polypropylene resin composition for foam molding according to the present embodiment is preferably 50% by weight or more when the entire polypropylene foam molded body 100 is 100% by weight. 100 mass% or less, More preferably, it is 70 mass% or more and 100 mass% or less, More preferably, it is 90 mass% or more and 100 mass% or less, Most preferably, it is 95 mass% or more and 100 mass% or less.
  • the polypropylene resin composition for foam molding according to the present embodiment contains a polypropylene resin as an essential component.
  • examples of the polypropylene resin according to the present embodiment include a propylene homopolymer, a copolymer of propylene and ethylene or an ⁇ -olefin having 4 to 20 carbon atoms.
  • Examples of the ⁇ -olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, Examples include 1-hexadecene, 1-octadecene, 1-eicosene and the like.
  • ethylene or an ⁇ -olefin having 4 to 10 carbon atoms is preferable, and ethylene is more preferable.
  • These ⁇ -olefins may form a random copolymer with propylene or may form a block copolymer.
  • the content of structural units derived from these ⁇ -olefins is preferably 5 mol% or less, more preferably 2 mol% or less in the polypropylene resin.
  • the polypropylene resin in the polypropylene resin composition for foam molding may be used alone or in combination of two or more. Among these, a propylene homopolymer is preferable as the polypropylene resin from the viewpoint of obtaining a polypropylene-based foam molded article having higher rigidity.
  • the polypropylene resin according to the present embodiment can be manufactured by various methods. For example, it can be produced using a known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst.
  • the melt flow rate (MFR) of the polypropylene resin according to this embodiment measured under conditions of 230 ° C. and 2.16 kg load in accordance with ASTM D1238 is preferably 0.5 g from the viewpoint of fluidity and moldability. / 10 minutes or more, more preferably 1 g / 10 minutes or more. From the viewpoint of further stabilizing the moldability and further suppressing foam breakage of the foamed cells, preferably 20 g / 10 minutes or less, more preferably 10 g / 10. Min. Or less, more preferably 7 g / 10 min or less.
  • the polypropylene resin according to this embodiment has a Z average molecular weight (Mz) / weight average molecular weight (Mw) measured by gel permeation chromatography (GPC). Preferably they are 7 or more and 20 or less, More preferably, they are 10 or more and 20 or less.
  • Mz Z average molecular weight
  • Mw weight average molecular weight measured by gel permeation chromatography
  • Polypropylene resins having a Mz / Mw value within the above range show a wide molecular weight distribution and contain a large amount of high molecular weight components. Therefore, the melt tension and melt elongation are high, and the moldability including foaming is excellent.
  • the foam moldability of the polypropylene resin composition for foam molding can be improved. Even if the inorganic filler is highly filled, foaming is possible. Cell uniformity can be made better, and perforation and sheet breakage of the polypropylene-based foamed molded product can be further suppressed. As a result, a polypropylene-based foamed molded product that is superior in appearance can be realized.
  • the content of the polypropylene resin having an Mz / Mw value within the above range is preferably 50% by mass or more when the total amount of the polypropylene resin contained in the polypropylene resin composition for foam molding is 100% by mass. Preferably it is 60 mass% or more.
  • the polypropylene resin composition for foam molding according to this embodiment contains an inorganic filler as an essential component.
  • the inorganic filler includes at least one selected from talc and silica from the viewpoint of obtaining a polypropylene-based foam-molded article excellent in lightness, mechanical properties, recyclability, handleability and appearance.
  • talc is preferable from the viewpoints of compatibility with polypropylene resin, foamability, moldability, colorability, low cost, safety, and the like.
  • the content of the inorganic filler in the polypropylene resin composition for foam molding according to the present embodiment is preferably 5 parts by mass or more when the total amount of the polypropylene resin and the inorganic filler is 100 parts by mass.
  • the amount is preferably 15 parts by mass or more, more preferably 25 parts by mass or more, still more preferably 35 parts by mass or more, and particularly preferably 45 parts by mass or more.
  • the content of the inorganic filler in the polypropylene resin composition for foam molding according to the present embodiment is preferably 90 parts by mass or less when the total amount of the polypropylene resin and the inorganic filler is 100 parts by mass. More preferably, it is 80 mass parts or less, More preferably, it is 70 mass parts or less, Most preferably, it is 65 mass parts or less.
  • the content of the inorganic filler By making the content of the inorganic filler more than the above lower limit value, it is possible to further improve mechanical properties such as bending properties and tensile properties, heat resistance, moisture resistance, dimensional stability, etc. of the obtained polypropylene-based foam molded article. it can. Moreover, by making the content of the inorganic filler not more than the above upper limit value, the balance of light weight and high rigidity of the obtained polypropylene foam molded article can be improved, and the moldability and foam cell of the polypropylene foam molded article can be improved. The uniformity of the resin can be further improved, and the perforation and sheet breakage of the polypropylene-based foam molded product can be further suppressed. As a result, a polypropylene-based foam molded product that is more excellent in appearance can be realized. .
  • the inorganic filler may be used without treatment, in order to improve the interfacial adhesion with the polypropylene resin and improve the dispersibility with respect to the polypropylene resin, a silane coupling agent, a titanium coupling agent,
  • the surface may be treated with a surfactant or the like.
  • the polypropylene resin composition for foam molding according to the present embodiment includes a heat stabilizer, an antioxidant, an ultraviolet absorber, a pigment, an antistatic agent, a copper damage inhibitor, a flame retardant, a neutralizing agent, if necessary.
  • FIG. 1 is a cross-sectional view schematically showing an example of the structure of a polypropylene foam molded body 100 according to an embodiment of the present invention.
  • the polypropylene-based foam molded body 100 according to the present embodiment is constituted by the above-described polypropylene-based resin composition for foam molding according to the present embodiment, and can be obtained by foam-molding the polypropylene-based resin composition for foam molding.
  • the shape of the polypropylene-type foaming molding 100 which concerns on this embodiment is not specifically limited, For example, it is a sheet form.
  • the density of the polypropylene-based foamed molded article 100 is preferably 1.0 g / cm 3 or less, less than 1.0 g / cm 3 is more preferable.
  • the density is not more than the above upper limit value or less than the above upper limit value, an even lighter polypropylene-based foam molded article 100 can be obtained.
  • a polypropylene-type foaming molding can float in water as a density is below the said upper limit or less, it becomes easy to fractionate a structural component and can improve recyclability.
  • the density of the polypropylene-based foamed molded article 100 is preferably 0.35 g / cm 3 or more, 0.40 g / cm 3 or more, more preferably, 0.45 g / cm 3 or more and more preferably, 0.50 g / cm 3 or more Is particularly preferred.
  • the density is equal to or higher than the lower limit, mechanical properties such as bending properties and tensile properties of the polypropylene foamed molded product 100 can be further improved.
  • the density of the polypropylene-based foam molded body 100 is controlled within the above range by appropriately controlling, for example, the type and blending amount of the polypropylene-based resin, inorganic filler, and the like, and the expansion ratio of the polypropylene-based foam molded body 100, respectively. be able to.
  • the flexural modulus of the polypropylene foam molded body 100 according to this embodiment measured in an environment of 23 ° C. and 50% RH is preferably 1.0 GPa or more, more preferably 1.5 GPa or more, and further 2.0 GPa or more. Preferably, 2.5 GPa or more is even more preferable, and 3.0 GPa or more is particularly preferable.
  • the rigidity of the polypropylene foam molded body 100 can be further improved. As a result, deformation of the polypropylene foam molded body 100 with respect to external stress can be suppressed, or It is possible to improve the scratch resistance, heat resistance, dimensional stability, etc. of the foam molded body 100.
  • the bending elastic modulus of the polypropylene-type foaming molding 100 which concerns on this embodiment, 9 GPa or less is more preferable.
  • the flexural modulus By setting the flexural modulus to be equal to or less than the above upper limit value, the balance between the deformation resistance against external stress and the toughness of the polypropylene foam molded body 100 can be improved.
  • the bending elastic modulus of the polypropylene-based foam molded body 100 can be measured by a three-point bending test. For example, with reference to the bending strength test described in JIS A5905, the specimen thickness t: 3 mm, specimen width b: 50 mm, specimen length: 150 mm, and span in an environment of 23 ° C.
  • the amount of deflection Y [mm] with respect to the test load F [N] is measured under the conditions of the distance L: 100 mm and the bending speed: 50 mm / min.
  • the gradient ⁇ F / ⁇ Y of the initial straight line portion in the obtained load-deflection diagram is obtained, and the flexural modulus: E [GPa] is obtained from the following equation (1).
  • E ⁇ L 3 / (4b ⁇ t 3 ) ⁇ ⁇ ( ⁇ F / ⁇ Y) (1)
  • One point is measured for each of the MD direction and the TD direction, and the average value thereof can be adopted as the bending elastic modulus.
  • the flexural modulus of the polypropylene-based foam molded body 100 is within the above range by appropriately controlling, for example, the type and blending amount of the polypropylene-based resin, inorganic filler, and the like, and the expansion ratio of the polypropylene-based foam molded body 100, respectively. Can be controlled.
  • the Young's modulus of the polypropylene foam molded body 100 is preferably 0.3 GPa or more, more preferably 0.5 GPa or more, further preferably 0.8 GPa or more, and particularly preferably 1.0 GPa or more.
  • the rigidity of the polypropylene foam molded body 100 can be further improved.
  • deformation of the polypropylene foam molded body 100 with respect to external stress can be suppressed, or the polypropylene foam can be expanded.
  • the scratch resistance, heat resistance, dimensional stability, and the like of the molded body 100 can be improved.
  • the Young's modulus of the polypropylene foam molded body 100 is preferably 5 GPa or less, and more preferably 3 GPa or less.
  • the Young's modulus of the polypropylene-based foam molded body 100 is an environment of 23 ° C. and 50% RH, and the shape of the test piece: strip shape, the width of the test piece: 10 mm, the distance between chucks: 50 mm, and the tensile speed: 20 mm.
  • the Young's modulus of the polypropylene-based foam molded body 100 is controlled within the above range by appropriately controlling, for example, the type and blending amount of the polypropylene-based resin, inorganic filler, and the like, and the expansion ratio of the polypropylene-based foam molded body 100, respectively. can do.
  • the arithmetic average roughness Ra of the surface of the polypropylene-based foamed molded product 100 is 2 from the viewpoint of further suppressing unevenness such as gloss unevenness and color unevenness on the surface and occurrence of vertical stripes (flow pattern) and improving the appearance. It is preferable that it is 5 ⁇ m or less.
  • the lower limit of the arithmetic average roughness Ra on the surface of the polypropylene-based foamed molded product 100 is not particularly limited, but is, for example, 0.1 ⁇ m or more.
  • the arithmetic average roughness Ra of the surface of the polypropylene-based foamed molded product 100 can be measured according to JIS-B0601-1994.
  • the types and blending amounts of polypropylene-based resin and inorganic filler, the expansion ratio of the polypropylene-based foamed molded product 100, etc. It is important to use an inorganic filler having a low moisture content while appropriately selecting each.
  • the thickness of the polypropylene foam molded body 100 is not particularly limited, but is, for example, from 0.5 mm to 30 mm, preferably from 1.0 mm to 20 mm, more preferably from 1.5 mm to 12 mm, and still more preferably. It is 2.0 mm or more and 9.0 mm or less. When the thickness of the polypropylene-based foam molded body 100 is within this range, the balance of lightness, mechanical properties, recyclability, handleability, appearance, moldability, etc. is more excellent.
  • the polypropylene-based foam molded body 100 can be obtained, for example, by foam-molding the polypropylene-based resin composition for foam molding according to the present embodiment into a predetermined shape.
  • the molding apparatus and molding conditions are not particularly limited, and conventionally known molding apparatuses and foam molding conditions can be employed.
  • each component is mixed or melted / kneaded by dry blending, tumbler mixer, Banbury mixer, single screw extruder, twin screw extruder, high speed twin screw extruder, hot roll, etc. Can be prepared.
  • the polypropylene-based foam-molded body 100 can be obtained, for example, by foam-molding the above-described foam-molded polypropylene-based resin composition into a predetermined shape using an extrusion molding machine or an injection molding machine.
  • the foaming agent for molding the polypropylene-based foam molded body 100 include a chemical foaming agent and carbon dioxide gas.
  • Chemical foaming agents include sodium bicarbonate, ammonium bicarbonate, various carboxylates, sodium borohydride, azodicarboxamide, N, N-dinitrosopentamethylenetetramine, P, P-oxybis (benzenesulfonylhydrazide) Azobisisobutyronitrile, paratoluenesulfonyl hydrazide and the like.
  • Carbon dioxide gas can be supplied in a gaseous state, a liquid state, or a supercritical state.
  • the chemical foaming agent is blended with the polypropylene resin composition for foam molding and mixed uniformly before being introduced into the extruder.
  • carbon dioxide gas is used as the foaming agent, it is preferable that the polypropylene resin composition for foam molding is kneaded and plasticized in the extruder and then directly pressed into the extruder.
  • the expansion ratio of the polypropylene resin composition for foam molding is not particularly limited, and can be appropriately determined in consideration of various physical properties of the polypropylene foam molded body 100 to be obtained.
  • Polypropylene-based foam molded article 100 has an excellent appearance, and also has a good balance between lightness and mechanical properties, so it can be used as a substitute for wood boards, especially hard boards, medium-density fiber boards, and other high-rigidity wood boards. It can be used as a product.
  • FIG. 2 is a cross-sectional view schematically showing an example of the structure of a polypropylene-based multilayer foamed molded product 200 according to an embodiment of the present invention.
  • the polypropylene-based multilayer foamed molded product 200 according to this embodiment is provided on one surface of the polypropylene-based foamed layer 100 constituted by the polypropylene-based foamed molded product 100 according to this embodiment, and the polypropylene-based foamed layer 100, and The first non-foamable resin layer 110 containing a thermoplastic resin and an inorganic filler, and the second non-foamable resin layer 120 provided on the other surface of the polypropylene foam layer 100 and containing a thermoplastic resin and an inorganic filler.
  • the machine Since the polypropylene-based multilayer foamed molded product 200 according to the present embodiment has an unfoamed inorganic filler-containing resin layer on the surface, the machine has bending characteristics, tensile properties, and the like compared to the polypropylene-based foamed molded product 100 according to the present embodiment. Characteristics can be improved.
  • the shape of the polypropylene-based multilayer foamed molded product 200 according to the present embodiment is not particularly limited, and is, for example, a sheet shape.
  • the thickness of the polypropylene-based multilayer foamed molded product 200 according to the present embodiment is not particularly limited, but is, for example, 0.5 mm to 30 mm, preferably 1.0 mm to 20 mm, and more preferably 1.5 mm to 12 mm. More preferably, it is 2.0 mm or more and 9.0 mm or less. When the thickness of the polypropylene-based multilayer foamed molded product 200 is within this range, the balance of lightness, mechanical properties, recyclability, handleability, appearance, moldability, etc. is more excellent.
  • the thickness of the first non-foamable resin layer 110 and the second non-foamable resin layer 120 is not particularly limited, but is preferably 0.05 mm or more and 5 mm or less, and preferably 0.1 mm or more and 3 mm or less. More preferred. Further, the ratio of the thickness of the first non-foamable resin layer 110 to the thickness of the polypropylene-based multilayer foamed molded article 200 is preferably 0.01 or more and 0.5 or less, more preferably 0.02 or more and 0.3 or less. Yes, more preferably 0.05 or more and 0.2 or less.
  • the ratio of the thickness of the second non-foamable resin layer 120 to the thickness of the polypropylene-based multilayer foamed molded article 200 is preferably 0.01 or more and 0.5 or less, more preferably 0.02 or more and 0.3 or less. Yes, more preferably 0.05 or more and 0.2 or less.
  • the first non-foamable resin layer 110 and the second non-foamable resin layer 120 according to the present embodiment include a thermoplastic resin as an essential component.
  • a thermoplastic resin for example, a polyolefin resin can be used.
  • polyolefin resins include homopolymers of ⁇ -olefins such as ethylene, propylene, butene-1,3-methylbutene-1,3-methylpentene-1,4-methylpentene-1, and copolymers thereof. Or the copolymer of these and other copolymerizable unsaturated monomers, etc. are mentioned.
  • high-density polyethylene More specifically, high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, ultrahigh molecular weight polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and other polyethylene-based polymers
  • examples thereof include resin; polypropylene resin; polybutene-1; poly-4-methylpentene-1.
  • One type of polyolefin resin may be used, or two or more types may be used in combination.
  • a polypropylene resin is preferable because it is excellent in lightness, rigidity, tensile strength, scratch resistance, low water absorption, and heat resistance.
  • a polypropylene resin the thing similar to the polypropylene resin used with the polypropylene foaming molding 100 which concerns on this embodiment mentioned above can be mentioned, for example.
  • the first non-foamable resin layer 110 and the second non-foamable resin layer 120 according to the present embodiment include an inorganic filler as an essential component.
  • the inorganic filler include talc, mica, clay, wollastonite, calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, kaolin, perlite, calcium sulfate, barium sulfate, potassium titanate, barium sulfate, calcium sulfite, Calcium silicate, silica, diatomaceous earth, alumina, titanium oxide, glass fiber, glass bead, glass balloon, milled fiber, montmorillonite, bentonite, guffite, aluminum powder, glass flake, carbon fiber, carbon flake, carbon balun, carbon Beads, carbon milled fiber, carbon black, graphite, carbon nanotube, ceramic fiber, molybdenum sulfide, aramid particles, aramid fiber, boron fiber, silicon
  • the inorganic filler in the first non-foamable resin layer 110 and the second non-foamable resin layer 120 a polypropylene-based multilayer foam molding excellent in lightness, mechanical properties, recyclability, handleability and appearance.
  • talc talc
  • mica talc
  • silica talc
  • talc and mica are preferable from the viewpoint of low cost
  • talc is more preferable from the viewpoint of compatibility with polypropylene resin, foamability, moldability, colorability, low price, safety, and the like.
  • the inorganic filler may be used without treatment, in order to improve the interfacial adhesion with the thermoplastic resin and improve the dispersibility to the thermoplastic resin, a silane coupling agent, a titanium coupling agent,
  • the surface may be treated with a surfactant or the like.
  • the water content of the inorganic filler according to this embodiment is preferably 0.10% by mass or less, more preferably 0.08% by mass or less, further preferably 0.07% by mass or less, based on the entire inorganic filler. More preferably, it is 0.06 mass% or less, Most preferably, it is 0.05 mass% or less.
  • the minimum of the moisture content rate of the inorganic filler which concerns on this embodiment is not specifically limited, For example, it is 0.001 mass% or more with respect to the whole inorganic filler.
  • the moisture content of the inorganic filler can be calculated, for example, by quantifying the moisture generated by heating the inorganic filler in a nitrogen stream and by the Karl Fischer coulometric titration method.
  • the inorganic filler having a moisture content of not more than the above upper limit value is, for example, obtained by heating the inorganic filler at 80 to 150 ° C. for about 0.5 to 48 hours using a dehumidifying dryer or a vacuum dryer. It can be obtained by removing moisture adsorbed inside.
  • the content of the inorganic filler in the first non-foamable resin layer 110 and the second non-foamable resin layer 120 is such that the thermoplastic resin contained in the first non-foamable resin layer 110 and the second non-foamable resin layer 120 and
  • each is preferably 5 parts by mass or more, more preferably 15 parts by mass or more, still more preferably 25 parts by mass or more, still more preferably 35 parts by mass or more, particularly preferably. Is 45 parts by mass or more.
  • the content of the inorganic filler in the first non-foamable resin layer 110 and the second non-foamable resin layer 120 is the thermoplasticity contained in the first non-foamable resin layer 110 and the second non-foamable resin layer 120.
  • each is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, still more preferably 70 parts by mass or less, and particularly preferably 65 parts by mass or less. .
  • the content of the inorganic filler in the first non-foamable resin layer 110 and the second non-foamable resin layer 120 is obtained. Characteristics, heat resistance, moisture resistance, and dimensional stability can be further improved. Further, by setting the content of the inorganic filler in the first non-foamable resin layer 110 and the second non-foamable resin layer 120 to be equal to or lower than the above upper limit value, the light weight and high rigidity of the polypropylene-based multilayer foamed molded body 200 can be improved.
  • the balance can be further improved, the moldability of the polypropylene-based multilayer foamed molded product 200 can be improved, and perforation and cutting of the polypropylene-based multilayer foamed molded product 200 can be suppressed.
  • a polypropylene-based multilayer foamed molded product 200 can be realized.
  • the first non-foamable resin layer 110 and the second non-foamable resin layer 120 have the same composition and have the same thickness.
  • the linear expansion coefficients of the first non-foamable resin layer 110 and the second non-foamable resin layer 120 can be made to be the same value, so that the dimensions are due to deformation such as warpage due to thermal stress or moisture absorption. It is possible to obtain a polypropylene-based multilayer foamed molded product 200 that can suppress the change more effectively and that is further superior in mechanical properties such as bending properties and tensile properties and heat resistance.
  • the first non-foamable resin layer 110 and the second non-foamable resin layer 120 include a heat stabilizer, an antioxidant, an ultraviolet absorber, a pigment, an antistatic agent, and copper damage prevention as necessary.
  • the polypropylene-based multilayer foamed molded product 200 according to the present embodiment is composed of, for example, an inorganic filler-containing thermoplastic resin composition containing an inorganic filler and a thermoplastic resin on both surfaces of the polypropylene-based foamed molded product 100 according to the present embodiment. It can be obtained by forming a resin layer.
  • inorganic filler-containing thermoplastic resin composition according to the present embodiment, each component is mixed or melted by dry blend, tumbler mixer, Banbury mixer, single screw extruder, twin screw extruder, high speed twin screw extruder, hot roll, etc. -It can be prepared by kneading.
  • the method for molding the polypropylene-based multilayer foamed molded product 200 according to the present embodiment can be performed by a known method using, for example, a multilayer extruder or a lamination molding machine.
  • the polypropylene-based multilayer foamed molded product 200 forms, for example, a foam-molded polypropylene-based resin composition for forming the polypropylene-based foamed layer 100, and the first non-foamable resin layer 110 and the second non-foamable resin layer 120.
  • the inorganic filler-containing thermoplastic resin composition to be obtained is supplied from the main extruder of the multilayer extruder and the hopper of the sub-extruder and is multilayer-extruded into a sheet form from the tip of the T die.
  • the polypropylene-based multilayer foamed molded body 200 is formed by separately molding the polypropylene-based foamed layer 100, the first non-foamable resin layer 110, and the second non-foamable resin layer 120, and laminating them to heat-mold them. Can also be obtained.
  • a polyolefin resin having a low melting point is formed between the polypropylene foam layer 100 and the first non-foamable resin layer 110 or between the polypropylene foam layer 100 and the second non-foamable resin layer 120.
  • a thermal adhesive layer may be interposed.
  • the polyolefin resin having such a low melting point is not particularly limited.
  • a polypropylene resin can be used, and a random copolymer of propylene and ⁇ -olefin is preferable.
  • the polypropylene-based multilayer foamed molded product 200 Since the polypropylene-based multilayer foamed molded product 200 according to the present embodiment has an excellent performance balance between lightness and mechanical properties, it is an alternative to a wooden board, particularly a high-rigidity wooden board such as a hard board or a medium density fiber board. It can be used as a product.
  • the separation column two trade names “TSKgel GMH6-HT” and two trade names “TSKgel GMH6-HTL” were used.
  • the column sizes are 7.5 mm in inner diameter and 300 mm in length, the column temperature is 140 ° C., the mobile phase is o-dichlorobenzene (manufactured by Wako Pure Chemical Industries, Ltd.), and the antioxidant is BHT (Wako Pure Chemical Industries, Ltd.). (0.025% by weight).
  • the mobile phase was moved at a rate of 1.0 ml / min, the sample injection volume was 400 ⁇ l, and a differential refractometer was used as a detector.
  • Standard polystyrene was manufactured by Tosoh Corporation.
  • the molecular weight is a value converted into a polypropylene resin after universal calibration.
  • flexural modulus of polypropylene-based foamed (multilayer) sheet was determined by referring to the flexural strength test described in JIS A5905 at an environment of 23 ° C. and 50% RH. Below, test piece thickness: 3 mm, test piece width: 50 mm, test piece length: 150 mm, span distance: 100 mm, bending speed: 50 mm / min. The average value was adopted.
  • Young's modulus of the polypropylene-based foamed (multilayer) sheet is 23 ° C. and 50% RH environment, and the specimen shape: strip shape, specimen width: 10 mm The distance between chucks was 50 mm, the tensile speed was 20 mm / min, one point was measured for each of the MD direction and the TD direction, and the average value thereof was adopted.
  • Arithmetic mean roughness Ra of the polypropylene-based foamed (multi-layer) sheet surface The arithmetic average roughness Ra of the surface of the polypropylene-based foamed (multilayer) sheet is based on JIS-B0601-1994, and is a surface roughness measuring machine manufactured by Tokyo Seimitsu Co., Ltd. (model: E-MD-S189A, stylus tip shape (tip Radius: 2 ⁇ m, 60 ° cone, material: diamond)), evaluation length: 10 mm, measurement speed: 0.3 mm / second, cut-off value: 0.8 mm, measurement direction: parallel to the TD direction of the sheet surface Measured under various orientation conditions.
  • Water content of inorganic filler was calculated by the following method. First, moisture generated by heating the inorganic filler at 200 ° C. for 15 minutes in a nitrogen stream (100 ml / min) was quantified by Karl Fischer coulometric titration. Next, the moisture content of the inorganic filler was calculated from the obtained moisture content.
  • Polypropylene resin PP1 Propylene homopolymer (VP103W manufactured by Prime Polymer, MFR: 3 g / 10 min, Mz / Mw value: 14)
  • PP Mica MB manufactured by Shiraishi Calcium Co., Ltd., Brand: HIFILLMER MAT-MPH80-60 (MFR: 3 g / 10 min, composition: containing 20% by mass of polypropylene composed of block copolymer and 80% by mass of mica, water content of mica) : 0.20% by mass) was heated at 120 ° C. for 18 hours, and the water content of mica was reduced to 0.075% by mass)
  • PP calcium carbonate MB produced by Toyo Ink Co., Ltd., brand: PPM10245AL (containing 20% by mass of propylene homopolymer and 80% by mass of calcium carbonate) heated at 120 ° C. for 18 hours
  • PPM10245AL containing 20% by mass of propylene homopolymer and 80% by mass of calcium carbonate
  • each raw material was dry blended with the formulation shown in Table 1 (the unit in the table is parts by mass), the resulting mixture was put into a hopper, and further from the carbon dioxide supply device to the middle of the cylinder of the extruder (position) 17.5D) was injected with carbon dioxide at a pressure of 10 to 19 MPa. At this time, the injection amount of carbon dioxide gas was adjusted to 0.17 to 0.33 mass% with respect to the extrusion amount.
  • Each component raw material is melted and kneaded under the conditions of a temperature of 173 to 193 ° C.
  • Example 7 to 10 Each raw material was put into the hopper with the formulation shown in Table 2 (units in the table are parts by mass) into the extrusion molding machine used in Examples 1 to 6, cylinder temperature 205 to 215 ° C, die temperature 220 ° C, screw rotation Each raw material was melted and kneaded under the condition of several 22 to 28 rpm, and extruded from a T-die at a resin temperature of 229 to 231 ° C. of the cylinder head so that the extrusion rate was 8 to 13 kg / hour.
  • the extruded foam sheet was taken up at a take-up speed of 1.0 m / min using a take-up machine, and polypropylene-based non-foamed sheets 1 to 4 having a sheet width of 290 to 300 mm were obtained.
  • polypropylene-based foamed multilayer sheets having the layer structure shown in Table 3 were produced and evaluated. The obtained results are shown in Table 3, respectively.
  • the polypropylene-based foamed multilayer sheet was laminated by inserting a thermal adhesive layer (a polypropylene film made of a random copolymer having a melting point of 139 ° C., thickness: 0.07 mm) between the layers.
  • a polyimide film having a mirror surface (arithmetic mean roughness Ra is 0.1 ⁇ m or less and thickness is 0.1 mm).
  • the hot pressing was performed at a temperature of 150 ° C. and a pressure of 2.5 MPa for 8 minutes, and then the hot pressing was performed at a temperature of 150 ° C. and a pressure of 10 MPa for 1 minute. Then, the multilayer sheet containing the upper and lower polyimide films was inserted into a cooling press apparatus and cooled at a temperature of 25 ° C.
  • the metal frame of thickness 3mm used as a spacer was previously arrange
  • the polypropylene foamed sheets of Examples 1 to 6 and the polypropylene foamed multilayer sheets of Examples 7 to 10 using talc having a water content of 0.10% by mass or less are It was found that the appearance was excellent. In addition, the density and flexural modulus showed the same level as that of wood boards such as hard boards and medium density fiber boards, and it was found that the performance balance of light weight and mechanical properties was excellent. That is, it can be understood that the polypropylene foam molded body 100 according to the present embodiment is suitable as a substitute for the wooden board. On the other hand, the polypropylene foam sheets of Comparative Examples 1 to 8 were all inferior in appearance. In addition, the polypropylene foam sheet of Comparative Example 9 had a poor performance balance between lightness and mechanical properties, and was not suitable as a substitute for a wooden board.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Mechanical Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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Abstract

L'invention concerne une composition de résine à base de polypropylène pour moulage de mousse, qui comprend une résine à base de polypropylène et une charge inorganique. La charge inorganique comprend au moins un type choisi parmi le talc ou la silice, et la teneur en eau de la charge inorganique n'est pas supérieure à 0,10% en masse de la totalité de la charge inorganique.
PCT/JP2017/036833 2016-10-31 2017-10-11 Composition de résine à base de polypropylène pour moulage de mousse, corps moulé en mousse à base de polypropylène, corps moulé en mousse multicouche à base de polypropylène, et procédé de production de corps moulé en mousse à base de polypropylène WO2018079261A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10330522A (ja) * 1997-05-29 1998-12-15 Denki Kagaku Kogyo Kk 熱可塑性樹脂発泡シート及び容器
JPH1180402A (ja) * 1997-09-05 1999-03-26 Denki Kagaku Kogyo Kk 熱可塑性樹脂発泡シート及び容器
JP2001192515A (ja) * 2000-01-11 2001-07-17 Du Pont Mitsui Polychem Co Ltd ポリプロピレン組成物
JP2002105874A (ja) * 2000-10-03 2002-04-10 Toppan Printing Co Ltd オレフィン系床材
JP2004122717A (ja) * 2002-10-07 2004-04-22 Kanegafuchi Chem Ind Co Ltd ポリプロピレン系樹脂押出発泡シート、その製造方法、およびその成形体
JP2004306405A (ja) * 2003-04-07 2004-11-04 Toppan Printing Co Ltd 木質樹脂発泡成形体及び化粧材

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10330522A (ja) * 1997-05-29 1998-12-15 Denki Kagaku Kogyo Kk 熱可塑性樹脂発泡シート及び容器
JPH1180402A (ja) * 1997-09-05 1999-03-26 Denki Kagaku Kogyo Kk 熱可塑性樹脂発泡シート及び容器
JP2001192515A (ja) * 2000-01-11 2001-07-17 Du Pont Mitsui Polychem Co Ltd ポリプロピレン組成物
JP2002105874A (ja) * 2000-10-03 2002-04-10 Toppan Printing Co Ltd オレフィン系床材
JP2004122717A (ja) * 2002-10-07 2004-04-22 Kanegafuchi Chem Ind Co Ltd ポリプロピレン系樹脂押出発泡シート、その製造方法、およびその成形体
JP2004306405A (ja) * 2003-04-07 2004-11-04 Toppan Printing Co Ltd 木質樹脂発泡成形体及び化粧材

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