WO2017155114A1 - 発泡樹脂成形体及びその製造方法 - Google Patents
発泡樹脂成形体及びその製造方法 Download PDFInfo
- Publication number
- WO2017155114A1 WO2017155114A1 PCT/JP2017/009805 JP2017009805W WO2017155114A1 WO 2017155114 A1 WO2017155114 A1 WO 2017155114A1 JP 2017009805 W JP2017009805 W JP 2017009805W WO 2017155114 A1 WO2017155114 A1 WO 2017155114A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyamide
- resin
- melt
- olefin
- mass
- Prior art date
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- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 130
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 21
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/22—Mixtures comprising a continuous polymer matrix in which are dispersed crosslinked particles of another polymer
Definitions
- the present invention relates to a foamed resin molded article having excellent impact resistance and a method for producing the same.
- Patent Document 1 discloses a foamed resin molded body containing polypropylene, the surface of which is formed of a skin layer and the inside of which is formed of a foam layer.
- the foam layer includes a plurality of first foam cells,
- Patent Document 2 discloses that a melt flow rate measured at a temperature of 190 ° C.
- the present invention is shown below.
- a foamed resin molded article comprising an olefin resin composition containing an olefin resin and a polyamide resin
- the olefin resin composition comprises a continuous phase containing the olefin resin, and a dispersed phase containing a polyamide resin dispersed in the continuous phase
- the foamed resin molded article wherein the dispersed phase contains a melt-kneaded product of the polyamide resin and an elastomer having a reactive group for the polyamide resin.
- the dispersed phase has a matrix phase containing the polyamide resin and a finely dispersed phase containing the reactive elastomer dispersed in the matrix phase.
- the polyamide resin is polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 614, polyamide 11, polyamide 12, polyamide 6T, polyamide 6I, polyamide 9T, polyamide M5T, polyamide 1010, polyamide 1012, polyamide 10T, [1] to [4] which are at least one selected from polyamide MXD6, polyamide 6T / 66, polyamide 6T / 6I, polyamide 6T / 6I / 66, polyamide 6T / 2M-5T and polyamide 9T / 2M-8T
- the foamed resin molded product according to any one of the above.
- a first melt-kneading step of melt-kneading a polyamide resin and an elastomer having a reactive group for the polyamide resin, a first melt-kneaded product obtained by the first melt-kneading step, and an olefin resin are melt-kneaded.
- a production raw material obtained by a method comprising a second melt-kneading step and a mixing step of mixing the second melt-kneaded product obtained by the second melt-kneading step and an olefin resin is foamed.
- the manufacturing method of a foamed resin molding is described in any one of [1] to [7]
- a first melt-kneading step of melt-kneading a polyamide resin and an elastomer having a reactive group for the polyamide resin, a first melt-kneaded product obtained by the first melt-kneading step, and an olefin resin are melt-kneaded.
- the foamed resin molded article of the present invention is superior in impact resistance and rigidity as compared with a foamed molded article made of an olefin resin, and is hardly broken even when subjected to a high impact. Therefore, it is suitable for a wide range of applications such as automobile-related parts, ship-related parts, aviation-related parts, office parts, daily goods, kitchenware, building material parts, sports goods, and the like.
- the dispersed phase has a matrix phase containing the polyamide resin, and a finely dispersed phase containing the reactive elastomer dispersed in the matrix phase, and foamed bubbles are formed in the dispersed phase and When it is not the finely dispersed phase but only the continuous phase, it has a multi-phase structure, and it can be a foamed resin molded article with excellent impact resistance, and it can be impact resistant while maintaining the phase structure.
- a foamed resin molded body having When the ratio of the dispersed phase is 70% by mass or less when the total of the continuous phase and the dispersed phase is 100% by mass, excellent impact resistance, rigidity and moldability can be obtained in a balanced manner. Can do.
- the polyamide resin is polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 614, polyamide 11, polyamide 12, polyamide 6T, polyamide 6I, polyamide 9T, polyamide M5T, polyamide 1010, polyamide 1012, polyamide 10T, polyamide MXD6, Foam with excellent impact resistance when at least one selected from polyamide 6T / 66, polyamide 6T / 6I, polyamide 6T / 6I / 66, polyamide 6T / 2M-5T and polyamide 9T / 2M-8T
- the resin molding can be selected from the above polyamides.
- the elastomer having the reactive group is an olefinic thermoplastic elastomer containing a structural unit derived from ethylene or propylene or a styrene thermoplastic elastomer containing a structural unit derived from an aromatic vinyl compound, Since the phase structure can be obtained more reliably, a foamed resin molded product that can exhibit excellent impact resistance can be obtained.
- the elastomer having the reactive group is at least one selected from an acid anhydride-modified elastomer, a carboxylic acid-modified elastomer, an epoxy-modified elastomer, and an oxazoline-modified elastomer
- a foamed resin molded with excellent impact resistance The body can be selected from the above elastomers. According to the method for producing a foamed resin molded body of the present invention, it is possible to efficiently obtain a foamed resin molded body that is not easily broken even when subjected to a high impact and has excellent appearance.
- the foamed resin molding of this invention provided with a mixing process, it can obtain at low cost, maintaining the outstanding impact resistance.
- a polyolefin resin suitable for producing the second melt-kneaded product or a polyolefin resin suitable for foaming is used. Can be used properly.
- the fluidity of the olefin resin used in the mixing step is higher than the fluidity of the olefin resin used in the second melt-kneading step, the fluidity in the mold is good during injection molding.
- the foamed resin molded body (1) of the present invention contains an olefin resin (hereinafter referred to as “olefin resin (A)”) and a polyamide resin (hereinafter referred to as “polyamide resin (B)”).
- olefin resin (A) olefin resin
- polyamide resin (B) polyamide resin
- An olefin resin composition having a structure that is, a continuous phase (X) containing the olefin resin (A), and a dispersed phase (Y) containing a polyamide resin dispersed in the continuous phase (X),
- the dispersed phase (Y) includes a melt-kneaded product of a polyamide resin (B) and an elastomer having a reactive group for the polyamide resin (B) (hereinafter referred to as “modified elastomer”) (FIG. 1).
- modified elastomer modified elastomer
- the foamed resin molded article of the present invention has a skin layer and a cell wall, and these parts are formed of the olefin-based resin composition.
- the olefin resin composition is preferably a thermoplastic resin composition.
- the continuous phase (X) constituting the olefin-based resin composition includes the olefin resin (A), and may further include other resins (described later) depending on the purpose, application, and the like.
- the structure of the said continuous phase is not specifically limited, Either a crosslinked structure and a non-crosslinked structure may be sufficient.
- the said olefin resin (A) is not specifically limited,
- the conventionally well-known polyolefin used for formation of a molded article can be used.
- ethylene homopolymer, copolymer of ethylene and unsaturated hydrocarbon having 3 or more carbon atoms hereinafter referred to as “ ⁇ -olefin”
- ⁇ -olefin copolymer of ethylene and unsaturated hydrocarbon having 3 or more carbon atoms
- ⁇ -olefin ethylene homopolymer, copolymer of ethylene and unsaturated hydrocarbon having 3 or more carbon atoms
- ⁇ -olefin copolymer etc. which consist of the above can be used individually or in combination of 2 or more types.
- the ⁇ -olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 3-methyl-1-butene and 4-methyl-1-pentene.
- the olefin resin (A) is preferably a homopolymer or copolymer of ⁇ -olefin, such as polypropylene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene / 1-butene copolymer.
- a polymer is more preferable, and a polymer including a structural unit derived from propylene is particularly preferable.
- the olefin resin preferably contains two or more different olefin resins from the viewpoint of foam moldability.
- olefin resins having high fluidity of the other olefin resin can be employed relative to one olefin resin. This difference in fluidity can be evaluated by the level of fluidity when compared at a constant temperature and a shear rate of 0 sec ⁇ 1 .
- different olefin resins having an MFR (temperature 230 ° C., 2.16 kg load) difference of 15 g / 10 min or more (usually 60 g / 10 min or less) can be adopted, and furthermore, as an olefin resin having low fluidity
- An olefin resin having an MFR (temperature 230 ° C., 2.16 kg load) of 30 g / 10 min or less (usually 1 g / 10 min or more) can be adopted, and MFR (temperature 230 ° C., 2.16 kg load) is used as an olefin resin having high fluidity.
- An olefin resin of 45 g / 10 min or more (usually 90 g / 10 min or less) can be employed.
- a propylene homopolymer can be employed as the olefin resin having low fluidity
- a propylene block polymer can be employed as the olefin resin having high fluidity.
- the weight average molecular weight (polystyrene conversion) of the olefin resin (A) by gel permeation chromatography (GPC) is preferably 10,000 from the viewpoint of the stability, impact resistance and rigidity of the foam cell of the foam resin molding. To 500,000, more preferably 100,000 to 450,000, and still more preferably 200,000 to 400,000.
- the continuous phase (X) may be composed only of the olefin resin (A), and as described above, as long as the continuous phase is formed together with the olefin resin (A), it further includes other resins. There may be. In the latter case, the other resin is preferably a resin that is compatible with the olefin resin (A) and incompatible with the polyamide resin (B). Although the said continuous phase contains a dispersed phase, you may contain the additive mentioned later in a dispersed state.
- the dispersed phase (Y) includes a melt-kneaded product of the polyamide resin (B) and the modified elastomer. A preferred structure of this dispersed phase will be described later.
- the polyamide resin (B) is not particularly limited as long as it has an amide bond (—NH—CO—) in the main chain, and conventionally known methods such as ring-opening polymerization of lactams, dehydration of amino acids. Resins obtained by condensation, polycondensation of diamine and dicarboxylic acid, polycondensation of aminocarboxylic acid, or the like can be used alone or in combination of two or more.
- the said polyamide resin (B) may use each raw material compound independently, and is obtained using two or more. It may be.
- lactams include ⁇ -caprolactam, undecane lactam, and ⁇ -lauryl lactam.
- amino acid include aminocaproic acid, aminoundecanoic acid, aminododecanoic acid, and paraaminomethylbenzoic acid.
- diamine examples include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1, 10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1, 17-diaminoheptadecane, 1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane, 2-methyl-1,5-diaminopentane, 2-methyl-1
- dicarboxylic acid examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassic acid, tetradecanedioic acid, pentadecanedioic acid.
- Examples thereof include aliphatic dicarboxylic acids such as acid and octadecanedioic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as orthophthalic acid, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid.
- polyamide resin (B) examples include polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 614, polyamide 11, polyamide 12, polyamide 6T, polyamide 6I, polyamide 9T, polyamide M5T, polyamide 1010, Polyamide 1012, Polyamide 10T, Polyamide MXD6, Polyamide 6T / 66, Polyamide 6T / 6I, Polyamide 6T / 6I / 66, Polyamide 6T / 2M-5T, Polyamide 9T / 2M-8T, and the like. These resins may be used alone or in combination of two or more. In the present invention, the polyamide 11 is particularly preferable, and both the embodiment in which the polyamide 11 is used alone and the embodiment in which the polyamide 11 and another polyamide resin are used in combination are preferable.
- polyamide 11, polyamide 610, polyamide 1010, polyamide 614 and polyamide 10T are plant-derived polyamide resins.
- the plant-derived polyamide resin is a resin that uses a monomer obtained from a plant-derived component such as vegetable oil, and is therefore desirable from the viewpoint of environmental protection (particularly from the viewpoint of carbon neutral).
- the polyamide 11 has a structure in which a monomer having 11 carbon atoms is bonded through an amide bond.
- aminoundecanoic acid made from castor oil can be used as a monomer.
- the content ratio of the structural unit derived from the monomer having 11 carbon atoms is preferably 50% or more of all the structural units of the polyamide 11, and may be 100%.
- the polyamide 610 has a structure in which a monomer having 6 carbon atoms and a monomer having 10 carbon atoms are bonded through an amide bond.
- sebacic acid using castor oil as a raw material can be used as a monomer.
- the total content of the structural unit derived from the monomer having 6 carbon atoms and the structural unit derived from the monomer having 10 carbon atoms is 50% or more of all the structural units of polyamide 610 It is preferable that it may be 100%.
- the polyamide 1010 has a structure in which a diamine having 10 carbon atoms and a dicarboxylic acid having 10 carbon atoms are copolymerized.
- 1,10-decanediamine (decamethylenediamine) and sebacic acid made from castor oil can be used as monomers.
- the total of the structural unit derived from the diamine having 10 carbon atoms and the structural unit derived from the dicarboxylic acid having 10 carbon atoms may be 50% or more of the total structural units of the polyamide 1010. Preferably, it may be 100%.
- the polyamide 614 has a structure in which a monomer having 6 carbon atoms and a monomer having 14 carbon atoms are bonded through an amide bond.
- a dicarboxylic acid derived from a plant and having 14 carbon atoms can be used as a monomer.
- the total of the structural units derived from the monomer having 6 carbon atoms and the structural units derived from the monomer having 14 carbon atoms is 50% or more of the total structural units of polyamide 614. It is preferable that it may be 100%.
- the polyamide 10T has a structure in which a diamine having 10 carbon atoms and terephthalic acid are bonded through an amide bond.
- 1,10-decanediamine (decamethylenediamine) using castor oil as a raw material can be used as a monomer.
- These structural units derived from diamines having 10 carbon atoms and structural units derived from terephthalic acid are preferably 50% or more of all structural units of polyamide 10T, even if they are 100%. Good.
- polyamide 11 is superior to the other four kinds of plant-derived polyamide resins in terms of low water absorption, low specific gravity, and high degree of planting.
- Polyamide 610 is inferior to polyamide 11 in terms of water absorption, chemical resistance and impact strength, but is superior in terms of heat resistance (melting point) and rigidity (strength). Furthermore, since it has low water absorption and good dimensional stability compared to polyamide 6 and polyamide 66, it can be used as an alternative to polyamide 6 and polyamide 66.
- Polyamide 1010 is superior to polyamide 11 in terms of heat resistance and rigidity. Furthermore, the degree of planting is equivalent to that of polyamide 11 and can be used for parts that require more durability. Since polyamide 10T includes an aromatic ring in the molecular skeleton, it has a higher melting point and higher rigidity than polyamide 1010. Therefore, it can be used in harsh environments (heat-resistant part, strength input part).
- the modified elastomer has a reactive group for the polyamide resin (B).
- the reactive group include an acid anhydride group (—CO—O—OC—), a carboxyl group (—COOH), and Examples thereof include an epoxy group (—C 2 O (a three-membered ring structure composed of two carbon atoms and one oxygen atom)), an oxazoline group (—C 3 H 4 NO), an isocyanate group (—NCO), and the like.
- the reactive group contained in the modified elastomer may be only one type or two or more types.
- the modification amount (the number of reactive groups) of the modified elastomer is not particularly limited, and is preferably 1 to 50, more preferably 3 to 30, and still more preferably 5 to 20.
- the modified elastomer is a modified elastomer made of a (co) polymer obtained using a monomer having a reactive group, and obtained by forming a reactive group by oxidative decomposition of the (co) polymer.
- modified elastomers modified elastomers obtained by graft polymerization using an organic acid for a (co) polymer, and the like. It can be used alone or in combination of two or more.
- the modified elastomer is preferably an olefin-based thermoplastic elastomer or a styrene-based thermoplastic elastomer provided with the reactive group.
- the olefin-based thermoplastic elastomer is preferably an ⁇ -olefin copolymer containing a structural unit derived from an ⁇ -olefin having 3 to 8 carbon atoms, more preferably a structure derived from ethylene or propylene.
- Non-conjugated dienes include linear acyclic diene compounds such as 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,6-hexadiene; 5-methyl-1,4-hexadiene 3,7-dimethyl-1,6-octadiene, 5,7-dimethylocta-1,6-diene, 3,7-dimethyl-1,7-octadiene, 7-methylocta-1,6-diene, dihydromil Branched acyclic diene compounds such as sen; tetrahydroindene, methyltetrahydroindene, dicyclopentadiene, bicyclo [2.2.1] -hepta-2,5-diene, 5-methylene-2-
- thermoplastic elastomer examples include an ethylene / propylene copolymer, an ethylene / 1-butene copolymer, an ethylene / 1-pentene copolymer, an ethylene / 1-hexene copolymer, and an ethylene / 1-octene copolymer. And a propylene / 1-butene copolymer, a propylene / 1-pentene copolymer, a propylene / 1-hexene copolymer, and a propylene / 1-octene copolymer. Ethylene / propylene copolymers, ethylene / 1-butene copolymers and ethylene / 1-octene copolymers are preferred.
- the weight average molecular weight (polystyrene conversion) of the olefinic thermoplastic elastomer by gel permeation chromatography (hereinafter referred to as “GPC”) is preferably 10,000 to 500,000, more preferably 20,000 to 500,000. More preferably, it is 30,000 to 300,000.
- styrenic thermoplastic elastomer examples include a block copolymer of an aromatic vinyl compound and a conjugated diene compound and a hydrogenated product thereof.
- the aromatic vinyl compound may be at least one selected from alkylstyrenes such as styrene, ⁇ -methylstyrene, p-methylstyrene, p-tert-butylstyrene; p-methoxystyrene, vinylnaphthalene, and the like. .
- the conjugated diene compound is selected from butadiene, isoprene, 1,3-pentadiene, methylpentadiene, phenylbutadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-diethyl-1,3-octadiene, and the like. At least one of them.
- styrenic thermoplastic elastomer examples include styrene / butadiene / styrene copolymer (SBS), styrene / isoprene / styrene copolymer (SIS), styrene / ethylene / butylene / styrene copolymer (SEBS), and styrene / ethylene.
- SBS styrene / butadiene / styrene copolymer
- SIS styrene / isoprene / styrene copolymer
- SEBS styrene / ethylene / butylene / styrene copolymer
- SEPS Propylene / styrene copolymer
- the modified elastomer is a modified product of an olefin-based thermoplastic elastomer, and is selected from an acid anhydride-modified olefin elastomer, a carboxylic acid-modified olefin elastomer, an epoxy-modified olefin elastomer, and an oxazoline-modified olefin elastomer. At least one kind. Of these, acid anhydride-modified olefin elastomers and carboxylic acid-modified olefin elastomers are particularly preferred. Hereinafter, these are referred to as “acid-modified olefin elastomers”.
- the acid-modified olefin elastomer is preferably an elastomer modified with an acid anhydride or carboxylic acid and having an acid anhydride group or a carboxyl group at the side chain or terminal of the molecule.
- the number of acid anhydride groups or carboxyl groups contained in one molecule of acid-modified olefin elastomer is preferably 1 from the viewpoints of stability, impact resistance and rigidity of the foamed cell of the foamed resin molded article. More preferably, it is 2 to 50, more preferably 3 to 30, particularly preferably 5 to 20.
- acid anhydrides for acid modification include maleic anhydride, phthalic anhydride, itaconic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, butenyl succinic anhydride, and the like. It is done. Of these, maleic anhydride, phthalic anhydride and itaconic anhydride are preferred.
- carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid and the like.
- the acid-modified olefin-based elastomer is preferably an elastomer modified with an acid anhydride.
- the acid-modified olefin elastomers can be used alone or in combination of two or more.
- a compound having a polymerizable unsaturated bond and an epoxy bond such as a glycidyl ester of ⁇ , ⁇ -unsaturated acid
- the modifying compound used when the epoxy-modified olefin elastomer is used is used.
- the modifying compound used when the oxazoline-modified olefin elastomer is used a compound having a polymerizable unsaturated bond and an oxazolyl group such as a vinyl oxazoline compound can be used.
- the weight average molecular weight (polystyrene conversion) of the modified elastomer by GPC is preferably 10,000 to 500,000, more preferably 35,000 to 500,000, and further preferably 35,000 to 300,000.
- the polyamide resin is preferably 0.3 to 60% by mass, preferably 0.00. 5 to 55% by mass, more preferably 1 to 50% by mass, still more preferably 1.5 to 40% by mass, still more preferably 2 to 30% by mass, particularly preferably 2.5 to 20% by mass, most preferably 3 to 15% by mass.
- the modified elastomer is preferably 0.2 to 55% by mass, preferably 0.4 to 50% by mass, more preferably 0.8 to 45% by mass, still more preferably 1.2 to 35% by mass, and still more.
- the amount is preferably 1.5 to 25% by mass, particularly preferably 1.8 to 17% by mass, and most preferably 2 to 12% by mass.
- the olefin resin is preferably 50 to 99.5% by mass, more preferably 57 to 98% by mass, still more preferably 62 to 96% by mass, still more preferably 67 to 95% by mass, and particularly preferably 72 to 94%. % By mass, most preferably 75 to 93% by mass.
- the dispersed phase (Y) is preferably 10 to 80% by mass and more preferably 20 to 90% by mass, respectively, when the total of the polyamide resin (B) and the modified elastomer is 100% by mass. Is 12 to 78% by mass and 22 to 88% by mass, more preferably 14 to 75% by mass and 25 to 86% by mass, still more preferably 20 to 70% by mass and 30 to 80% by mass, and particularly preferably 50 to 65% by mass. % And 35-50% by mass and melt-kneaded at a quantitative ratio.
- the dispersed phase (Y) is preferably a finely dispersed phase comprising a reaction product of a part of the polyamide resin (B) and a modified elastomer in a matrix phase (Y 1 ) containing the polyamide resin (B).
- (Y 2) having a structure including a (see FIG. 1).
- the parent phase (Y 1 ) may be a phase composed only of the polyamide resin (B), and may further contain other resins (excluding the olefin resin (A)) depending on the purpose and application. Good.
- the other resin is preferably a resin having compatibility with the polyamide resin (B) and incompatible with the polyolefin resin (A).
- the structure of the said mother phase is not specifically limited, Either a crosslinked structure and a non-crosslinked structure may be sufficient.
- the olefin resin constituting the continuous phase (X) is foamed. That is, the foamed resin molded article (1) is composed of an olefin resin composition, and this olefin resin composition is composed of a continuous phase (X) and a dispersed phase (Y) dispersed in the continuous phase (X). ). Furthermore, the olefin-based resin composition includes bubbles (Z). The bubble (Z) may be located anywhere, but preferably exists in the continuous phase (X). In this case, in other words, it can be said that the dispersed phase (Y) and the bubbles (Z) are dispersed in the continuous phase (X).
- the dispersed phase (Y) is a matrix phase containing a polyamide resin (Y 1 ) and a finely dispersed phase containing an elastomer dispersed in the matrix phase (Y 1 ).
- (Y 2) and has, foamed bubbles (Z) is the dispersed phase (Y) and finely dispersed phase (Y 2) rather than, particularly preferably in the form which is only the continuous phase (X) ( (See FIG. 1).
- the foamed resin molded body of the present invention has an impact resistance because foaming is performed while maintaining a phase structure (salami structure) such as a dispersed phase (Y) or a finely dispersed phase (Y 2 ). Excellent.
- the general shape of the dispersed phase (Y) and the finely dispersed phase (Y 2 ) is not limited.
- a substantially circular cross section three-dimensionally substantially spherical shape.
- FIG. 1B it may be a shape that is deformed (elongated) into a substantially elliptical shape or a flat shape as the bubble (Z) is formed.
- a co-continuous phase composed of a continuous phase A1 composed of a first resin and a continuous phase A2 composed of a second resin can be taken.
- the co-continuous phase refers to a structure in which two or more kinds of continuous phases (continuous phases A1 and A2) are continuously connected three-dimensionally.
- the matrix phase (Y 1 ) includes a finely dispersed phase (Y 2 ) composed of a melt-kneaded product of the polyamide resin (B) and the modified elastomer.
- the reaction product constituting the finely dispersed phase (Y 2 ) is an equimolar reaction product of the reactive group contained in the modified elastomer and the amide bond of the polyamide resin.
- the shape and size of the finely dispersed phase (Y 2 ) are not particularly limited, but from the viewpoints of stability, impact resistance and rigidity of the foamed cell of the foamed resin molded article, the average diameter (average particle diameter) is The thickness is 5 to 1200 nm, preferably 5 to 1000 nm, more preferably 5 to 600 nm, still more preferably 10 to 400 nm, and particularly preferably 15 to 350 nm.
- the average diameter of this finely dispersed phase (Y 2 ) can be a measured value obtained from an image of an electron microscope or the like. More specifically, the longest diameter obtained by measuring the longest diameter of each of 20 finely dispersed phases (Y 2 ) randomly selected from within a predetermined region in the magnified image of 1000 times or more described below. Is the first average value. Then, a further average value of the first average value measured at five different regions of the image, a finely dispersed phase above the average diameter of the (Y 2) (major axis average dispersion diameter).
- the treated surface of the test piece (the test piece of the foamed resin molding) subjected to the osmium coating treatment is further enlarged by a field emission scanning electron microscope (FE-SEM). Enlarged images can be used.
- the dispersed phase may include only the finely dispersed phase, or may further include an elastomer component.
- elastomer component a styrene elastomer, a non-modified olefin elastomer, or the like can be used.
- the dispersed phase may contain an additive described later in a dispersed state.
- the shape of the dispersed phase may be a regular shape such as a spherical shape or an elliptical spherical shape, or a deformed form (irregular shape) thereof, and may have a concave portion or a convex portion on the surface.
- the upper limit of the maximum diameter of the dispersed phase is preferably 10,000 nm, more preferably 8,000 nm, and still more preferably 4,000 nm, from the viewpoints of shape stability, impact resistance and rigidity of the foamed resin molded product. is there.
- a minimum is 50 nm normally, Preferably it is 100 nm.
- the maximum diameter can be a measured value obtained from an electron microscope image.
- the olefin-based resin composition includes a continuous phase and a dispersed phase dispersed in the continuous phase.
- the mass ratio of the continuous phase and the dispersed phase is preferably 30 masses when the total of both is 100 mass% from the viewpoint of stability, impact resistance, and rigidity of the foamed cell of the foamed resin molded body.
- % To 70% by mass more preferably 50 to 99.5% by mass and 0.5 to 50% by mass, still more preferably 52 to 98% by mass and 2 to 48% by mass, particularly preferably 55 to 96% by mass. And 4 to 45% by mass.
- the dispersed phase may be included as it is in the continuous phase, or in a state having a modified layer at least at a part of the interface between the continuous phase and the dispersed phase. May be.
- the modified layer may be made of a modified elastomer or a styrene elastomer. These materials may be those described above.
- the thickness of the modified layer is not particularly limited.
- the foamed resin molded body of the present invention includes a skin layer and a cell wall made of the olefin resin composition.
- the thickness of the skin layer is not particularly limited, but is preferably 0.2 to 0.8 mm, more preferably 0.3 to 0, from the viewpoint of the stability, impact resistance, and rigidity of the foamed cell of the foamed resin molding. .6 mm.
- additives that the continuous phase or dispersed phase can contain include nucleating agents, antioxidants, heat stabilizers, weathering agents, light stabilizers, plasticizers, ultraviolet absorbers, antistatic agents, flame retardants, Examples thereof include slip agents, antiblocking agents, antifogging agents, lubricants, pigments, dyes, dispersants, copper damage prevention agents, neutralizing agents, antifoaming agents, weld strength improvers, natural oils, synthetic oils, waxes and the like.
- nucleating agent examples include silicates such as talc, silica, clay, montmorillonite and kaolin; carbonates such as calcium carbonate, lithium carbonate and magnesium carbonate; metal oxides such as alumina, titanium oxide and zinc oxide; aluminum, Metals such as iron, silver and copper; hydroxides such as aluminum hydroxide and magnesium hydroxide; sulfides such as barium sulfate; carbides such as charcoal and bamboo charcoal; titanates such as potassium titanate and barium titanate; cellulose micro Examples thereof include celluloses such as fibrils and cellulose acetate; resin fibers such as polyethylene terephthalate fiber, nylon fiber, polyethylene naphthalate fiber, aramid fiber, vinylon fiber, and polyarylate fiber; carbons such as fullerene and carbon nanotube.
- silicates such as talc, silica, clay, montmorillonite and kaolin
- carbonates such as calcium carbonate, lithium carbonate and magnesium carbonate
- metal oxides such as alumina,
- antioxidant examples include phenol compounds, organic phosphite compounds, thioether compounds, and the like.
- examples of the heat stabilizer include hindered amine compounds.
- examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, and benzoate compounds.
- examples of the antistatic agent include nonionic compounds, cationic compounds, and anionic compounds.
- examples of the metal deactivator include hydrazine compounds and amine compounds.
- Examples of the flame retardant include halogen compounds, phosphorus compounds (nitrogen-containing phosphate compounds, phosphate esters, etc.), nitrogen compounds (guanidine, triazine, melamine, or derivatives thereof), inorganic compounds (metal hydroxides) Etc.), boron compounds, silicone compounds, sulfur compounds, red phosphorus compounds and the like.
- Examples of the flame retardant aid include antimony compounds, zinc compounds, bismuth compounds, magnesium hydroxide, and clay silicates.
- the foamed resin molded product of the present invention is obtained by foaming the olefin resin composition described above. That is, for example, the olefin resin composition can be obtained by chemical foaming or physical foaming using a foaming agent.
- This foamed resin molded body may be foamed by any method, and conventionally known methods can be used.
- a foaming agent if a foaming agent is a conventionally well-known thing, any of a decomposable foaming agent and a volatile foaming chemical
- medical agent a volatile foaming agent is included
- Specific compounds are described in “2. Method for producing foamed resin molded article”.
- the expansion ratio of the foamed resin molded article of the present invention is preferably 1.2 to 3.5 times, more preferably 1.3 to 2.5 times, still more preferably 1.4 to 2.0 times, particularly preferably. Is 1.5 to 1.8 times.
- the basis weight of the foamed resin molded article of the present invention is preferably 0.1 to 2.1 g / m 2 , more preferably 0.5 to 2.0 g / m 2 , and still more preferably 0.8 to 1. 9 g / m 2 , particularly preferably 1.0 to 1.8 g / m 2 .
- the solid portion volume in the foamed resin molded article and V 0, the hollow portion volume when the V 1, the expansion ratio is expressed by "(V 0 + V 1) / V 0 ".
- the total volume of the continuous phase (X) and the dispersed phase (Y) corresponds to the solid part volume V 0
- the volume of the bubbles (Z) corresponds to the hollow part volume V 1 .
- the foamed resin molded article of the present invention preferably has closed cells, and the foamed cell formed by the skin layer and the cell wall usually contains a decomposition gas or a volatile gas of the foaming agent.
- the size of the foam cell is not particularly limited, but in the foamed resin molded article of the present invention, fine foam cells are formed although the size is not uniform.
- the method for producing a foamed resin molded body includes a first melt-kneading step of melt-kneading a polyamide resin and an elastomer having a reactive group for the polyamide resin (modified elastomer),
- the production raw material obtained by a method (preparation method) comprising the first melt-kneaded product obtained by the first melt-kneading step and the second melt-kneading step of melt-kneading the olefin resin is foamed.
- the foaming in this manufacturing method should just be foamed as a result, for example, may be chemical foaming and may be physical foaming.
- blending another component can be further provided as needed.
- the production raw material is preferably a composition mainly containing a thermoplastic resin and containing a foaming agent for chemical foaming or a foaming agent for physical foaming (both described later).
- excluding an additive has the same structure as the olefin resin composition which comprises the foamed resin molding of the said invention.
- the manufacturing raw material in this case can contain other resin.
- the first melt-kneading step is preferably a step of melt-kneading the first raw material containing the polyamide resin and the modified elastomer.
- the first raw material can further include other resins, additives, and the like.
- the modified elastomer is preferably a modified product of an olefin-based thermoplastic elastomer, and in particular, a modified product of an ⁇ -olefin copolymer containing a structural unit derived from an ⁇ -olefin having 3 to 8 carbon atoms ( Acid anhydride-modified olefin elastomers, carboxylic acid-modified olefin elastomers, epoxy-modified olefin elastomers, oxazoline-modified olefin elastomers, etc.), and those described above are applied.
- the performance of the polyamide resin may vary depending on the type, and the preferred amount used for obtaining the effect of the present invention is shown below.
- the amount used is preferably 1 to 50% by mass, more preferably 5 to 40% by mass when the total of the polyamide resin, modified elastomer and olefin resin is 100% by mass. %, More preferably 10 to 35% by mass.
- polyamide 610 is used as the polyamide resin, the amount used is preferably 1 to 40% by mass, more preferably 5 to 40% by mass when the total of the polyamide resin, the modified elastomer and the olefin resin is 100% by mass. %, More preferably 10 to 40% by mass.
- the amount used is preferably 1 to 55% by mass, more preferably 10 to 55% by mass when the total of the polyamide resin, the modified elastomer and the olefin resin is 100% by mass. %, More preferably 15 to 55% by mass.
- the amount used is preferably 1 to 35% by mass, more preferably 5 to 35% by mass when the total of the polyamide resin, the modified elastomer and the olefin resin is 100% by mass. %, More preferably 10 to 35% by mass.
- the amount used is preferably 1 to 55% by mass, more preferably 5 to 55% by mass when the total of the polyamide resin, the modified elastomer and the olefin resin is 100% by mass. %, More preferably 10 to 55% by mass.
- the amount used is preferably 1 to 45% by mass, more preferably 5 to 45% by mass when the total of the polyamide resin, the modified elastomer and the olefin resin is 100% by mass. %, More preferably 10 to 45% by mass.
- the amount used is preferably 1 to 40% by mass, more preferably 5 to 40% by mass when the total of the polyamide resin, the modified elastomer and the olefin resin is 100% by mass. %, More preferably 10 to 40% by mass.
- the second melt-kneading step is a step of melt-kneading the second raw material containing the first melt-kneaded product obtained by the first melt-kneading step and the olefin resin.
- the second raw material can further include other resins, additives, and the like.
- the olefin resin (A) may be used as it is, and as the olefin resin (A), polypropylene and an ethylene / propylene copolymer are preferable.
- the olefin resin (A) polypropylene and an ethylene / propylene copolymer are preferable.
- block type polypropylene Alternatively, a mixed resin composed of polypropylene, polyethylene, and ethylene / propylene rubber (non-modified olefin elastomer) may be used.
- the above block type polypropylene (ie, propylene block polymer) may also be referred to as impact copolymer, polypropylene impact copolymer, heterophasic polypropylene, heterophasic block polypropylene, and the like.
- the melt kneading in the first melt kneading step and the second melt kneading step are all extruders (single screw extruders, twin screw kneading extruders, etc.), kneaders, mixers (high-speed fluid mixers, paddle mixers, ribbon mixers). Etc.).
- the polyamide resin and the modified elastomer may be melt-kneaded all at once, or may be performed while either one is divided and added.
- the kneading temperature is preferably 190 ° C to 250 ° C, more preferably 200 ° C to 230 ° C, still more preferably 205 ° C to 220 ° C.
- the melt-kneading of the second raw material containing the first melt-kneaded product and the olefin resin may be carried out all at once, while adding either one in a divided manner. You may go.
- the kneading temperature is preferably 190 ° C to 250 ° C, more preferably 200 ° C to 230 ° C, still more preferably 205 ° C to 220 ° C.
- the ratio of the polyamide resin, the modified elastomer and the olefin resin used in this method is not particularly limited.
- the total of the polyamide resin, the modified elastomer and the olefin resin contained in the above-described foamed resin molded product (olefin resin composition) is 100. What is necessary is just to mix
- the amounts of the polyamide resin, the modified elastomer and the olefin resin, which are the main components of the production raw material, in the first melt kneading step and the second melt kneading step are as follows.
- the amount of polyamide resin used is preferably 1 to 60% by mass, more preferably 3 to 50% by mass, still more preferably 5 to 45% by mass, and still more preferably. Is 7 to 40% by mass, particularly preferably 9 to 35% by mass, and most preferably 12 to 30% by mass.
- the amount of the modified elastomer used is preferably 1 to 70% by mass, more preferably 2 to 65% by mass. More preferably, it is 3 to 60% by mass, still more preferably 5 to 55% by mass, still more preferably 7 to 50% by mass, particularly preferably 13 to 47% by mass, and most preferably 17 to 45% by mass.
- the composition obtained by the first melt-kneading step and the second melt-kneading step can be used, and the second melt-kneaded product obtained by the second melt-kneading step is mixed with the olefin resin.
- a mixture obtained by performing the step (hereinafter referred to as “mixing step”) after the second melt-kneading step can be used.
- the mixing step the second melt-kneaded product and either one of the olefin resin and the foaming agent may be mixed, or the second melt-kneaded product, the olefin resin and foaming. You may mix both of an agent.
- the olefin resin used in the mixing step may be the same as or different from the olefin resin used in the second melt kneading step. That is, the foamed resin molded article of the present invention can also be obtained by foaming the olefin resin composition described above. Moreover, after adding a part of olefin resin contained in the above-mentioned olefin resin composition after addition, it can also obtain by foaming the obtained mixture.
- a mixing process is a process of mixing a 2nd melt-kneaded material and an olefin resin
- a 2nd melt-kneaded material and an olefin resin ( The post-added olefin resin) and the foaming agent may be mixed (dry blended) as they are.
- the post-added olefin resin containing the foaming agent previously blended (kneaded) in the post-added olefin Two melt-kneaded materials may be mixed (dry blended).
- olefin resins mean olefin resins of different types, or olefin resins of different fluidity and the like even if the types are the same.
- the olefin resin used in the mixing step should have a higher fluidity than the olefin resin used in the second melt-kneading step. preferable.
- the above-described difference in fluidity can be evaluated by the level of fluidity when compared at a constant temperature and a shear rate of 0 sec ⁇ 1 . Specifically, it can be compared by MFR (temperature 230 ° C., 2.16 kg load). That is, an olefin resin having a large relative MFR value can be said to be an olefin resin having a higher fluidity than the other olefin resin to be compared. In addition, an olefin resin having a small relative MFR value can be said to be an olefin resin having low fluidity with respect to the other olefin resin to be compared.
- MFR temperature 230 ° C., 2.16 kg load
- the MFR (temperature 230 ° C., 2.16 kg load) difference is not particularly limited, but can be 15 g / 10 min or more (usually 60 g / 10 min or less). Furthermore, the specific ranges of these MFR values are not particularly limited. For example, as a low-flowing olefin resin, MFR (temperature 230 ° C., 2.16 kg load) is 30 g / 10 min or less (usually 1 g / 10 min or more). ) Olefin resin.
- the high fluidity olefin resin an olefin resin having an MFR (temperature of 230 ° C., 2.16 kg load) of 45 g / 10 min or more (usually 90 g / 10 min or less) can be employed. Furthermore, a propylene homopolymer can be adopted as the low flow olefin resin, and a propylene block polymer can be adopted as the high flow olefin resin.
- MFR temperature of 230 ° C., 2.16 kg load
- a propylene homopolymer can be adopted as the low flow olefin resin
- a propylene block polymer can be adopted as the high flow olefin resin.
- the production method by chemical foaming is particularly suitable.
- the foamed resin molding which has the effect of this invention can be efficiently manufactured by using the manufacturing raw material obtained by dry blending a 2nd melt-kneaded material, an olefin resin, and a foaming agent.
- the ratio of the polyamide resin, the modified elastomer and the olefin resin used in this method is not particularly limited.
- the total of the polyamide resin, the modified elastomer and the olefin resin contained in the above-described foamed resin molded product (olefin resin composition) is 100. What is necessary is just to mix
- the proportion of the polyamide resin is preferably 0.5 to 30% by mass, more preferably 1 to 22% by mass, still more preferably 2 to 15% by mass
- the ratio of the modified elastomer is preferably 0.5 to 30% by mass, more preferably 1 to 22% by mass, and further preferably 2 to 15% by mass.
- the amount of the foaming agent used is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass when the total amount of polyamide resin, modified elastomer and olefin resin is 100 parts by mass. More preferably, it is 1 to 6 parts by mass.
- the foaming agent is preferably a decomposable foaming agent and will be described later.
- a predetermined production raw material is foamed to obtain a foamed resin molded body.
- foaming the production raw material conventionally known methods such as injection foam molding, press foam molding, extrusion foam molding, stampable foam molding, and heat foam molding can be applied.
- injection foam molding is preferred.
- any foaming method may be used, but when a foamed resin molded body is produced by chemical foaming, a production raw material containing a decomposable foaming agent is used.
- a foamed resin molded article is produced by physical foaming, a volatile foaming chemical or a production raw material including a capsule in which a volatile foaming chemical is enclosed is used.
- the gas in the atmosphere can be introduced into the production raw material as bubbles by mechanical stirring.
- the above decomposable foaming agent is preferably supplied to a non-molten production raw material to an injection molding machine and decomposes or reacts when the cylinder temperature of the injection molding machine is equal to or higher than the melting temperature of the olefin resin, Those that produce carbon dioxide or nitrogen are particularly preferred.
- an inorganic foaming agent or an organic foaming agent may be used. Moreover, you may use combining these.
- the inorganic foaming agent include sodium bicarbonate (sodium bicarbonate), sodium carbonate, ammonium bicarbonate (ammonium bicarbonate), ammonium carbonate, ammonium nitrite and the like.
- Organic foaming agents include N-nitroso compounds such as N, N′-dinitrosotephthalamide, N, N′-dinitrosopentamethylenetetramine; azodicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile, azo Azo compounds such as diaminobenzene and barium azodicarboxylate; sulfonyl hydrazide compounds such as benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, p, p'-oxybis (benzenesulfenyl hydrazide), diphenylsulfone-3,3'-disulfonyl hydrazide Azide compounds such as calcium azide, 4,4′-diphenyldisulfonyl azide, p-toluenesulfonyl azide; citric acid, sodium citrate, tartaric acid,
- the volatile foaming chemicals are prepared by absorbing or dissolving the volatile foaming chemicals in a molten olefin resin composition and supplying the raw materials to an injection molding machine to evaporate them in a mold.
- inert or nonflammable gas nitrogen, carbon dioxide, argon, neon, helium, etc.
- water aliphatic hydrocarbon such as propane, n-butane, isobutane, n-pentane, isopentane, n-hexane
- Aromatic hydrocarbons such as toluene; halogenated hydrocarbons such as trifluorochloromethane; ethers such as dimethyl ether and petroleum ether; ketones such as acetone and the like can be used.
- carbon dioxide, nitrogen or a mixture thereof is preferable because it is inexpensive and highly safe.
- supercritical carbon dioxide, supercritical nitrogen or a mixture thereof has compressibility like liquid and diffusibility like gas, so that high diffusibility and high solubility of gas in the resin.
- a material called a microballoon or a medium air ball can be used as the capsule in which the above-described volatile foaming chemical is enclosed.
- a material called a microballoon or a medium air ball can be used as the capsule in which the above-described volatile foaming chemical is enclosed.
- the amount of the foaming agent used is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 8 parts by weight, and still more preferably when the total amount of the resin components contained in the production raw material is 100 parts by weight. 1 to 6 parts by mass.
- the resin in the mold can be applied a method in which foaming.
- the core back method is preferred from the viewpoint that a foamed resin molded article having a skin layer can be easily obtained and the expansion ratio of the entire foamed resin molded article can be easily controlled.
- FIG. 2A shows a schematic view of a mold including a fixed mold 11, a movable mold 12, and a sprue 13, and the mold is brought into a clamped state by bringing the fixed mold 11 and the movable mold 12 closest to each other. .
- the fixed mold 11 and the movable mold 12 are arranged so as to form a cavity 14 (clearance L 0 ) having a volume smaller than the total volume of manufacturing raw materials used for molding.
- a predetermined amount of production raw material is introduced (injected) from the sprue 13 into the cavity 14 and the filling of the production raw material is completed while the movable mold 12 is retracted (FIG. 2B).
- the temperature of the production raw material to be injected is preferably 180 ° C. to 240 ° C., more preferably 200 ° C. to 230 ° C., and further preferably 210 ° C. to 220 ° C.
- the temperature of the fixed mold 11 and the movable mold 12 is preferably 10 ° C. to 80 ° C., more preferably 20 ° C. to 70 ° C., and further preferably 30 ° C. to 50 ° C.
- the movable mold 12 is further retracted to foam the production raw material.
- the inside of the cavity 14 is depressurized, and foam molding proceeds with the movement of the movable mold 12.
- foaming does not progress at all or hardly, a skin layer is formed, and the inside of the manufacturing raw material part 16 ( The foamed resin molded body 18 is formed by foaming the core layer (FIGS. 2B and 2C).
- the end point of the retraction of the movable mold 12 can be determined by the expansion ratio of the foamed resin molded body 18. That is, when manufacturing the foamed resin molding 18 having a high expansion ratio, the receding distance is increased.
- the core layer of the foamed resin molded body 18 is difficult to be cooled and the skin layer is cooled quickly, so that it is difficult to adjust the foaming ratio.
- the injection filling of the manufacturing raw material is started from the state where the volume of the cavity 14 is small. Therefore, the flow rate of the production raw material inside the cavity 14 is high, the blowing of the foaming gas in the flow causing the silver streak is suppressed, and the production raw material in contact with the inner surfaces of the fixed mold 11 and the movable mold 12 is Since it is quickly filled and cooled quickly, it is possible to obtain a foamed resin molded body 18 that has a skin layer with excellent appearance and is not easily destroyed even under high impact.
- Another method for producing a foamed resin molded body is a method using a high-pressure gas as a foaming agent, and an olefin-based resin composition is previously molded into a sheet shape or the like to form an unfoamed resin molded body. (Unfoamed molded product) After this, the unfoamed resin molded body is impregnated with a high-pressure gas and foamed by releasing the pressure, and the olefin resin composition is pressurized under high pressure. It is possible to obtain a continuous production method in which molding and foaming are simultaneously carried out by kneading together with the above gas, molding and releasing pressure at the same time.
- a high-pressure gas composed of an inert gas such as carbon dioxide is injected (introduced) into a pressure-resistant container (high-pressure container) on which an unfoamed resin molding is placed.
- a gas impregnation step for impregnating the unfoamed resin molded body with a high-pressure gas release the pressure at the time of sufficiently impregnating the high-pressure gas (usually up to atmospheric pressure), and bubble nuclei in the unfoamed resin molded body
- a decompression step to be generated and, if necessary, a heating step of growing bubble nuclei by heating are sequentially advanced to form bubbles in the unfoamed resin molded body.
- bubble nuclei may be grown at room temperature without providing a heating step. In this way, after the bubbles are grown, if necessary, the shape can be fixed by rapid cooling with cold water or the like.
- the high pressure which consists of inert gas, such as a carbon dioxide, kneading
- the molding decompression step in which molding and foaming are performed simultaneously can be sequentially performed.
- bubbles may be grown by performing a heating operation. In this way, after the bubbles are grown, the shape can be fixed by rapid cooling with cold water if necessary.
- the foamed resin molded body of the present invention is a vehicle part (for automobiles and bicycles), a ship part, an aircraft part, an industrial material, an office part, a household item, a toy, a sporting part, a building material part. Suitable for structures, medical supplies, agricultural, forestry and fishery related parts. In vehicle parts, marine parts or aircraft parts, it is suitable as an exterior part, an interior part or a base material thereof.
- automotive parts include exterior parts such as body panels and bumpers; door trims, pockets, decorative panels, ornament panels, EA materials, quarter trims, pillar garnishes, cowl side garnishes, shields, and backboards.
- Side airbag peripheral parts instrument panel, center cluster, register, center box (door), grab door, center console, overhead console, sun visor, deck board (luggage board), package tray, high-mount stop lamp cover, CRS Examples include interior parts such as covers, seat side garnishes, CTR clusters, and shock absorbers; electrical parts such as cleaner cases and filter cases.
- Industrial materials include transport containers, trays, trolleys, pylons, center poles, and construction equipment.
- household goods include food trays, helmets, shoes, book stands, tableware, and cleaning tools.
- sports equipment include protectors (baseball, soccer, motor sports), outdoor equipment, and mountaineering equipment.
- Examples of building material parts include heat insulating materials.
- Examples of the structure include road signs.
- Examples of medical supplies include a mouthpiece, a medical device, and a pharmaceutical container.
- Agricultural, forestry and fishery-related parts include floats, flower pots (planters), aquaculture equipment, and the like.
- Example 1 25 parts by mass of pellets made of polyamide 11 resin “Rilsan BMN O” (trade name, weight average molecular weight 17,000, melting point 190 ° C.) manufactured by Arkema Co., Ltd., and maleic anhydride-modified ethylene / butene copolymer “Tuffmer” manufactured by Mitsui Chemicals, Inc.
- the mixed resin pellet (2nd melt-kneaded material) was obtained using the pelletizer. Thereafter, 100 parts by mass of mixed resin pellets (second melt-kneaded product) and 4 parts by mass of sodium hydrogen carbonate as a foaming agent were dry blended to obtain a production raw material (C1) made of the mixture.
- Preparation Example 2 22.5 parts by mass of pellets made of polyamide 11 resin “Rilsan BMN O” (trade name, weight average molecular weight 17,000, melting point 190 ° C.) manufactured by Arkema, and maleic anhydride-modified ethylene / butene copolymer manufactured by Mitsui Chemicals, Inc.
- the mixed resin pellet (2nd melt-kneaded material) was obtained using the pelletizer. Thereafter, 90 parts by mass of mixed resin pellets (second melt-kneaded product), 10 parts by mass of propylene block polymer (MFR 50 to 70 g / 10 min, melting point 165 ° C.), and 4 parts by mass of sodium hydrogen carbonate as a foaming agent are dry blended. As a result, a production raw material (C2) comprising a mixture was obtained.
- a polypropylene resin used with a foaming agent at a mixing process a polypropylene resin with better foam moldability can also be used compared with the said polypropylene resin "NOVATEC MA1B" (brand name). Specifically, as described above, a polypropylene resin having a large MFR (temperature 230 ° C., 2.16 kg load) of 29 to 49 g / 10 min can be used.
- Preparation Example 3 10 parts by mass of pellets made of polyamide 11 resin “Rilsan BMN O” (trade name, weight average molecular weight 17,000, melting point 190 ° C.) manufactured by Arkema, and maleic anhydride-modified ethylene / butene copolymer “Tuffmer” manufactured by Mitsui Chemicals, Inc.
- the mixed resin pellet (2nd melt-kneaded material) was obtained using the pelletizer. Thereafter, 40 parts by mass of mixed resin pellets (second melt-kneaded product), 60 parts by mass of a propylene block polymer (MFR 50 to 70 g / 10 min, melting point 165 ° C.) and 4 parts by mass of sodium hydrogen carbonate as a foaming agent are dry blended. As a result, a production raw material (C3) comprising a mixture was obtained.
- Preparation Example 4 5 parts by mass of pellets made of polyamide 11 resin “Rilsan BMN O” (trade name, weight average molecular weight 17,000, melting point 190 ° C.) manufactured by Arkema, and maleic anhydride-modified ethylene / butene copolymer “Toughmer” manufactured by Mitsui Chemicals, Inc.
- Preparation Example 5 3.75 parts by mass of pellets made of polyamide 11 resin “Rilsan BMN O” (trade name, weight average molecular weight 17,000, melting point 190 ° C.) manufactured by Arkema Co., Ltd., and maleic anhydride-modified ethylene / butene copolymer manufactured by Mitsui Chemicals, Inc. After dry blending 3 parts by mass of pellets made of “Tuffmer MH7020” (trade name, weight average molecular weight 199,000), the mixed pellets were put into a twin screw melt kneading extruder manufactured by Coperion (model “ZSK50”).
- Melt kneading was performed under conditions of a kneading temperature of 210 ° C., an extrusion speed of 150 kg / hour, and a screw rotation speed of 200 revolutions / minute. And the mixed resin pellet (1st melt kneaded material) was obtained using the pelletizer. Next, 6.75 parts by mass of mixed resin pellets (first melt-kneaded product) and 8.25 parts by mass of polypropylene resin “Novatech MA1B” (trade name, propylene homopolymer, melting point 165 ° C.) manufactured by Nippon Polypro Co., Ltd. were dried.
- the mixed pellets are put into a twin-screw melt kneading extruder (model “ZSK50”) manufactured by Coperion Co., Ltd., and kneaded at a kneading temperature of 210 ° C., an extrusion speed of 150 kg / hour, and a screw rotation speed of 200 revolutions / minute. went. And the mixed resin pellet (2nd melt-kneaded material) was obtained using the pelletizer.
- a twin-screw melt kneading extruder model “ZSK50” manufactured by Coperion Co., Ltd.
- Preparation Example 6 2.5 parts by mass of pellets made of polyamide 11 resin “Rilsan BMN O” (trade name, weight average molecular weight 17,000, melting point 190 ° C.) manufactured by Arkema, and maleic anhydride-modified ethylene / butene copolymer manufactured by Mitsui Chemicals, Inc.
- the mixed resin pellet (2nd melt-kneaded material) was obtained using the pelletizer. Thereafter, 10 parts by mass of mixed resin pellets (second melt-kneaded product), 90 parts by mass of propylene block polymer (MFR 50 to 70 g / 10 min, melting point 165 ° C.), and 4 parts by mass of sodium hydrogen carbonate as a foaming agent are dry blended.
- the manufacturing raw material (C6) which consists of a mixture was obtained.
- Preparation Example 7 1.25 parts by mass of pellets made of polyamide 11 resin “Rilsan BMN O” (trade name, weight average molecular weight 17,000, melting point 190 ° C.) manufactured by Arkema Co., Ltd., and maleic anhydride-modified ethylene / butene copolymer manufactured by Mitsui Chemicals, Inc.
- the mixed resin pellet (2nd melt-kneaded material) was obtained using the pelletizer. Thereafter, 5 parts by mass of mixed resin pellets (second melt-kneaded product), 95 parts by mass of propylene block polymer (MFR 50 to 70 g / 10 min, melting point 165 ° C.), and 4 parts by mass of sodium hydrogen carbonate as a foaming agent are dry blended. As a result, a production raw material (C7) comprising a mixture was obtained.
- Preparation Example 8 100 parts by mass of pellets made of Nippon Polypro's polypropylene resin “NOVATEC MA1B” (trade name, propylene homopolymer, melting point 165 ° C.) and 4 parts by mass of sodium hydrogen carbonate as a foaming agent are dry blended to produce a mixture A raw material (C8) was obtained.
- NOVATEC MA1B trade name, propylene homopolymer, melting point 165 ° C.
- the dispersed phase and the finely dispersed phase are observed in an image magnified 1000 times or more (usually 10,000 times or less).
- the components constituting each phase are specified by performing energy dispersive X-ray analysis (EDS) at the time of observation using the FE-SEM.
- EDS energy dispersive X-ray analysis
- FIG. 3 schematically shows an outline of a side collision test on the front door.
- a dummy 40 simulating an adult male called “Euro SID-2” (height approximately 170 cm, weight approximately 72 kg) is prepared, and this dummy 40 is placed in the driver's seat of a stationary test vehicle.
- Euro SID-2 the average length of an adult male
- a cart 60 having a mass of 950 kg is caused to collide with the side surface of the test vehicle at a speed of 55 km / h.
- the side airbag 30 When the side airbag 30 is mounted, the side airbag 30 also operates.
- the occupant protection performance is evaluated based on the impact received on the head, chest, abdomen, and lower back of the dummy 40. At present, it is required to ensure passenger protection performance based on such tests.
- the present inventor conducted such a test or a single product test equivalent thereto, and visually observed whether or not the front door trim base material 20 had broken behavior. The observation results are determined according to the following criteria and are shown in Table 1. ⁇ : The destruction behavior of the front door trim base material was not seen or destroyed due to the collision, but it did not scatter. ⁇ : The destruction behavior of the front door trim base material was found to scatter due to the collision.
- the door trim base material does not scatter. That is, it can be seen that the foamed resin molded article of the present invention has high impact resistance. That is, it was shown that when the expansion ratio is less than 2.4 times, the foamed resin molded body does not show a fracture behavior or is not scattered even when it is destroyed. That is, it is possible to obtain a foamed resin molded body within a wide range of the blending ratio of the second melt-kneaded product from 5 to 100% by mass. Furthermore, when the expansion ratio was 2.4 times, it was shown that by increasing the blending ratio of the second melt-kneaded material in the corresponding region, the fracture behavior was not observed or even if it was broken, it was not scattered.
- the foamed resin molded article of the present invention is suitable for automobile-related parts, ship-related parts, aviation-related parts, office parts, daily goods, kitchenware, building material parts, sports goods, and the like. Particularly, among automobile-related parts, ship-related parts or aviation-related parts, it is suitable as an exterior material, interior material, or a base material thereof.
- Foamed resin molding 11: Fixed type, 12: Movable type, 13: Sprue 14: cavity, 16: Production raw material department, 18: Foamed resin molding, 20: Front door trim base material, 25: Armrest part, 30: Side airbag, 40: dummy 50: Door panel, 60: Dolly, X: continuous phase, Y: disperse phase, Y 1 ; parent phase (continuous phase in dispersed phase Y), Y 2 ; finely dispersed phase (dispersed phase in dispersed phase Y), Z: Air bubbles.
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Abstract
Description
特許文献1には、表面がスキン層で形成され、内部が発泡層で形成された、ポリプロピレンを含む発泡樹脂成形体であって、発泡層には、複数の第1の発泡セルと、第1の発泡セル同士の間に形成され、第1の発泡セルより小さい複数の第2の発泡セルと、が形成された発泡樹脂成形体が開示されている。
また、特許文献2には、少なくともポリプロピレン系樹脂、ASTM 1238に準拠し、温度190℃、荷重2.16kgで測定したメルトフローレートが1g/10分以上10g/10分未満、溶融張力が150mN以上、歪硬化性を有し、JIS K6760に準拠した密度が915kg/m3以上970kg/m3以下のポリエチレン系樹脂(A)、並びにアルケニル芳香族化合物単位含有ゴム及びJIS K6760に準拠した密度が850kg/m3以上910kg/m3以下、ASTM 1238に準拠し、温度190℃、荷重2.16kgで測定したメルトフローレートが3g/10分以上のエチレン・α-オレフィン系共重合体からなる群より選ばれる少なくとも1種以上の熱可塑性樹脂(B)を含有する射出発泡用樹脂組成物を用いて得られた発泡成形体が開示されている。
本発明は、耐衝撃性及び剛性に優れ、高い衝撃を受けても破壊され難い発泡樹脂成形体及びその製造方法を提供することを目的とする。
〔1〕オレフィン樹脂及びポリアミド樹脂を含有するオレフィン系樹脂組成物からなる発泡樹脂成形体において、
上記オレフィン系樹脂組成物は、上記オレフィン樹脂を含む連続相と、該連続相の中に分散されたポリアミド樹脂を含む分散相とを備え、
上記分散相は、上記ポリアミド樹脂と、該ポリアミド樹脂に対する反応性基を有するエラストマーとの溶融混練物を含むことを特徴とする発泡樹脂成形体。
〔2〕上記分散相が、上記ポリアミド樹脂を含む母相と、該母相の中に分散された、上記反応性を有する上記エラストマーを含む微分散相とを有し、発泡された気泡は上記分散相及び上記微分散相ではなく上記連続相のみにある上記〔1〕に記載の発泡樹脂成形体。
〔3〕上記分散相の割合が、上記連続相及び上記分散相の合計を100質量%とした場合に、70質量%以下である上記〔1〕又は〔2〕に記載の発泡樹脂成形体。
〔4〕上記オレフィン樹脂がプロピレンに由来する構造単位を含む重合体である上記〔1〕乃至〔3〕のいずれか一項に記載の発泡樹脂成形体。
〔5〕上記ポリアミド樹脂が、ポリアミド6、ポリアミド66、ポリアミド610、ポリアミド612、ポリアミド614、ポリアミド11、ポリアミド12、ポリアミド6T、ポリアミド6I、ポリアミド9T、ポリアミドM5T、ポリアミド1010、ポリアミド1012、ポリアミド10T、ポリアミドMXD6、ポリアミド6T/66、ポリアミド6T/6I、ポリアミド6T/6I/66、ポリアミド6T/2M-5T及びポリアミド9T/2M-8Tから選ばれた少なくとも1つである上記〔1〕乃至〔4〕のいずれか一項に記載の発泡樹脂成形体。
〔6〕上記反応性基を有する上記エラストマーが、エチレン又はプロピレンに由来する構造単位を含むオレフィン系熱可塑性エラストマー又は芳香族ビニル化合物に由来する構造単位を含むスチレン系熱可塑性エラストマーである上記〔1〕乃至〔5〕のいずれか一項に記載の発泡樹脂成形体。
〔7〕上記反応性基を有する上記エラストマーが、酸無水物変性エラストマー、カルボン酸変性エラストマー、エポキシ変性エラストマー及びオキサゾリン変性エラストマーから選ばれた少なくとも1種である上記〔1〕乃至〔6〕のいずれか一項に記載の発泡樹脂成形体。
〔8〕上記〔1〕乃至〔7〕のいずれか一項に記載の発泡樹脂成形体の製造方法であって、
ポリアミド樹脂と、該ポリアミド樹脂に対する反応性基を有するエラストマーとを溶融混練する第1溶融混練工程と、該第1溶融混練工程により得られた第1溶融混練物と、オレフィン樹脂とを溶融混練する第2溶融混練工程と、該第2溶融混練工程により得られた第2溶融混練物とオレフィン樹脂とを混合する混合工程とを備える方法により得られた製造原料を、発泡させることを特徴とする、発泡樹脂成形体の製造方法。
〔9〕上記混合工程で用いる上記オレフィン樹脂は、上記第2溶融混練工程で用いるオレフィン樹脂と異なる上記〔8〕に記載の発泡樹脂成形体の製造方法。
〔10〕上記混合工程で用いる上記オレフィン樹脂の流動性が、上記第2溶融混練工程で用いるオレフィン樹脂の流動性より高い上記〔9〕に記載の発泡樹脂成形体の製造方法。
〔11〕上記〔1〕乃至〔7〕のいずれか一項に記載の発泡樹脂成形体の製造方法であって、
ポリアミド樹脂と、該ポリアミド樹脂に対する反応性基を有するエラストマーとを溶融混練する第1溶融混練工程と、該第1溶融混練工程により得られた第1溶融混練物と、オレフィン樹脂とを溶融混練する第2溶融混練工程とを備える方法により得られた製造原料を、発泡させることを特徴とする、発泡樹脂成形体の製造方法。
上記分散相が、上記ポリアミド樹脂を含む母相と、該母相の中に分散された、上記反応性を有する上記エラストマーを含む微分散相とを有し、発泡された気泡が上記分散相及び上記微分散相ではなく上記連続相のみにある場合には、多重の相構造となり、耐衝撃性により優れた発泡樹脂成形体とすることができ、また、相構造を保持した状態で耐衝撃性を有する発泡樹脂成形体とすることができる。
上記分散相の割合が、上記連続相及び上記分散相の合計を100質量%とした場合に、70質量%以下である場合には、優れた耐衝撃性、剛性及び成形性をバランスよく得ることができる。
上記オレフィン樹脂がプロピレンに由来する構造単位を含む重合体である場合には、耐衝撃性に優れた発泡樹脂成形体を安価に入手することができる。
上記ポリアミド樹脂が、ポリアミド6、ポリアミド66、ポリアミド610、ポリアミド612、ポリアミド614、ポリアミド11、ポリアミド12、ポリアミド6T、ポリアミド6I、ポリアミド9T、ポリアミドM5T、ポリアミド1010、ポリアミド1012、ポリアミド10T、ポリアミドMXD6、ポリアミド6T/66、ポリアミド6T/6I、ポリアミド6T/6I/66、ポリアミド6T/2M-5T及びポリアミド9T/2M-8Tから選ばれた少なくとも1つである場合には、耐衝撃性に優れた発泡樹脂成形体を上記ポリアミドより選択することができる。
上記反応性基を有する上記エラストマーが、エチレン又はプロピレンに由来する構造単位を含むオレフィン系熱可塑性エラストマー又は芳香族ビニル化合物に由来する構造単位を含むスチレン系熱可塑性エラストマーである場合には、特定の相構造をより確実に得ることができるため、優れた耐衝撃性を発揮できる発泡樹脂成形体とすることができる。
上記反応性基を有する上記エラストマーが、酸無水物変性エラストマー、カルボン酸変性エラストマー、エポキシ変性エラストマー及びオキサゾリン変性エラストマーから選ばれた少なくとも1種である場合には、耐衝撃性に優れた発泡樹脂成形体を上記エラストマーより選択することができる。
本発明の発泡樹脂成形体の製造方法によれば、高い衝撃を受けても破壊され難く、外観性に優れた発泡樹脂成形体を効率よく得ることができる。
また、混合工程を備える本発明の発泡樹脂成形体の他の製造方法によれば、優れた耐衝撃性を保持したまま、安価に得ることができる。
上記混合工程で用いる上記オレフィン樹脂は、上記第2溶融混練工程で用いるオレフィン樹脂と異なる場合には、第2溶融混練物を生成するのに適したポリオレフィン樹脂あるいは発泡させるのに適したポリオレフィン樹脂を使い分けることができる。
上記混合工程で用いる上記オレフィン樹脂の流動性が、上記第2溶融混練工程で用いるオレフィン樹脂の流動性より高い場合には、射出成形する際に、型内での流動性が良好である。
本発明の発泡樹脂成形体(1)は、オレフィン樹脂(以下、「オレフィン樹脂(A)」という)及びポリアミド樹脂(以下、「ポリアミド樹脂(B)」という)を含有し、特定構造を有するオレフィン系樹脂組成物、即ち、オレフィン樹脂(A)を含む連続相(X)と、この連続相(X)の中に分散されたポリアミド樹脂を含む分散相(Y)とを備え、分散相(Y)は、ポリアミド樹脂(B)と、該ポリアミド樹脂(B)に対する反応性基を有するエラストマー(以下、「変性エラストマー」という)との溶融混練物を含むことを特徴とする(図1参照)。本発明の発泡樹脂成形体は、スキン層及びセル壁を有し、これらの部位が上記オレフィン系樹脂組成物により形成されている。
尚、上記α-オレフィンとしては、プロピレン、1-ブテン、1-ペンテン、1-ヘキセン、1-ヘプテン、3-メチル-1-ブテン、4-メチル-1-ペンテン等が挙げられる。
上記オレフィン樹脂(A)としては、α-オレフィンの単独重合体又は共重合体が好ましく、ポリプロピレン、エチレン・プロピレン共重合体、エチレン・1-ブテン共重合体、エチレン・プロピレン・1-ブテン共重合体等がより好ましく、プロピレンに由来する構造単位を含む重合体が特に好ましい。
上記連続相は、分散相を含むが、後述する添加剤を、分散状態で含んでもよい。
上記ラクタム類としては、ε-カプロラクタム、ウンデカンラクタム、ω-ラウリルラクタム等が挙げられる。
上記アミノ酸としては、アミノカプロン酸、アミノウンデカン酸、アミノドデカン酸、パラアミノメチル安息香酸等が挙げられる。
上記ジアミンとしては、エチレンジアミン、1,3-ジアミノプロパン、1,4-ジアミノブタン、1,6-ジアミノヘキサン、1,7-ジアミノヘプタン、1,8-ジアミノオクタン、1,9-ジアミノノナン、1,10-ジアミノデカン、1,11-ジアミノウンデカン、1,12-ジアミノドデカン、1,13-ジアミノトリデカン、1,14-ジアミノテトラデカン、1,15-ジアミノペンタデカン、1,16-ジアミノヘキサデカン、1,17-ジアミノヘプタデカン、1,18-ジアミノオクタデカン、1,19-ジアミノノナデカン、1,20-ジアミノエイコサン、2-メチル-1,5-ジアミノペンタン、2-メチル-1,8-ジアミノオクタン等の脂肪族ジアミン;シクロヘキサンジアミン、ビス-(4-アミノシクロヘキシル)メタン等の脂環式ジアミン;m-フェニレンジアミン、p-フェニレンジアミン、m-キシリレンジアミン、p-キシリレンジアミン等の芳香族ジアミン等が挙げられる。
上記ジカルボン酸としては、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ウンデカン二酸、ドデカン二酸、ブラシリン酸、テトラデカン二酸、ペンタデカン二酸、オクタデカン二酸等の脂肪族ジカルボン酸;シクロヘキサンジカルボン酸等の脂環式ジカルボン酸;オルトフタル酸、テレフタル酸、イソフタル酸、ナフタレンジカルボン酸等の芳香族ジカルボン酸等が挙げられる。
ポリアミド610は、炭素原子数6である単量体と、炭素原子数10である単量体と、がアミド結合を介して結合された構造を有する。ポリアミド610の形成には、単量体として、ヒマシ油を原料とするセバシン酸を用いることができる。炭素原子数6である単量体に由来する構成単位、及び、炭素原子数10である単量体に由来する構成単位の含有量の合計は、ポリアミド610の全構成単位のうちの50%以上であることが好ましく、100%であってもよい。
ポリアミド1010は、炭素原子数10であるジアミンと、炭素原子数10であるジカルボン酸と、が共重合された構造を有する。ポリアミド1010の形成には、単量体として、ヒマシ油を原料とする1,10-デカンジアミン(デカメチレンジアミン)及びセバシン酸を用いることができる。これらの炭素原子数10であるジアミンに由来する構成単位、及び、炭素原子数10であるジカルボン酸に由来する構成単位の合計は、ポリアミド1010の全構成単位のうちの50%以上であることが好ましく、100%であってもよい。
ポリアミド10Tは、炭素原子数10であるジアミンと、テレフタル酸と、がアミド結合を介して結合された構造を有する。ポリアミド10Tの形成には、単量体として、ヒマシ油を原料とする1,10-デカンジアミン(デカメチレンジアミン)を用いることができる。これらの炭素原子数10であるジアミンに由来する構成単位、及び、テレフタル酸に由来する構成単位は、ポリアミド10Tの全構成単位のうちの50%以上であることが好ましく、100%であってもよい。
ポリアミド610は、吸水率、耐薬品性及び衝撃強度の点ではポリアミド11よりも劣るが、耐熱性(融点)及び剛性(強度)の観点において優れている。更には、ポリアミド6やポリアミド66と比べ、低吸水性で寸法安定性が良いため、ポリアミド6やポリアミド66の代替材として使用することができる。
ポリアミド1010は、ポリアミド11に比べて、耐熱性及び剛性の観点において優れている。更には、植物化度もポリアミド11と同等であり、より耐久性の必要な部位に使用することができる。
ポリアミド10Tは、分子骨格に芳香環を含むため、ポリアミド1010に比べて、より融点が高く高剛性である。そのため、過酷環境下での使用(耐熱部位、強度入力部位)が可能である。
また、上記変性エラストマーの変性量(反応性基の数)は、特に限定されず、好ましくは1~50、より好ましくは3~30、更に好ましくは5~20である。
上記芳香族ビニル化合物は、スチレン、α-メチルスチレン、p-メチルスチレン、p-tert-ブチルスチレン等のアルキルスチレン;p-メトキシスチレン、ビニルナフタレン等から選ばれた少なくとも1種とすることができる。
また、上記共役ジエン化合物は、ブタジエン、イソプレン、1,3-ペンタジエン、メチルペンタジエン、フェニルブタジエン、3,4-ジメチル-1,3-ヘキサジエン、4,5-ジエチル-1,3-オクタジエン等から選ばれた少なくとも1種とすることができる。
また、カルボン酸としては、アクリル酸、メタクリル酸、マレイン酸、フマル酸、イタコン酸、シトラコン酸等が挙げられる。
上記酸変性オレフィン系エラストマーは、単独で、又は、2種以上を組み合わせて用いることができる。
また、上記オキサゾリン変性オレフィン系エラストマーとする際に用いる変性用化合物としては、ビニルオキサゾリン化合物等の、重合性不飽和結合及びオキサゾリル基を有する化合物を用いることができる。
また、分散相(Y)及び微分散相(Y2)の概形は限定されず、例えば、図1(a)に示すように、略円形状の断面(三次元的には略球形状)をなしてもよいし、例えば、図1(b)に示すように、気泡(Z)の形成に伴って、略楕円形や偏平形状へと変形した(伸びた)形状であってもよい。
本発明の発泡樹脂成形体の相構造としては、第1の樹脂からなる連続相A1と第2の樹脂からなる連続相A2とからなる共連続相をとることもできる。共連続相とは、2種以上の連続相(連続相A1及びA2)が3次元的に連続してつながっている構造をいう。
上記分散相は、後述する添加剤を、分散状態で含んでもよい。
また、上記分散相の最大径の上限は、発泡樹脂成形体の形状安定性、耐衝撃性及び剛性の観点から、好ましくは10,000nm、より好ましくは8,000nm、更に好ましくは4,000nmである。また、下限は、通常、50nmであり、好ましくは100nmである。上記最大径は、電子顕微鏡画像から得られた測定値とすることができる。
上記連続相及び上記分散相の質量割合は、発泡樹脂成形体の発泡セルの安定性、耐衝撃性、剛性の観点から、両者の合計を100質量%とした場合に、それぞれ、好ましくは30質量%以上及び70質量%以下、より好ましくは50~99.5質量%及び0.5~50質量%、更に好ましくは52~98質量%及び2~48質量%、特に好ましくは55~96質量%及び4~45質量%である。
上記熱安定剤としては、ヒンダードアミン系化合物等が挙げられる。
上記紫外線吸収剤としては、ベンゾフェノン系化合物、ベンゾトリアゾール系化合物、ベンゾエート系化合物等が挙げられる。
上記帯電防止剤としては、ノニオン系化合物、カチオン系化合物、アニオン系化合物等が挙げられる。
上記金属不活性剤としては、ヒドラジン系化合物、アミン系化合物等が挙げられる。
上記難燃剤としては、ハロゲン系化合物、リン系化合物(窒素含有リン酸塩化合物、リン酸エステル等)、窒素系化合物(グアニジン、トリアジン、メラミン又はこれらの誘導体等)、無機化合物(金属水酸化物等)、ホウ素系化合物、シリコーン系化合物、硫黄系化合物、赤リン系化合物等が挙げられる。
上記難燃助剤としては、アンチモン化合物、亜鉛化合物、ビスマス化合物、水酸化マグネシウム、粘土質珪酸塩等が挙げられる。
本発明の発泡樹脂成形体の発泡倍率は、好ましくは1.2~3.5倍、より好ましくは、1.3~2.5倍、更に好ましくは1.4~2.0倍、特に好ましくは1.5~1.8倍である。また、本発明の発泡樹脂成形体の目付は、好ましくは0.1~2.1g/m2、より好ましくは、0.5~2.0g/m2、更に好ましくは0.8~1.9g/m2、特に好ましくは1.0~1.8g/m2である。
尚、本発泡樹脂成形体における中実部体積をV0とし、中空部体積をV1とした場合に、上記発泡倍率は「(V0+V1)/V0」で表される。即ち、相構造を用いて説明すると、連続相(X)と分散相(Y)との合計体積が中実部体積V0に相当し、気泡(Z)の体積が中空部体積V1に相当する。
上記発泡セルの大きさは、特に限定されないが、本発明の発泡樹脂成形体では、サイズは不均一ではあるが微細な発泡セルが形成されている。
本発明において、発泡樹脂成形体の製造方法は、ポリアミド樹脂と、該ポリアミド樹脂に対する反応性基を有するエラストマー(変性エラストマー)とを溶融混練する第1溶融混練工程と、該第1溶融混練工程により得られた第1溶融混練物と、オレフィン樹脂とを溶融混練する第2溶融混練工程とを備える方法(調製方法)により得られた製造原料を、発泡させることを特徴とする。本製造方法における発泡は、結果的に発泡されていればよく、例えば、化学発泡であってもよく、物理発泡であってもよい。また、この製造方法では、必要に応じて、他の成分を配合する工程を更に備えることができる。
上記ポリアミド樹脂として、ポリアミド6を用いる場合、その使用量は、ポリアミド樹脂、変性エラストマー及びオレフィン樹脂の合計を100質量%とした場合に、好ましくは1~50質量%、より好ましくは5~40質量%、更に好ましくは10~35質量%である。
上記ポリアミド樹脂として、ポリアミド610を用いる場合、その使用量は、ポリアミド樹脂、変性エラストマー及びオレフィン樹脂の合計を100質量%とした場合に、好ましくは1~40質量%、より好ましくは5~40質量%、更に好ましくは10~40質量%である。
上記ポリアミド樹脂として、ポリアミド11を用いる場合、その使用量は、ポリアミド樹脂、変性エラストマー及びオレフィン樹脂の合計を100質量%とした場合に、好ましくは1~55質量%、より好ましくは10~55質量%、更に好ましくは15~55質量%である。
上記ポリアミド樹脂として、ポリアミド12を用いる場合、その使用量は、ポリアミド樹脂、変性エラストマー及びオレフィン樹脂の合計を100質量%とした場合に、好ましくは1~35質量%、より好ましくは5~35質量%、更に好ましくは10~35質量%である。
上記ポリアミド樹脂として、ポリアミド1010を用いる場合、その使用量は、ポリアミド樹脂、変性エラストマー及びオレフィン樹脂の合計を100質量%とした場合に、好ましくは1~55質量%、より好ましくは5~55質量%、更に好ましくは10~55質量%である。
上記ポリアミド樹脂として、ポリアミド10Tを用いる場合、その使用量は、ポリアミド樹脂、変性エラストマー及びオレフィン樹脂の合計を100質量%とした場合に、好ましくは1~45質量%、より好ましくは5~45質量%、更に好ましくは10~45質量%である。
上記ポリアミド樹脂として、ポリアミドMXD6を用いる場合、その使用量は、ポリアミド樹脂、変性エラストマー及びオレフィン樹脂の合計を100質量%とした場合に、好ましくは1~40質量%、より好ましくは5~40質量%、更に好ましくは10~40質量%である。
また、上記第2溶融混練工程において、第1溶融混練物及びオレフィン樹脂を含む第2原料の溶融混練は、これらの全量を一括して行ってよいし、いずれか一方を分割して添加しながら行ってもよい。尚、混練温度は、好ましくは190℃~250℃、より好ましくは200℃~230℃、更に好ましくは205℃~220℃である。
尚、「互いに異なるオレフィン樹脂」とは、互いに種類が異なるオレフィン樹脂、又は、種類が同一であっても、流動性等が互いに異なるオレフィン樹脂を意味する。互いに異なるオレフィン樹脂を用いる場合、種類が同一であるか否かに関わらず、混合工程で用いるオレフィン樹脂の流動性が、第2溶融混練工程で用いるオレフィン樹脂の流動性より高いものを用いることが好ましい。
また、上記発泡剤の使用量は、ポリアミド樹脂、変性エラストマー及びオレフィン樹脂の全量を100質量部とした場合に、好ましくは0.1~10質量部、より好ましくは0.5~8質量部、更に好ましくは1~6質量部である。尚、上記発泡剤は、好ましくは分解性発泡剤であり、後述される。
上記製造原料を発泡させる場合、射出発泡成形、プレス発泡成形、押出発泡成形、スタンパブル発泡成形、加熱発泡成形等の、従来、公知の方法を適用することができる。本発明においては、射出発泡成形が好ましい。
無機系発泡剤としては、重炭酸ナトリウム(炭酸水素ナトリウム)、炭酸ナトリウム、重炭酸アンモニウム(炭酸水素アンモニウム)、炭酸アンモニウム、亜硝酸アンモニウム等が挙げられる。
有機系発泡剤としては、N,N’-ジニトロソテレフタルアミド、N,N’-ジニトロソペンタメチレンテトラミン等のN-ニトロソ化合物;アゾジカルボンアミド、アゾビスイソブチロニトリル、アゾシクロヘキシルニトリル、アゾジアミノベンゼン、バリウムアゾジカルボキシレート等のアゾ化合物;ベンゼンスルフォニルヒドラジド、トルエンスルフォニルヒドラジド、p,p’-オキシビス(ベンゼンスルフェニルヒドラジド)、ジフェニルスルフォン-3,3’-ジスルフォニルヒドラジド等のスルフォニルヒドラジド化合物;カルシウムアジド、4,4’-ジフェニルジスルフォニルアジド、p-トルエンスルフォニルアジド等のアジド化合物;クエン酸、クエン酸ナトリウム、酒石酸、リンゴ酸、コハク酸、シュウ酸、アジピン酸、マロン酸、フタル酸、セバシン酸、マレイン酸、フマル酸、マロン酸、イタコン酸、グルタル酸、グルコン酸、グルタコン酸、ペンテン二酸等の多価カルボン酸又はその塩等が挙げられる。
更に、上述した揮発性発泡薬品が封入されたカプセルとしては、例えば、マイクロバルーンや中空気球等と称される材料を用いることができる。具体的には、ガスバリア性を有した熱可塑性樹脂組成物(例えば、ポリアクリルニトリル)により形成された外皮を有し、当該外皮内に上述した揮発性発泡薬品が封入されたカプセルが挙げられる。
本発明においては、容易にスキン層を有する発泡樹脂成形体が得られ、発泡樹脂成形体全体の発泡倍率が容易に制御できるという観点から、コアバック法が好ましい。
図2(A)は、固定型11、可動型12及びスプルー13を備える金型であって、固定型11と可動型12とを最も接近させて型締め状態とした金型の概略図を示す。固定型11及び可動型12の配置は、成形に使用する製造原料の全容積より小さい容積のキャビティ14(クリアランスL0)を形成するようにしている。そして、スプルー13からキャビティ14に所定量の製造原料を導入(射出)して、可動型12を後退させながら、製造原料の充填を完了する(図2(B))。これにより、クリアランスL1の状態から製造原料の射出を開始する場合に比べて、早期にスキン層が形成され、外観性に優れた発泡樹脂成形体が得られる。
型締め圧力より高い射出圧力で射出すると、製造原料の充填とともに、キャビティ14の断面の長さ(クリアランス)が増加する。キャビティ断面長さの制御は、型締め圧力が射出圧力に負けて受動的に開くようにしてもよいし、キャビティ断面長さの変化速度を能動的に制御してもよい。
その後、型開により、発泡樹脂成形体18は回収される。
本発明の発泡樹脂成形体は、車両用部品(自動車用、自転車用)、船舶用部品、航空用部品、産業資材、事務部品、生活用品、玩具、スポーツ用品、建材部品、構造物、医療用品、農林水産業関連部品等に好適である。車両用部品、船舶用部品又は航空用部品では、外装部品、内装部品又はこれらの基材として好適である。
生活用品としては、食品トレイ、ヘルメット、靴、本立て、食器、掃除用具等が挙げられる。
スポーツ用品としては、プロテクター(野球、サッカー、モータースポーツ)、アウトドア用品、登山用具等が挙げられる。
構造物としては、道路標識等が挙げられる。
医療用品としては、マウスピース、医療機器、医薬品容器等が挙げられる。
農林水産業関連部品としては、浮き具、植木鉢(プランタ)、養殖関係器具等が挙げられる。
調製例1
アルケマ社製ポリアミド11樹脂「Rilsan BMN O」(商品名、重量平均分子量17,000、融点190℃)からなるペレット25質量部と、三井化学社製無水マレイン酸変性エチレン・ブテン共重合体「タフマー MH7020」(商品名、重量平均分子量199,000)からなるペレット20質量部とをドライブレンドした後、混合ペレットをコペリオン社製二軸溶融混練押出機(型式「ZSK50」)に投入し、混練温度210℃、押出速度150kg/時間、スクリュー回転数200回転/分の条件で溶融混練を行った。そして、ペレタイザーを用いて混合樹脂ペレット(第1溶融混練物)を得た。
次に、混合樹脂ペレット(第1溶融混練物)45質量部と、日本ポリプロ社製ポリプロピレン樹脂「ノバテック MA1B」(商品名、プロピレンホモポリマー、融点165℃、MFR21g/10min)55質量部とをドライブレンドした後、混合ペレットをコペリオン社製二軸溶融混練押出機(型式「ZSK50」)に投入し、混練温度210℃、押出速度150kg/時間、スクリュー回転数200回転/分の条件で溶融混練を行った。そして、ペレタイザーを用いて混合樹脂ペレット(第2溶融混練物)を得た。
その後、混合樹脂ペレット(第2溶融混練物)100質量部と、発泡剤としての炭酸水素ナトリウム4質量部とをドライブレンドし、混合物からなる製造原料(C1)を得た。
アルケマ社製ポリアミド11樹脂「Rilsan BMN O」(商品名、重量平均分子量17,000、融点190℃)からなるペレット22.5質量部と、三井化学社製無水マレイン酸変性エチレン・ブテン共重合体「タフマー MH7020」(商品名、重量平均分子量199,000)からなるペレット18質量部とをドライブレンドした後、混合ペレットをコペリオン社製二軸溶融混練押出機(型式「ZSK50」)に投入し、混練温度210℃、押出速度150kg/時間、スクリュー回転数200回転/分の条件で溶融混練を行った。そして、ペレタイザーを用いて混合樹脂ペレット(第1溶融混練物)を得た。
次に、混合樹脂ペレット(第1溶融混練物)40.5質量部と、日本ポリプロ社製ポリプロピレン樹脂「ノバテック MA1B」(商品名、プロピレンホモポリマー、融点165℃)49.5質量部とをドライブレンドした後、混合ペレットをコペリオン社製二軸溶融混練押出機(型式「ZSK50」)に投入し、混練温度210℃、押出速度150kg/時間、スクリュー回転数200回転/分の条件で溶融混練を行った。そして、ペレタイザーを用いて混合樹脂ペレット(第2溶融混練物)を得た。
その後、混合樹脂ペレット(第2溶融混練物)90質量部と、プロピレンブロックポリマー(MFR50~70g/10min、融点165℃)10質量部と、発泡剤としての炭酸水素ナトリウム4質量部とをドライブレンドし、混合物からなる製造原料(C2)を得た。
尚、混合工程で発泡剤とともに用いるポリプロピレン樹脂としては、上記ポリプロピレン樹脂「ノバテック MA1B」(商品名)に比べて、より発泡成形性の良いポリプロピレン樹脂を用いることもできる。具体的には、上述のように、MFR(温度230℃、2.16kg荷重)が29~49g/10min大きいポリプロピレン樹脂を用いることができる。
アルケマ社製ポリアミド11樹脂「Rilsan BMN O」(商品名、重量平均分子量17,000、融点190℃)からなるペレット10質量部と、三井化学社製無水マレイン酸変性エチレン・ブテン共重合体「タフマー MH7020」(商品名、重量平均分子量199,000)からなるペレット8質量部とをドライブレンドした後、混合ペレットをコペリオン社製二軸溶融混練押出機(型式「ZSK50」)に投入し、混練温度210℃、押出速度150kg/時間、スクリュー回転数200回転/分の条件で溶融混練を行った。そして、ペレタイザーを用いて混合樹脂ペレット(第1溶融混練物)を得た。
次に、混合樹脂ペレット(第1溶融混練物)18質量部と、日本ポリプロ社製ポリプロピレン樹脂「ノバテック MA1B」(商品名、プロピレンホモポリマー、融点165℃)22質量部とをドライブレンドした後、混合ペレットをコペリオン社製二軸溶融混練押出機(型式「ZSK50」)に投入し、混練温度210℃、押出速度150kg/時間、スクリュー回転数200回転/分の条件で溶融混練を行った。そして、ペレタイザーを用いて混合樹脂ペレット(第2溶融混練物)を得た。
その後、混合樹脂ペレット(第2溶融混練物)40質量部と、プロピレンブロックポリマー(MFR50~70g/10min、融点165℃)60質量部と、発泡剤としての炭酸水素ナトリウム4質量部とをドライブレンドし、混合物からなる製造原料(C3)を得た。
アルケマ社製ポリアミド11樹脂「Rilsan BMN O」(商品名、重量平均分子量17,000、融点190℃)からなるペレット5質量部と、三井化学社製無水マレイン酸変性エチレン・ブテン共重合体「タフマー MH7020」(商品名、重量平均分子量199,000)からなるペレット4質量部とをドライブレンドした後、混合ペレットをコペリオン社製二軸溶融混練押出機(型式「ZSK50」)に投入し、混練温度210℃、押出速度150kg/時間、スクリュー回転数200回転/分の条件で溶融混練を行った。そして、ペレタイザーを用いて混合樹脂ペレット(第1溶融混練物)を得た。
次に、混合樹脂ペレット(第1溶融混練物)9質量部と、日本ポリプロ社製ポリプロピレン樹脂「ノバテック MA1B」(商品名、プロピレンホモポリマー、融点165℃)11質量部とをドライブレンドした後、混合ペレットをコペリオン社製二軸溶融混練押出機(型式「ZSK50」)に投入し、混練温度210℃、押出速度150kg/時間、スクリュー回転数200回転/分の条件で溶融混練を行った。そして、ペレタイザーを用いて混合樹脂ペレット(第2溶融混練物)を得た。
その後、混合樹脂ペレット(第2溶融混練物)20質量部と、プロピレンブロックポリマー(MFR50~70g/10min、融点165℃)80質量部と、発泡剤としての炭酸水素ナトリウム4質量部とをドライブレンドし、混合物からなる製造原料(C4)を得た。
アルケマ社製ポリアミド11樹脂「Rilsan BMN O」(商品名、重量平均分子量17,000、融点190℃)からなるペレット3.75質量部と、三井化学社製無水マレイン酸変性エチレン・ブテン共重合体「タフマー MH7020」(商品名、重量平均分子量199,000)からなるペレット3質量部とをドライブレンドした後、混合ペレットをコペリオン社製二軸溶融混練押出機(型式「ZSK50」)に投入し、混練温度210℃、押出速度150kg/時間、スクリュー回転数200回転/分の条件で溶融混練を行った。そして、ペレタイザーを用いて混合樹脂ペレット(第1溶融混練物)を得た。
次に、混合樹脂ペレット(第1溶融混練物)6.75質量部と、日本ポリプロ社製ポリプロピレン樹脂「ノバテック MA1B」(商品名、プロピレンホモポリマー、融点165℃)8.25質量部とをドライブレンドした後、混合ペレットをコペリオン社製二軸溶融混練押出機(型式「ZSK50」)に投入し、混練温度210℃、押出速度150kg/時間、スクリュー回転数200回転/分の条件で溶融混練を行った。そして、ペレタイザーを用いて混合樹脂ペレット(第2溶融混練物)を得た。
その後、混合樹脂ペレット(第2溶融混練物)15質量部と、プロピレンブロックポリマー(MFR50~70g/10min、融点165℃)85質量部と、発泡剤としての炭酸水素ナトリウム4質量部とをドライブレンドし、混合物からなる製造原料(C5)を得た。
アルケマ社製ポリアミド11樹脂「Rilsan BMN O」(商品名、重量平均分子量17,000、融点190℃)からなるペレット2.5質量部と、三井化学社製無水マレイン酸変性エチレン・ブテン共重合体「タフマー MH7020」(商品名、重量平均分子量199,000)からなるペレット2質量部とをドライブレンドした後、混合ペレットをコペリオン社製二軸溶融混練押出機(型式「ZSK50」)に投入し、混練温度210℃、押出速度150kg/時間、スクリュー回転数200回転/分の条件で溶融混練を行った。そして、ペレタイザーを用いて混合樹脂ペレット(第1溶融混練物)を得た。
次に、混合樹脂ペレット(第1溶融混練物)4.5質量部と、日本ポリプロ社製ポリプロピレン樹脂「ノバテック MA1B」(商品名、プロピレンホモポリマー、融点165℃)5.5質量部とをドライブレンドした後、混合ペレットをコペリオン社製二軸溶融混練押出機(型式「ZSK50」)に投入し、混練温度210℃、押出速度150kg/時間、スクリュー回転数200回転/分の条件で溶融混練を行った。そして、ペレタイザーを用いて混合樹脂ペレット(第2溶融混練物)を得た。
その後、混合樹脂ペレット(第2溶融混練物)10質量部と、プロピレンブロックポリマー(MFR50~70g/10min、融点165℃)90質量部と、発泡剤としての炭酸水素ナトリウム4質量部とをドライブレンドし、混合物からなる製造原料(C6)を得た。
アルケマ社製ポリアミド11樹脂「Rilsan BMN O」(商品名、重量平均分子量17,000、融点190℃)からなるペレット1.25質量部と、三井化学社製無水マレイン酸変性エチレン・ブテン共重合体「タフマー MH7020」(商品名、重量平均分子量199,000)からなるペレット1質量部とをドライブレンドした後、混合ペレットをコペリオン社製二軸溶融混練押出機(型式「ZSK50」)に投入し、混練温度210℃、押出速度150kg/時間、スクリュー回転数200回転/分の条件で溶融混練を行った。そして、ペレタイザーを用いて混合樹脂ペレット(第1溶融混練物)を得た。
次に、混合樹脂ペレット(第1溶融混練物)2.25質量部と、日本ポリプロ社製ポリプロピレン樹脂「ノバテック MA1B」(商品名、プロピレンホモポリマー、融点165℃)2.75質量部とをドライブレンドした後、混合ペレットをコペリオン社製二軸溶融混練押出機(型式「ZSK50」)に投入し、混練温度210℃、押出速度150kg/時間、スクリュー回転数200回転/分の条件で溶融混練を行った。そして、ペレタイザーを用いて混合樹脂ペレット(第2溶融混練物)を得た。
その後、混合樹脂ペレット(第2溶融混練物)5質量部と、プロピレンブロックポリマー(MFR50~70g/10min、融点165℃)95質量部と、発泡剤としての炭酸水素ナトリウム4質量部とをドライブレンドし、混合物からなる製造原料(C7)を得た。
日本ポリプロ社製ポリプロピレン樹脂「ノバテック MA1B」(商品名、プロピレンホモポリマー、融点165℃)からなるペレット100質量部と、発泡剤としての炭酸水素ナトリウム4質量部とをドライブレンドし、混合物からなる製造原料(C8)を得た。
実施例1~7及び比較例1
上記の製造原料を射出発泡成形に供し、発泡倍率として、1.5倍、1.8倍又は2.4倍としたフロントドアトリム基材を得た。これらの実施例1~7の発泡樹脂成形体では、酸素プラズマエッチング処理した後、更に、オスミウムコート処理を施した試験片(発泡樹脂成形体の試験片)の処理面を電界放出形走査型電子顕微鏡(FE-SEM)で観察することで、連続相(X)、分散相(Y)、母相(Y1)及び微分散相(Y2)の存在が確認される。特に、分散相及び微分散相は、1000倍以上(通常10,000倍以下)に拡大した画像で観察される。また、各相を構成する成分は、このFE-SEMを用いた観察時にエネルギー分散型X線分析(EDS)を行うことで特定される。
○:衝突によりフロントドアトリム基材の破壊挙動が見られない又は破壊したが飛散しなかった
×:衝突によりフロントドアトリム基材の破壊挙動が見られ飛散した
11:固定型、
12:可動型、
13:スプルー、
14:キャビティ、
16:製造原料部、
18:発泡樹脂成形体、
20:フロントドアトリム基材、
25:アームレスト部、
30:サイドエアバッグ、
40:ダミー、
50:ドアパネル、
60:台車、
X;連続相、
Y;分散相、
Y1;母相(分散相Y内の連続相)、
Y2;微分散相(分散相Y内の分散相)、
Z;気泡。
Claims (11)
- オレフィン樹脂及びポリアミド樹脂を含有するオレフィン系樹脂組成物からなる発泡樹脂成形体において、
前記オレフィン系樹脂組成物は、前記オレフィン樹脂を含む連続相と、該連続相の中に分散されたポリアミド樹脂を含む分散相とを備え、
前記分散相は、前記ポリアミド樹脂と、該ポリアミド樹脂に対する反応性基を有するエラストマーとの溶融混練物を含むことを特徴とする発泡樹脂成形体。 - 前記分散相が、前記ポリアミド樹脂を含む母相と、該母相の中に分散された、前記反応性を有する前記エラストマーを含む微分散相とを有し、発泡された気泡は前記分散相及び前記微分散相ではなく前記連続相のみにある請求項1に記載の発泡樹脂成形体。
- 前記分散相の割合が、前記連続相及び前記分散相の合計を100質量%とした場合に、70質量%以下である請求項1又は2に記載の発泡樹脂成形体。
- 前記オレフィン樹脂がプロピレンに由来する構造単位を含む重合体である請求項1乃至3のいずれか一項に記載の発泡樹脂成形体。
- 前記ポリアミド樹脂が、ポリアミド6、ポリアミド66、ポリアミド610、ポリアミド612、ポリアミド614、ポリアミド11、ポリアミド12、ポリアミド6T、ポリアミド6I、ポリアミド9T、ポリアミドM5T、ポリアミド1010、ポリアミド1012、ポリアミド10T、ポリアミドMXD6、ポリアミド6T/66、ポリアミド6T/6I、ポリアミド6T/6I/66、ポリアミド6T/2M-5T及びポリアミド9T/2M-8Tから選ばれた少なくとも1つである請求項1乃至4のいずれか一項に記載の発泡樹脂成形体。
- 前記反応性基を有する前記エラストマーが、エチレン又はプロピレンに由来する構造単位を含むオレフィン系熱可塑性エラストマー又は芳香族ビニル化合物に由来する構造単位を含むスチレン系熱可塑性エラストマーである請求項1乃至5のいずれか一項に記載の発泡樹脂成形体。
- 前記反応性基を有する前記エラストマーが、酸無水物変性エラストマー、カルボン酸変性エラストマー、エポキシ変性エラストマー及びオキサゾリン変性エラストマーから選ばれた少なくとも1種である請求項1乃至6のいずれか一項に記載の発泡樹脂成形体。
- 請求項1乃至7のいずれか一項に記載の発泡樹脂成形体の製造方法であって、
ポリアミド樹脂と、該ポリアミド樹脂に対する反応性基を有するエラストマーとを溶融混練する第1溶融混練工程と、該第1溶融混練工程により得られた第1溶融混練物と、オレフィン樹脂とを溶融混練する第2溶融混練工程と、該第2溶融混練工程により得られた第2溶融混練物とオレフィン樹脂とを混合する混合工程とを備える方法により得られた製造原料を、発泡させることを特徴とする、発泡樹脂成形体の製造方法。 - 前記混合工程で用いる前記オレフィン樹脂が、前記第2溶融混練工程で用いるオレフィン樹脂と異なる請求項8に記載の発泡樹脂成形体の製造方法。
- 前記混合工程で用いる前記オレフィン樹脂の流動性が、前記第2溶融混練工程で用いるオレフィン樹脂の流動性より高い請求項9に記載の発泡樹脂成形体の製造方法。
- 請求項1乃至7のいずれか一項に記載の発泡樹脂成形体の製造方法であって、
ポリアミド樹脂と、該ポリアミド樹脂に対する反応性基を有するエラストマーとを溶融混練する第1溶融混練工程と、該第1溶融混練工程により得られた第1溶融混練物と、オレフィン樹脂とを溶融混練する第2溶融混練工程とを備える方法により得られた製造原料を、発泡させることを特徴とする、発泡樹脂成形体の製造方法。
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EP3705283A4 (en) * | 2017-10-30 | 2021-08-11 | Lotte Chemical Corporation | METHOD OF MANUFACTURING A FOAM AND FOAM SO MANUFACTURED |
US11535722B2 (en) | 2017-10-30 | 2022-12-27 | Lotte Chemical Corporation | Method for producing foam, and foam produced thereby |
DE112019006611T5 (de) | 2019-01-09 | 2021-09-23 | Toyota Boshoku Kabushiki Kaisha | Schwingungsabsorbierendes Material |
Also Published As
Publication number | Publication date |
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KR101954335B1 (ko) | 2019-03-05 |
US20190022903A1 (en) | 2019-01-24 |
CN108473707B (zh) | 2019-06-14 |
EP3428224A1 (en) | 2019-01-16 |
RU2682581C1 (ru) | 2019-03-19 |
US11992980B2 (en) | 2024-05-28 |
SG11201806672XA (en) | 2018-09-27 |
BR112018007294A2 (pt) | 2018-10-23 |
CN108473707A (zh) | 2018-08-31 |
KR20180094115A (ko) | 2018-08-22 |
BR112018007294B1 (pt) | 2022-08-23 |
EP3428224B1 (en) | 2020-12-23 |
JPWO2017155114A1 (ja) | 2018-03-15 |
EP3428224A4 (en) | 2019-11-06 |
JP6311852B2 (ja) | 2018-04-18 |
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