Polypropylene resin expanded beads and polypropylene resin expanded bead molded body

Abstract

To provide polypropylene-based resin foamed particles capable of producing a foamed particles molded article that has a desired shape and excels in appearance and rigidity even in the case of omitting a curing step.SOLUTION: Polypropylene-based resin foamed particles 1 of the present invention have through holes 11. The through hole 11 has an average hole diameter d of 1 mm or less. The foamed particle 1 has a closed cell content of 85% or more. The foamed particle 1 has an average cell diameter La of 50 μm or more and 300 μm or less, and has an inner surface layer on the inner circumferential side of the foamed particle 1. The average cell diameter Li of the inner surface layer on the inner circumferential side of the foamed particle 1 is between 5 μm and 150 μm, and the average cell diameter Li of the inner surface layer is smaller than the average cell diameter La of the foamed particle 1.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to expanded polypropylene resin beads having through-holes and to an expanded bead molding obtained by molding the expanded beads in a mold. [Background technology]

[0002] Polypropylene resin expanded bead molded articles are used in various applications because they are lightweight and have excellent cushioning properties, rigidity, etc. Examples of methods for producing polypropylene resin expanded bead molded articles include an in-mold molding method in which expanded polypropylene resin beads are filled into a mold and heated with steam to secondary expand the expanded beads and melt their surfaces to fuse them together, thereby forming a desired shape, and then cooled in the mold with water, air, etc., and then released from the mold.

[0003] However, if the expanded bead molding is stored at room temperature after in-mold molding, the steam that flowed into the cells of the expanded bead molding during in-mold molding and remained therein condenses in the cells, creating a negative pressure within the cells and causing the volumetric shrinkage of the expanded bead molding, which can result in significant deformation of the molding. Therefore, after releasing the expanded bead molding from the mold, a curing step is usually required in which the expanded bead molding is left to stand for a predetermined time in a high-temperature atmosphere adjusted to a temperature of about 60°C to 80°C, for example, to restore its shape.

[0004] If the curing step could be omitted in the manufacturing process of expanded polypropylene resin bead moldings, productivity could be significantly improved. For example, Patent Document 1 discloses a technique for fusing multilayer expanded beads consisting of a foamed core layer and a coating layer while maintaining voids between the beads, and Patent Document 1 states that the curing step can be omitted. Furthermore, Patent Document 2 discloses a technique for in-mold molding expanded beads using a polypropylene resin having a specific melting point, melt flow index, Z-average molecular weight, etc., and Patent Document 2 states that the curing time can be shortened. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2003-39565 [Patent Document 2] Japanese Patent Application Laid-Open No. 2000-129028 Summary of the Invention [Problem to be solved by the invention]

[0006] The technology described in Patent Document 1 can omit the curing step, but because numerous voids are formed between the expanded beads in the molded body, the resulting expanded bead molding has a significantly poor appearance and insufficient rigidity, making it unusable for some applications. The technology described in Patent Document 2 can shorten the curing step, but requires the use of special raw materials, leaving room for improvement in terms of raw material procurement, etc. Furthermore, although the curing step can be shortened, the curing step is still required. With the technology described in Patent Document 2, if the curing step is omitted, the resulting expanded bead molding shrinks and deforms significantly, making it difficult to obtain an expanded bead molding having the desired shape.

[0007] The present invention has been made in view of the above background, and provides expanded beads that can give expanded bead moldings having a desired shape and excellent appearance and rigidity, even if the curing step is omitted. [Means for solving the problem]

[0008] According to the present invention, the following expanded polypropylene resin particles are provided. [1] Polypropylene-based resin foam particles having through-holes, The through holes have an average diameter d of 1 mm or less, The foamed beads have a closed cell rate of 85% or more, The average cell diameter La of the expanded beads is 50 μm or more and 300 μm or less, The polypropylene-based resin expanded beads are characterized in that the average cell diameter Li of the inner surface layer on the inner peripheral surface side of the expanded beads is 5 μm or more and 150 μm or less, and the average cell diameter Li of the inner surface layer is smaller than the average cell diameter La of the expanded beads. [2] The expanded polypropylene resin particles according to [1], wherein the average cell diameter Li of the inner surface layer is 30 μm or more and 100 μm or less. [3] Expanded polypropylene resin particles according to [1] or [2], wherein the ratio Li / La of the average cell diameter Li of the inner surface layer to the average cell diameter La of the expanded particles is 0.65 or less. [4] Expanded polypropylene resin beads according to any one of [1] to [3], wherein the ratio d / D of the average pore diameter d of the through-holes of the expanded beads to the average outer diameter D of the expanded beads is 0.4 or less. [5] The apparent density of the expanded particles is 10 kg / m 3 More than 150kg / m 3 The expanded polypropylene resin particles according to any one of the above [1] to [4], which are as follows: [6] The expanded polypropylene-based resin beads according to any one of [1] to [5], which are multi-layer expanded beads having an expanded polypropylene-based resin core layer and a polyolefin-based resin coating layer that coats the expanded core layer. [7] A foamed polypropylene resin bead molded article obtained by molding the foamed polypropylene resin beads according to any one of [1] to [6] above in a mold. [Effects of the Invention]

[0009] The expanded polypropylene resin beads of the present invention can be molded in a mold to produce an expanded bead molding having a desired shape and excellent appearance and rigidity, even without a curing step. Furthermore, the expanded polypropylene resin beads of the present invention can improve production efficiency because of their short molding cycle. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 is a schematic perspective view of the appearance of the expanded beads of the present invention. [Figure 2] FIG. 2 is a photograph of a cross section of an expanded bead, showing a vertical cross section of the expanded bead cut perpendicular to the penetration direction of the through-holes of the expanded bead. [Figure 3] FIG. 3 is a cross-sectional photograph of an expanded bead, showing a cross section of an expanded bead cut into equal parts parallel to the penetration direction of the through-holes of the expanded bead. [Figure 4] FIG. 4 is an explanatory diagram of a DSC curve of expanded beads. DETAILED DESCRIPTION OF THE INVENTION

[0011] The expanded polypropylene resin particles of the present invention will be described in detail below. In this specification, expanded polypropylene resin beads are referred to as "expanded beads" where appropriate, and expanded bead molded articles are referred to as "molded articles" where appropriate. A foamed bead molded article can be obtained by filling a large number of the foamed beads into a mold and supplying a heating medium such as steam to fuse the foamed beads together. That is, a molded article can be obtained by molding the foamed beads in a mold.

[0012] The expanded beads of the present invention have a foamed layer composed of a polypropylene-based resin. In this specification, the polypropylene-based resin refers to a homopolymer of a propylene monomer and a propylene-based copolymer containing 50% by mass or more of structural units derived from propylene. The polypropylene-based resin is preferably a propylene-based copolymer in which propylene is copolymerized with another monomer. Preferred examples of the propylene-based copolymer include copolymers of propylene and an α-olefin having 4 to 10 carbon atoms, such as an ethylene-propylene copolymer, a butene-propylene copolymer, a hexene-propylene copolymer, and an ethylene-propylene-butene copolymer. These copolymers are, for example, random copolymers or block copolymers, and are preferably random copolymers. The polypropylene-based resin may also contain multiple types of polypropylene-based resins.

[0013] The polypropylene-based resin constituting the expanded beads is preferably a propylene-based random copolymer such as a propylene-ethylene random copolymer or a propylene-ethylene-butene random copolymer, and the content of the comonomer component in the copolymer is preferably 0.5% by mass or more and 10% by mass or less. The total of the comonomer component and the propylene component in the propylene-based random copolymer is 100% by mass. In this case, it becomes possible to mold a good molded article with excellent rigidity at a lower molding heating temperature.

[0014] From the viewpoint of obtaining a molded article having superior rigidity and exhibiting less deformation and shrinkage when a curing step is omitted, it is preferable that the polypropylene-based resin constituting the expanded beads is a propylene-ethylene random copolymer, and that the ethylene content in the propylene-ethylene random copolymer is 0.5% by mass or more and less than 2.0% by mass. On the other hand, from the viewpoint of improving the moldability of the expanded beads and obtaining a molded article having excellent energy absorption properties, it is preferable that the polypropylene-based resin constituting the expanded beads is a propylene-ethylene random copolymer, and that the ethylene content in the propylene-ethylene random copolymer is more than 2.0% by mass and less than 4.5% by mass, more preferably 2.5% by mass or more and less than 4.0% by mass, and even more preferably 2.8% by mass or more and less than 3.5% by mass. The content of the comonomer component in the copolymer can be determined by a known method using IR spectroscopy. In this specification, for example, the ethylene component and propylene component of a propylene-ethylene copolymer refer to the propylene-derived structural units and ethylene-derived structural units in the propylene-ethylene copolymer, respectively. The content of each monomer component in the copolymer means the content of the constituent units derived from each monomer in the copolymer.

[0015] The polypropylene resin constituting the expanded beads may contain other polymers besides the polypropylene resin as long as the objects and effects of the present invention are not impaired. Examples of other polymers include thermoplastic resins other than polypropylene resins, such as polyethylene resins and polystyrene resins, and thermoplastic elastomers. The content of other polymers in the polypropylene resin constituting the expanded beads is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less. It is particularly preferable that the content of other polymers is 0, i.e., the expanded beads contain only polypropylene resin as a polymer.

[0016] The melting point Tmc of the polypropylene resin constituting the expanded beads is preferably 155°C or lower. In this case, a molded article having excellent appearance and rigidity can be molded at a lower molding temperature (low molding pressure). From the viewpoint of enabling molding at a low molding pressure, the melting point Tmc of the polypropylene resin constituting the expanded beads is more preferably 153°C or lower. On the other hand, in order to further improve the heat resistance and mechanical strength of the molded article, the melting point Tmc of the polypropylene resin constituting the expanded beads is preferably 135°C or higher, more preferably 138°C or higher, and even more preferably 140°C or higher.

[0017] The melting point of a polypropylene resin is determined in accordance with JIS K7121:1987. Specifically, the conditioning is performed using "(2) Measurement of melting temperature after a certain heat treatment," and the conditioned test piece is heated from 30°C to 200°C at a heating rate of 10°C / min to obtain a DSC curve, with the apex temperature of the melting peak being taken as the melting point. Note that if multiple melting peaks appear on the DSC curve, the apex temperature of the melting peak with the largest area is taken as the melting point.

[0018] To further improve expandability and moldability, the melt flow rate (MFR) of the polypropylene resin constituting the expanded beads is preferably 5 g / 10 min or more, more preferably 6 g / 10 min or more, and even more preferably 7 g / 10 min or more. On the other hand, to further increase the rigidity of the molded body, the MFR is preferably 12 g / 10 min or less, more preferably 10 g / 10 min or less. The MFR of the polypropylene resin is the melt mass flow rate value measured according to JIS K7210-1:2014 at a test temperature of 230°C and a load of 2.16 kg.

[0019] The flexural modulus of the polypropylene-based resin constituting the expanded beads is preferably 800 MPa or more and 1600 MPa or less. To increase the rigidity of the molded article and more reliably suppress dimensional change even when a curing step is omitted, the flexural modulus of the polypropylene-based resin constituting the expanded beads is preferably 800 MPa or more, more preferably 850 MPa or more, and even more preferably 900 MPa or more. On the other hand, since a molded article with excellent appearance and rigidity can be molded at a lower molding temperature and an expanded bead molded article with excellent energy absorption properties can be obtained, the flexural modulus of the polypropylene-based resin constituting the expanded beads is preferably less than 1200 MPa, more preferably 1100 MPa or less, and even more preferably 1000 MPa or less. The flexural modulus of the polypropylene-based resin can be determined in accordance with JIS K7171:2008. In the past, when expanded beads made of a polypropylene resin having a flexural modulus of less than 1200 MPa were molded in a mold, the molded product tended to shrink and deform significantly if the curing step was omitted, possibly because the resistance to shrinkage and deformation after demolding was low. With the expanded beads of the present invention, the curing step can be omitted even when the expanded beads are made of a polypropylene resin having a flexural modulus of less than 1200 MPa.

[0020] Next, the characteristic shape, cell diameter, etc. of the expanded beads of the present invention will be described. The expanded beads of the present invention are formed by forming through holes in expanded beads of a known shape such as a sphere, a cylinder, etc. The overall shape of the expanded beads is preferably a columnar shape such as a cylinder or a prism because it is easy to produce.

[0021] The through-hole is preferably at least one cylindrical hole that penetrates the columnar expanded bead in the axial direction. It is more preferable that the expanded bead is cylindrical and has one cylindrical hole that penetrates the columnar expanded bead in the axial direction.

[0022] The expanded beads of the present invention have a specific cell structure in addition to through-holes, as described below. By molding such expanded beads in a mold, it is possible to obtain an expanded bead molding having a desired shape and excellent appearance and rigidity, even if the curing step is omitted. Similarly, even if the curing temperature or curing time in the curing step is set lower than conventional, an expanded bead molding having a desired shape and excellent appearance and rigidity can be obtained. When the curing step is omitted, the shape of the molded product can be stabilized, for example, by leaving the molded product after demolding in an environment of 23°C for 12 hours. In this specification, obtaining a molded product by omitting the curing step in the in-mold molding of expanded beads as described above is also referred to as "no-curing molding."

[0023] 1 to 3 show examples of the shape of the expanded beads of the present invention. However, the present invention is not limited to these drawings. As shown in FIGS. 1 to 3, the expanded beads 1 of the present invention are cylindrical and have through holes 11. Furthermore, as shown in FIGS. 2 and 3, the inner surface layer on the inner circumferential side of the expanded beads has a predetermined average cell diameter Li. In this specification, the inner surface layer of the expanded beads refers to the portion extending from the inner circumferential surface of the expanded beads (i.e., the outer periphery of the through holes) to 300 μm toward the outer surface.

[0024] The through-holes formed in the expanded beads form new passages in addition to the gaps between the expanded beads, allowing a heating medium such as steam to easily flow throughout the expanded beads during molding. As a result, the heat transfer efficiency of the heating medium is improved, allowing for reductions in heating time and amount of heating medium used, thereby improving production efficiency. Furthermore, the molding cycle is shortened and the curing process can be omitted, further improving production efficiency.

[0025] If the expanded beads do not have through-holes, omitting the curing step may result in significant shrinkage and deformation of the molded product. On the other hand, even if the expanded beads have through-holes, if the average pore diameter d is too large, the through-holes may not be easily blocked in the resulting molded product, which may result in a deterioration in the appearance and rigidity of the molded product. For these reasons, the average pore diameter d of the expanded beads must be 1 mm or less. From the viewpoint of being able to obtain a molded product having the desired shape and superior appearance and rigidity even when the curing step is omitted, the average pore diameter d of the expanded beads is preferably 0.9 mm or less, more preferably 0.8 mm or less, and particularly preferably 0.7 mm or less. The lower limit of the average pore diameter d of the expanded beads is preferably 0.1 mm or more, more preferably 0.2 mm or more, from the viewpoint of being able to more reliably suppress shrinkage and deformation of the molded product when the curing step is omitted.

[0026] When small-diameter through-holes are formed in the expanded beads, a good expanded bead molding can be obtained without shrinkage or deformation, even when the curing step is omitted. The reasons for this are unclear, but are thought to be as follows: It is believed that the molded body obtained by in-mold molding of the expanded beads of the present invention is likely to have minute voids communicating with the outside of the molded body. Therefore, air quickly flows into the bubbles inside the molded body after demolding, increasing the internal pressure of the entire molded body, which is thought to facilitate early dimensional stabilization of the molded body. Furthermore, the formation of through-holes facilitates the inflow of a heating medium such as steam into the molded body through the through-holes during in-mold molding, allowing molding to be performed at a lower molding steam pressure. The combination of these phenomena allows a good expanded bead molding to be obtained without shrinkage or deformation, even when the curing step is omitted. The minute voids formed in the molded body are formed by a complex combination of interconnected voids between the expanded beads, interconnected voids due to through-holes that have not been completely blocked, interconnected voids between the through-holes and the voids between the expanded beads, and open-cell portions of the expanded beads resulting from the rupture of bubbles in the inner layer.

[0027] The average pore diameter d of the expanded beads can be adjusted by adjusting the pore diameter dr of the through-holes in the resin beads, which will be described later, as well as by adjusting the apparent density and high-temperature peak calorific value of the expanded beads. Furthermore, by producing the expanded beads as two-stage expanded beads by a two-stage expansion method, the average pore diameter d can be more easily adjusted to a small value.

[0028] The average pore diameter d of the through holes of expanded beads is determined as follows: An expanded bead is cut perpendicular to the penetration direction of the through holes at a position where the area of ​​the cross section is approximately maximum. A photograph of the cut surface of each expanded bead is taken, the cross-sectional area of ​​the through hole portion (specifically, the opening area) is determined, and the diameter of an imaginary perfect circle having the same area as that area is calculated, and this is taken as the pore diameter of the through holes of one expanded bead. This operation is performed on 50 or more expanded beads randomly selected from the expanded bead group, and the arithmetic mean value of the obtained measurements is taken as the average pore diameter d. Note that even if the pore diameters of the through holes of each expanded bead are not uniform in the penetration direction, the pore diameter of the through holes of each expanded bead is determined by measurement at a position where the area of ​​the cross section of the expanded bead is approximately maximum, as described above.

[0029] In this specification, when an expanded bead is cut perpendicular to the penetration direction of the through holes at a position where the area of ​​the cross section is approximately maximum, if it is difficult to identify this position, the cross section can be obtained by the following method. First, the expanded bead is cut perpendicular to the penetration direction of the through holes at positions that divide the length of the through holes in the penetration direction into four equal parts to obtain three cross sections. Of the obtained cross sections, the cross section with the largest area can be used as the measurement object.

[0030] The average cell diameter La of the expanded beads is 50 μm or more and 300 μm or less. When the average cell diameter La of the expanded beads is within this range, the secondary expandability of the expanded beads and the heat resistance to heating during in-mold molding are appropriately adjusted, resulting in good in-mold moldability of the expanded beads. In addition, the mechanical properties of the resulting expanded bead molded article are excellent. From this perspective, the average cell diameter La of the expanded beads is preferably 80 μm or more and 280 μm or less, and more preferably 100 μm or more and 250 μm or less.

[0031] The average cell diameter La of expanded beads is measured as follows. An expanded bead is cut perpendicular to the penetration direction of the through-holes at a position where the cross-sectional area is approximately maximum. One of the cut sections of the expanded bead is photographed, and four lines are drawn at equal angles (i.e., 45°) on the vertical cross-sectional photograph from the outermost surface of the expanded bead through the center of the through-hole to the outermost surface on the opposite side. Next, the number of cells intersecting each line is counted. The total length of the line segments intersecting with the cells being measured is then divided by the total number of cells counted to determine the cell diameter of the expanded beads. This procedure is performed on 50 or more expanded beads randomly selected from the expanded bead group, and the arithmetic mean value of the obtained measurements is defined as the average cell diameter La of the expanded beads.

[0032] The average cell diameter Li of the inner surface layer on the inner peripheral side of the expanded beads of the present invention is within a predetermined range and is smaller than the average cell diameter La. That is, in the present invention, in addition to the formation of small through-holes as described above, an inner surface layer with fine cells is formed on the inner peripheral side of the expanded beads. Therefore, the appearance of the resulting molded article is improved, its rigidity is further improved, and significant shrinkage and deformation of the molded article is prevented even if a curing step is omitted. The reason why the appearance and rigidity are further improved when the average cell diameter Li of the inner surface layer of the expanded beads is within a predetermined range and smaller than the average cell diameter La is unclear, but it is thought to be because the through-holes are more easily blocked after molding in a mold. Blocking the through-holes of the expanded beads in the molded article reduces the visibility of irregularities caused by the through-holes, improving the appearance and suppressing a decrease in rigidity.

[0033] The average cell diameter Li of the bubbles constituting the inner surface layer is 5 μm or more and 150 μm or less. If the average cell diameter Li is within this range, the through holes are more likely to be closed reliably after molding in the mold, and a molded article with superior rigidity and appearance can be obtained. The molded article also has excellent energy absorption properties. From this perspective, the average cell diameter Li of the inner surface layer of the expanded beads is preferably 100 μm or less, and more preferably 80 μm or less. On the other hand, from the perspective of preventing the bubbles in the inner surface layer from excessively breaking, the average cell diameter Li of the bubbles constituting the inner surface layer is preferably 10 μm or more, and more preferably 30 μm or more.

[0034] Furthermore, the average cell diameter Li of the inner surface layer must be smaller than the average cell diameter La of the expanded beads. If the average cell diameter Li of the inner surface layer is equal to or larger than the average cell diameter La of the expanded beads, the above-mentioned effects of improving the appearance, further improving the rigidity, and suppressing significant shrinkage and deformation of the molded body even if the curing step is omitted may not be fully achieved.

[0035] In the past, when expanded beads having through holes were used, numerous voids originating from the through holes were formed in the resulting molded article after molding in a mold, causing deterioration in the appearance and mechanical properties such as compressive strength of the molded article. This problem was solved by the expanded beads of the present invention, in that the average pore diameter d of the through holes is a predetermined value or less, and the average cell diameter of the inner surface layer formed around the through holes is within a predetermined range.

[0036] The average cell diameter Li of the inner surface layer is measured as follows. An expanded bead is cut perpendicular to the penetration direction of the through holes at a position where the cross-sectional area is approximately maximum. One of the cut sections of the expanded bead is photographed, and four lines are drawn at equal angles (i.e., 45°) on the vertical cross-sectional photograph from the outermost surface of the expanded bead through the center of the through hole to the outermost surface on the opposite side. The number of bubbles that intersect with each line from the outer periphery of the through hole to 300 μm (i.e., the 300 μm portion of each line from the outer periphery of the through hole toward the outer surface of the expanded bead) is counted. The total length of the line segments intersecting with the bubbles being measured is then divided by the total number of bubbles counted to determine the cell diameter of the inner surface layer. This procedure is performed on 50 or more expanded beads randomly selected from the expanded bead group, and the arithmetic mean value of the measured values ​​is defined as the average cell diameter Li of the inner surface layer.

[0037] Expanded beads having an average cell diameter Li in the inner surface layer within the fine range described above can be produced, for example, by using a die having a shape that strongly orients the resin particles on the through-hole side in the resin particle granulation process described below. It is thought that the resin particles obtained by such a production process have resin orientation imparted to the cell membrane on the through-hole side, promoting crystallization, and that the crystallized resin acts as a nucleus during foaming, making the cell diameter likely to be small.

[0038] In order to improve the in-mold moldability of the expanded beads and to reliably improve the appearance and rigidity of the expanded bead molding when the curing step is shortened or omitted, the ratio Li / La of the average cell diameter Li of the inner layer to the average cell diameter La of the expanded beads is preferably 0.65 or less, more preferably 0.6 or less, and even more preferably 0.55 or less. The lower limit of the ratio Li / La is about 0.2, preferably 0.4.

[0039] The closed cell ratio of the expanded beads is 85% or more. If the closed cell ratio is within this range, the expanded beads can be easily molded in a mold, and the appearance and rigidity of the expanded beads are good. From this viewpoint, the closed cell ratio of the expanded beads is preferably 92% or more, and more preferably 95% or more.

[0040] The closed cell content of the expanded particles can be measured using an air comparison hydrometer in accordance with ASTM-D2856-70 Procedure C. Specifically, it is measured as follows: Bulk volume after conditioning: about 20 cm 3 The expanded beads are used as measurement samples, and their apparent volume Va is accurately measured by the ethanol immersion method as described below. After the measurement sample whose apparent volume Va has been measured is thoroughly dried, the true volume value Vx of the measurement sample is measured using an air comparison hydrometer in accordance with procedure C described in ASTM-D2856-70. Based on these volume values ​​Va and Vx, the closed cell ratio is calculated using the following formula (1), and the arithmetic average value of five samples (N=5) is taken as the closed cell ratio of the expanded beads.

[0041] Closed cell ratio (%)=(Vx-W / ρ)×100 / (Va-W / ρ) (1) however, Vx: The true volume of the expanded beads measured by the above method, i.e., the sum of the volume of the resin constituting the expanded beads and the total volume of the closed cells in the expanded beads (unit: cm 3 ) Va: The apparent volume (unit: cm) of the foamed particles measured from the rise in the water level when the foamed particles are submerged in a measuring cylinder containing ethanol. 3 ) W: Weight of the sample for measuring foam particles (unit: g) ρ: Density of the resin that makes up the foamed particles (unit: g / cm 3 )

[0042] The average outer diameter D of the expanded beads is preferably 2 mm or more, more preferably 2.5 mm or more, and even more preferably 3 mm or more. If the average outer diameter D is within this range, the secondary expandability of the cylindrical expanded beads and the rigidity of the resulting molded article will be good. On the other hand, the average outer diameter D is preferably 5 mm or less, more preferably 4.5 mm or less, and even more preferably 4.3 mm or less. If the average outer diameter D is within this range, the filling property into the molding die during molding will be good.

[0043] The ratio d / D of the average pore diameter d to the average outer diameter D of the expanded beads is preferably 0.4 or less, more preferably 0.3 or less, and even more preferably 0.25 or less. The lower limit of the ratio d / D is preferably 0.1. If the ratio d / D is within this range, the cylindrical expanded beads have a sufficient wall thickness, the expanded beads have good secondary expandability, and the resulting molded article has good appearance and rigidity.

[0044] The average outer diameter D of the expanded beads is determined as follows. An expanded bead is cut perpendicular to the penetration direction of the through holes at a position where the area of ​​the cross section is approximately maximum. A photograph of the cut surface of each expanded bead is taken, and the cross-sectional area of ​​the expanded bead (specifically, the cross-sectional area including the openings of the through holes) is determined. The diameter of an imaginary circle having the same area as this area is calculated and used as the outer diameter of the expanded bead. This operation is performed on 50 or more expanded beads randomly selected from the expanded bead group, and the arithmetic mean value of the obtained measurements is used as the average outer diameter D. Even if the outer diameter of each expanded bead is not uniform in the penetration direction, the outer diameter of each expanded bead is determined by measuring at the position where the area of ​​the cross section of the expanded bead in the direction perpendicular to the penetration direction is approximately maximum, as described above.

[0045] The average wall thickness t of the expanded beads is preferably 1 mm or more and 2 mm or less. If the average wall thickness t is within this range, the expanded beads will have a sufficiently large wall thickness, which will further improve the secondary foaming properties during in-mold molding. In addition, the expanded beads will be more resistant to crushing by external forces, which will further improve the rigidity of the molded product. From this perspective, the average wall thickness t of the expanded beads is more preferably 1.1 mm or more.

[0046] The average thickness t of the expanded beads is the distance from the surface (outer surface) of the expanded beads to the outer periphery of the through-holes (inner surface of the expanded beads), and is a value calculated by the following formula (2). t=(Dd) / 2 (2) d: Average hole diameter of through hole (mm) D: Average outer diameter of foam particles (mm)

[0047] Furthermore, the ratio t / D of the average wall thickness t of the expanded beads to the average outer diameter D is preferably 0.35 or more and 0.5 or less. When t / D is within this range, the expanded beads have good filling properties during in-mold molding, and the secondary foaming properties are further improved. Therefore, molded articles with excellent appearance and rigidity can be produced at lower molding heating temperatures.

[0048] The apparent density of the foam particles is 10 kg / m 3 More than 150kg / m 3 It is preferably 15 kg / m or less, and more preferably 15 kg / m 3 More than 100kg / m 3 or less, more preferably 20 kg / m 3 More than 80kg / m 3 and particularly preferably 25 kg / m 3 More than 60kg / m 3 If the apparent density is within this range, the resulting molded article will have a good balance between light weight and rigidity.

[0049] In the past, when a molded body was produced using expanded beads having a low apparent density, the molded body was prone to significant deformation after demolding, making it difficult to omit the curing step. In contrast, according to the present invention, even when a low-density molded body was produced using expanded beads having a low apparent density, the curing step can be omitted, and a molded body having little dimensional change and excellent rigidity and appearance can be produced without curing.

[0050] The apparent density of the expanded particles is measured by submerging a group of expanded particles (weight W (g) of expanded particles) that has been left in a measuring cylinder containing alcohol (e.g., ethanol) at 23°C for one day under conditions of 50% relative humidity, 23°C, and 1 atm using a wire netting or the like, and calculating the volume V (cm) of the expanded particles from the rise in the water level. 3) and divide the weight of the expanded particles by the volume of the expanded particles (W / V) to convert the unit.

[0051] The ratio of the apparent density of the expanded beads to the bulk density of the expanded beads (apparent density / bulk density) is preferably 1.7 or more. If the ratio is within this range, significant shrinkage and deformation of the molded body can be further suppressed even if the curing step is omitted. On the other hand, the ratio (apparent density / bulk density) is preferably 2.1 or less, more preferably 2.0 or less, and even more preferably 1.9 or less. If the ratio is within this range, the rigidity of the molded body can be further increased and the appearance can be made better.

[0052] The bulk density of the expanded beads can be calculated as follows: Expanded beads are randomly taken from the expanded bead group and placed in a measuring cylinder with a volume of 1 L. A large number of expanded beads are placed up to the 1 L mark so as to form a natural pile. The mass W2 [g] of the expanded beads placed is calculated based on the volume V2 (1000 cm). 3 ) and convert it into units to obtain the bulk density of the expanded beads.

[0053] Next, the crystalline structure of the expanded beads of the present invention, as analyzed by differential scanning calorimetry (DSC), will be described. The expanded beads preferably have a crystalline structure in which a melting peak specific to polypropylene resins (intrinsic peak) and one or more melting peaks (high-temperature peaks) appear on the higher temperature side of the DSC curve obtained when heated from 23°C to 200°C at a heating rate of 10°C / min. The DSC curve is obtained by differential scanning calorimetry (DSC) in accordance with JIS K7121:1987 using 1 to 3 mg of the expanded beads as a test sample.

[0054] The intrinsic peak is an endothermic peak specific to the polypropylene resin constituting the expanded beads, and is believed to be due to the endothermic heat generated during melting of the polypropylene resin's inherent crystals. On the other hand, the endothermic peak (high-temperature peak) on the higher temperature side of the intrinsic peak is an endothermic peak that appears higher than the intrinsic peak on the DSC curve. The appearance of this high-temperature peak is presumed to indicate the presence of secondary crystals in the resin. In addition, the DSC curve obtained by heating from 23°C to 200°C at a heating rate of 10°C / min (first heating), cooling from 200°C to 23°C at a cooling rate of 10°C / min, and then heating again from 23°C to 200°C at a heating rate of 10°C / min (second heating) shows only the intrinsic peak, making it possible to distinguish between the intrinsic peak and the high-temperature peak. The peak temperature of this intrinsic peak may differ slightly between the first and second heatings, but the difference is usually within 5°C.

[0055] The heat of fusion of the expanded beads at the high-temperature peak is preferably 5 J / g or more and 40 J / g or less. If the heat of fusion of the high-temperature peak is within this range, the moldability of the expanded beads can be further improved and a molded product with superior rigidity can be obtained. For these reasons, the heat of fusion of the high-temperature peak is more preferably 7 J / g or more and 30 J / g or less, and even more preferably 10 J / g or more and 20 J / g or less.

[0056] Furthermore, the ratio of the heat of fusion of the high-temperature peak to the heat of fusion of the total melting peak on the DSC curve (heat of fusion of the high-temperature peak / heat of fusion of the total melting peak) is preferably 0.05 or more and 0.3 or less, more preferably 0.1 or more and 0.28 or less, and even more preferably 0.15 or more and 0.25 or less. By setting the ratio of the heat of fusion of the high-temperature peak to the heat of fusion of the total melting peak within this range, it is believed that the presence of secondary crystals appearing as a high-temperature peak will result in the expanded beads having particularly excellent mechanical strength and excellent in-mold moldability. Here, the heat of fusion of all melting peaks refers to the total heat of fusion determined from the area of ​​all melting peaks on a DSC curve.

[0057] The heat of fusion of each peak in the DSC curve of expanded beads is determined as follows. First, one expanded bead is sampled from a group of expanded beads. This expanded bead is used as a test specimen, and a DSC curve is obtained by heating the test specimen from 23°C to 200°C at a heating rate of 10°C / min using a differential scanning calorimeter. Figure 4 shows an example of a DSC curve. As shown in Figure 4, the DSC curve shows an intrinsic peak ΔH1 and a high-temperature peak ΔH2, which has a peak at a higher temperature than the peak of the intrinsic peak ΔH1. Next, a line L1 is obtained by connecting point α at 80°C on the DSC curve with point β at the melting end temperature T of the expanded beads. Next, a line L2 parallel to the vertical axis of the graph is drawn from point γ on the DSC curve, which corresponds to the valley between the intrinsic peak ΔH1 and the high-temperature peak ΔH2, and the point where lines L1 and L2 intersect is designated as δ. Point γ can also be considered a maximum point between the intrinsic peak ΔH1 and the high-temperature peak ΔH2. The area of ​​the intrinsic peak ΔH1 is the area surrounded by the curve of the intrinsic peak ΔH1 portion of the DSC curve, the line segment α-δ, and the line segment γ-δ, and this is taken as the heat of fusion of the intrinsic peak. The area of ​​the high-temperature peak ΔH2 is the area surrounded by the curve of the high-temperature peak ΔH2 portion of the DSC curve, the line segment δ-β, and the line segment γ-δ, and this is the heat of fusion of the high-temperature peak (high-temperature peak heat quantity). The area of ​​the total melting peak is the area enclosed by the curve of the intrinsic peak ΔH1 part of the DSC curve, the curve of the high-temperature peak ΔH2 part, and the line segment α-β (straight line L1), and this is the heat of fusion of the total melting peak.

[0058] The expanded beads of the present invention can be molded by a known in-mold molding method, and even if a curing step is omitted, significant shrinkage, deformation, etc. can be suppressed, resulting in a molded product having a desired shape and excellent appearance and rigidity. The reason for this is as described above. Specifically, a molded product obtained by in-mold molding of the expanded beads of the present invention has minute voids that communicate with the outside of the molded product. This minute void structure is formed by a complex combination of voids between the expanded beads, voids resulting from incompletely closed through-holes, voids connecting voids resulting from through-holes and voids between the expanded beads, and open-cell portions resulting from the collapse of cells in the inner layer. Therefore, after demolding, air quickly flows into the cells inside the molded product, increasing the internal pressure of the entire molded product, and as a result, the dimensions of the molded product are quickly stabilized. Therefore, it is believed that significant shrinkage and deformation of the molded product can be suppressed even if a curing step is omitted.

[0059] The expanded beads of the present invention can be multilayer expanded beads having a multilayer structure including an expanded core layer and a coating layer covering the expanded core layer. That is, the multilayer expanded beads are composed of an expanded core layer made of the above-mentioned polypropylene-based resin and a coating layer covering the expanded core layer. The coating layer is preferably made of a polyolefin-based resin. Examples of polyolefin-based resins include polyethylene-based resins, polypropylene-based resins, and polybutene-based resins. Because of their excellent adhesion to the expanded core layer, the polyolefin-based resin is preferably a polyethylene-based resin or a polypropylene-based resin, and more preferably a polypropylene-based resin. Examples of polypropylene-based resins include propylene-ethylene copolymers, ethylene-butene copolymers, propylene-ethylene-butene copolymers, and propylene homopolymers, among which propylene-ethylene copolymers and propylene-ethylene-butene copolymers are preferred.

[0060] The melting point Tms of the polyolefin resin constituting the coating layer is preferably lower than the melting point Tmc of the polypropylene resin constituting the foamed core layer. That is, it is preferably Tms < Tmc. In this case, the fusion property of the foamed particles is improved, and molding at a lower temperature becomes possible. Furthermore, in this case, it becomes easier to suppress significant shrinkage and deformation when the curing process is omitted. Although the reason for this is not clear, it is considered that when in-mold molding is performed at a low molding heating temperature, the amount of heat received by the foamed particles from a heating medium such as steam can be more effectively suppressed, and dimensional changes due to thermal shrinkage of the molded body are more effectively suppressed. Since the fusion property is further improved and molding at a lower temperature becomes possible, it is preferably Tmc - Tms ≥ 5 (°C), more preferably Tmc - Tms ≥ 6 (°C), and even more preferably Tmc - Tms ≥ 8 (°C). From the viewpoint of suppressing peeling between the foamed core layer and the coating layer, and mutual adhesion between the foamed particles, etc., it is preferably Tmc - Tms ≤ 35 (°C), more preferably Tmc - Tms ≤ 20 (°C), and even more preferably Tmc - Tms ≤ 15 (°C).

[0061] The melting point Tms of the polyolefin resin constituting the coating layer is preferably 120°C or higher and 145°C or lower, and more preferably 125°C or higher and 140°C or lower. If the melting point Tms is within this range, the fusion property of the foamed particles during molding can be further enhanced. The melting point of the polyolefin resin constituting the coating layer is determined based on JIS K7121:1987. Specifically, it is determined under the same conditions and by the same method as the melting point of the polypropylene resin constituting the aforementioned foamed particles.

[0062] The MFR of the polyolefin resin constituting the coating layer is preferably approximately the same as the MFR of the polypropylene resin constituting the foamed core layer. Specifically, it is preferably 2 g / 10 min or higher and 15 g / 10 min or lower, more preferably 3 g / 10 min or higher and 12 g / 10 min or lower, and even more preferably 4 g / 10 min or higher and 10 g / 10 min or lower. If the MFR is within this range, peeling between the foamed core layer and the coating layer can be reliably suppressed. When the polyolefin resin is a polypropylene resin, its MFR is the melt mass-flow rate measured in accordance with JIS K7210-1:2014 at a test temperature of 230°C and a load of 2.16 kg. When the polyolefin resin is a polyethylene resin, its MFR is the melt mass-flow rate measured in accordance with JIS K7210-1:2014 at a test temperature of 190°C and a load of 2.16 kg.

[0063] The coating layer may be in a foamed or non-foamed state, but is preferably in a substantially non-foamed state, which makes it easier to achieve the effects of increasing fusion properties and lowering the molding temperature. The term "substantially non-foamed" refers to a state in which the coating layer is not foamed and does not contain bubbles, and a state in which the bubbles have disappeared after foaming, meaning that there is almost no bubble structure in the coating layer. The thickness of the coating layer is, for example, 0.5 μm or more and 100 μm or less. An intermediate layer may also be provided between the foamed core layer and the coating layer.

[0064] The mass ratio (mass %) of the resin constituting the foamed core layer to the resin constituting the coating layer is preferably 99.5:0.5 to 80:20, more preferably 99:1 to 85:15, and even more preferably 97:3 to 90:10. If the mass ratio is within this range, the moldability can be improved while maintaining the rigidity of the molded article. The mass ratio is expressed as the ratio "resin constituting the foamed core layer:resin constituting the coating layer."

[0065] Next, the method for producing the expanded beads of the present invention will be described. The expanded particles can be produced, for example, by a method in which polypropylene-based resin particles are produced using a polypropylene-based resin as a base resin, the resulting resin particles are dispersed in a dispersion medium (e.g., water), the resin particles are impregnated with a foaming agent, and the resin particles containing the foaming agent are released under low pressure together with the dispersion medium (dispersion medium release foaming method). In the dispersion medium release foaming method, resin particles are preferably dispersed in a dispersion medium in a sealed container, heated, and then a foaming agent is injected to impregnate the resin particles. After a holding step to grow secondary crystals at a constant temperature, the contents of the sealed container are released under low pressure to expand the resin particles containing the foaming agent, thereby obtaining expanded particles. When producing multilayer expanded particles having a coating layer, multilayer resin particles having a multilayer structure are produced, each having a core layer for forming an expanded core layer and a coating layer coating the core layer, and at least the core layer is expanded to obtain multilayer expanded particles having a multilayer structure having an expanded core layer and a coating layer coating the expanded core layer.

[0066] Resin particles are produced, for example, as follows. First, a polypropylene resin serving as the base resin and, if necessary, additives such as a bubble nucleating agent are fed into an extruder, heated, and kneaded to form a resin melt mixture. The resin melt mixture is then extruded through a small hole in a die attached to the tip of the extruder into a cylindrical strand having through-holes, which is then cooled and cut to obtain resin particles. The cylindrical strand having through-holes is formed by passing the molten resin mixture through a die having a flow path formed by a metal fitting attached to the tip of the die when the molten resin mixture is extruded through the small hole in the die attached to the tip of the extruder. The extrudate is then cut, for example, using a pelletizer. The cutting method can be selected from a strand cutting method, a hot cutting method, an underwater cutting method, etc. Cylindrical resin particles having through-holes can be obtained in this manner. When forming the coating layer, a resin molten mixture of each raw material is obtained using an extruder for forming a core layer and an extruder for forming a coating layer, and each molten mixture is extruded into a die and merged in the die to form a sheath-core composite molten resin mixture consisting of a molten resin mixture for forming a non-foamed tubular core layer and a molten resin mixture for forming a non-foamed coating layer that coats the outer surface of the molten resin mixture for forming the tubular core layer.The composite molten resin mixture is extruded in the form of strands through the holes in a nozzle attached to the tip of the extruder, and is cooled and cut to obtain multilayer resin particles.

[0067] The particle diameter of the resin particles is preferably 0.1 mm to 3.0 mm, more preferably 0.3 mm to 1.5 mm. The length / outer diameter ratio of the resin particles is preferably 0.5 to 5.0, more preferably 1.0 to 3.0. The average mass per particle (calculated from the masses of 200 randomly selected particles) is preferably 0.1 mg to 20 mg, more preferably 0.2 mg to 10 mg, even more preferably 0.3 mg to 5 mg, and particularly preferably 0.4 mg to 2 mg. In the case of multilayered resin particles, the mass ratio of the core layer to the coating layer is preferably 99.5:0.5 to 80:20, more preferably 99:1 to 85:15, and even more preferably 97:3 to 90:10. The mass ratio is expressed as the mass of the core layer:the mass of the coating layer.

[0068] The average diameter d of the through holes of the expanded beads can be adjusted to a desired range by adjusting the diameter dr of the through holes of the resin beads. The diameter dr of the through holes can be adjusted, for example, by the diameter of the small holes in the die used to form the through holes (the inner diameter of the die). Furthermore, the average outer diameter and average wall thickness of the expanded beads can be adjusted to the desired ranges by adjusting the particle diameter and average mass of the resin beads.

[0069] The average pore diameter dr of the through holes of the resin particles is preferably less than 0.25 mm, more preferably less than 0.24 mm, and even more preferably 0.22 mm or less. If the average pore diameter dr is within this range, expanded particles having an average pore diameter d of 1 mm or less and a ratio d / D of the average pore diameter d to the average outer diameter D of 0.4 or less can be more reliably produced. The average pore diameter dr of the through holes of the resin particles is preferably 0.1 mm or more. If the average pore diameter dr is within this range, stable production of resin particles having through holes is ensured.

[0070] For the same reasons as those for the expanded particles, the ratio dr / Dr of the average pore diameter dr to the average outer diameter Dr of the resin particles is preferably 0.4 or less, more preferably 0.3 or less, even more preferably 0.25 or less, and particularly preferably 0.2 or less. The ratio dr / Dr of the average pore diameter dr to the average outer diameter Dr of the resin particles is preferably 0.1 or more.

[0071] The average pore diameter dr of the through holes of a resin particle is determined as follows: A resin particle is cut perpendicular to the penetration direction of the through holes at a position where the area of ​​the cut surface is approximately maximum. A photograph of the cut surface of each resin particle is taken, the cross-sectional area of ​​the through hole portion (specifically, the opening area) is determined, and the diameter of an imaginary perfect circle having the same area is calculated. The arithmetic mean of these values ​​is used as the pore diameter of the through holes of one resin particle. This operation is performed on 50 or more expanded beads randomly selected from the expanded particle group, and the arithmetic mean of the obtained measurements is used as the average pore diameter dr. In addition, if the size of the through hole of each resin particle is not uniform in the through hole diameter in the through hole direction, the through hole diameter of each resin particle is determined by measurement at the position where the area of ​​the cross section of the resin particle is approximately maximum, as described above.

[0072] The average outer diameter Dr of resin particles is determined as follows: One resin particle is cut perpendicular to the penetration direction of the through holes at a position where the area of ​​the cut surface is approximately maximum. A photograph of the cut surface of each resin particle is taken, and the cross-sectional area of ​​the resin particle (specifically, the cross-sectional area including the openings of the through holes) is determined. The diameter of an imaginary circle having the same area as this area is calculated and used as the outer diameter of one resin particle. This operation is performed on 50 or more expanded particles randomly selected from the expanded particle group, and the arithmetic mean value of the obtained measurements is used as the average outer diameter Dr. In addition, if the outer diameter of each resin particle is not uniform in the penetration direction, the outer diameter of each resin particle is determined by measuring at the position where the area of ​​the cross section of the resin particle in the direction perpendicular to the penetration direction is approximately maximum, as described above.

[0073] In the strand cutting method, the particle diameter, length / outer diameter ratio, and average mass of the resin particles can be adjusted by appropriately changing the extrusion speed, take-up speed, cutter speed, etc. when extruding the molten resin mixture.

[0074] The resin particles obtained as described above can be expanded by a dispersion medium release foaming method to obtain expanded particles. In the dispersion medium release foaming method, an aqueous dispersion medium is used as a dispersion medium (specifically, a liquid) for dispersing in a sealed container. The aqueous dispersion medium is a dispersion medium (specifically, a liquid) containing water as a main component. The proportion of water in the aqueous dispersion medium is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more. Examples of dispersion mediums other than water in the aqueous dispersion medium include ethylene glycol, glycerin, methanol, and ethanol.

[0075] If necessary, additives such as bubble adjusters, crystal nucleating agents, colorants, flame retardants, flame retardant aids, plasticizers, antistatic agents, antioxidants, UV inhibitors, light stabilizers, conductive fillers, and antibacterial agents can be added to the resin particles. Examples of bubble adjusters include inorganic powders such as talc, mica, zinc borate, calcium carbonate, silica, titanium oxide, gypsum, zeolite, borax, aluminum hydroxide, and carbon; and organic powders such as phosphoric acid-based nucleating agents, phenolic-based nucleating agents, amine-based nucleating agents, and polyethylene fluoride-based resin powder. When a bubble adjuster is added, the content of the bubble adjuster is preferably 0.01 to 1 part by mass per 100 parts by mass of the polypropylene-based resin.

[0076] In the dispersion medium release foaming method, it is preferable to add a dispersant to the dispersion medium to prevent the resin particles heated in the container from fusing together. Any dispersant can be used as long as it prevents the resin particles from fusing together in the container, regardless of whether it is organic or inorganic. However, particulate inorganic materials are preferred for ease of handling. Examples of dispersants include clay minerals such as amsnite, kaolin, mica, and clay. Clay minerals may be natural or synthetic. Examples of dispersants include aluminum oxide, titanium oxide, basic magnesium carbonate, basic zinc carbonate, calcium carbonate, and iron oxide. One or more dispersants may be used. Among these, it is preferable to use a clay mineral as the dispersant. It is preferable to add 0.001 to 5 parts by mass of the dispersant per 100 parts by mass of the resin particles.

[0077] When a dispersant is used, it is preferable to use an anionic surfactant such as sodium dodecylbenzenesulfonate, sodium alkylbenzenesulfonate, sodium lauryl sulfate, sodium oleate, etc. as a dispersing aid in combination. The amount of the dispersing aid added is preferably 0.001 part by mass or more and 1 part by mass or less per 100 parts by mass of the resin particles.

[0078] A physical foaming agent is preferably used as the foaming agent for expanding the resin particles. Examples of physical foaming agents include inorganic and organic physical foaming agents. Examples of inorganic physical foaming agents include carbon dioxide, air, nitrogen, helium, and argon. Examples of organic physical foaming agents include aliphatic hydrocarbons such as propane, butane, and hexane; cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; and halogenated hydrocarbons such as hydrofluoroolefins such as 1-chloro-3,3,3-trifluoropropene and 1,3,3,3-tetrafluoropropene. Physical foaming agents may be used alone or in combination. Inorganic and organic physical foaming agents may also be used in combination. Inorganic physical foaming agents are preferred because of their environmental friendliness and ease of handling, and carbon dioxide is more preferred. When using an organic physical foaming agent, n-butane, i-butane, n-pentane, and i-pentane are preferred because of their excellent solubility in polypropylene resins and foamability.

[0079] The amount of the foaming agent added relative to 100 parts by mass of the resin particles is preferably 0.1 parts by mass or more and 30 parts by mass or less, and more preferably 0.5 parts by mass or more and 15 parts by mass or less.

[0080] In the dispersion medium release foaming method, a method of impregnating resin particles with a foaming agent is preferably used in which resin particles are dispersed in an aqueous dispersion medium in a sealed container, and the foaming agent is injected under pressure while being heated to impregnate the resin particles with the foaming agent.

[0081] The internal pressure of the sealed container during expansion is preferably 0.5 MPa (G: gauge pressure) or more. On the other hand, the internal pressure of the sealed container is preferably 4.0 MPa (G) or less. Within this range, the expanded beads can be produced safely without risk of damage or explosion of the sealed container.

[0082] In the dispersion medium release foaming method, the temperature of the aqueous dispersion medium is increased at a rate of 1° C. / min or more and 5° C. / min or less, so that the temperature during foaming can be kept within an appropriate range.

[0083] Expanded beads having a crystalline structure in which the intrinsic peak and the high-temperature peak appear in a DSC curve obtained by heat flux differential scanning calorimetry (DSC) can be obtained, for example, as follows.

[0084] During heating in the dispersion medium release foaming method, a first-stage holding step is performed in which a temperature is maintained at a temperature of at least (the melting point of the polypropylene-based resin -20°C) but less than (the melting end temperature of the polypropylene-based resin) for a sufficient time, preferably 10 to 60 minutes. The temperature is then adjusted to between (the melting point of the polypropylene-based resin -15°C) and (the melting end temperature of the polypropylene-based resin +10°C). If necessary, a second-stage holding step is performed in which the temperature is maintained for an additional sufficient time, preferably 10 to 60 minutes. Expandable resin particles containing a blowing agent are then released from a sealed container under low pressure and expanded to obtain expanded particles having the aforementioned crystalline structure. The expansion is preferably performed at a temperature in the sealed container of at least (the melting point of the polypropylene-based resin -10°C), more preferably at least (the melting point of the polypropylene-based resin) but less than (the melting point of the polypropylene-based resin +20°C).

[0085] In particular, when producing expanded beads having a low apparent density, expanded beads (first-stage expanded beads) obtained by the dispersion medium release expansion method are placed in a pressurizable sealed container, and pressurized gas such as air is injected into the container to increase the internal pressure of the expanded beads.The expanded beads are then heated in the container for a predetermined period of time using a heating medium such as steam (second-stage expansion), thereby producing expanded beads having a particularly low apparent density.

[0086] As described above, a molded article can be obtained by in-mold molding of expanded beads (in-mold molding method). In-mold molding method is carried out by filling a mold with expanded beads, introducing a heating medium into the mold, and heating. Specifically, after filling the mold with expanded beads, a heating medium is introduced into the mold, which heats the expanded beads to cause secondary expansion and fuses them together to obtain a molded article having the shape of the molding space. An example of the heating medium is steam.

[0087] The expanded bead molding obtained from the expanded beads of the present invention is obtained by molding the expanded beads in a mold, and is composed of a large number of expanded beads fused together.

[0088] The density of the foamed bead molding is 10 kg / m 3 More than 100kg / m 3 If the density is within this range, the light weight and rigidity of the molded body can be improved in a well-balanced manner. In order to further improve the rigidity of the molded body, the density of the molded body is preferably 20 kg / m or less. 3 In order to make the compact lighter, the density of the compact is preferably 80 kg / m or more. 3 More preferably, it is 50 kg / m or less. 3 The density of the compact is calculated by multiplying the weight (g) of the compact by the volume (cm) calculated from the external dimensions of the compact. 3 ) is calculated. Note that, for example, when a molded body has at least a partially complex shape and it is not easy to determine the volume from the outer dimensions of the molded body, the volume of the molded body can be determined by the submersion method. Conventionally, when producing a molded body with a low density, it has been particularly difficult to omit the curing step because the molded body is prone to significant deformation after demolding. In contrast, according to the present invention, even when the density is low, it is possible to omit the curing step, and a molded body having a desired shape and excellent appearance and rigidity can be obtained without curing. From the viewpoint of effectively exerting this effect, it is preferable that the density of the molded body be within the above range.

[0089] From the viewpoint of more sufficiently suppressing dimensional changes even when the curing step is omitted, the porosity of the molded body is preferably 4% or more, more preferably 4.5% or more, and even more preferably 5% or more. On the other hand, in order to further improve rigidity and appearance, the porosity of the molded body is preferably 12% or less, more preferably 10% or less, and even more preferably 8% or less.

[0090] The porosity of a green body is measured and calculated, for example, as follows. Specifically, first, a rectangular parallelepiped test piece (20 mm long x 100 mm wide x 20 mm high) is cut out from the center of the green body. Next, this test piece is submerged in a measuring cylinder containing ethanol, and the true volume Vc [L] of the test piece is determined from the rise in the ethanol liquid level. Meanwhile, the external volume Vd [L] is determined from the external dimensions of the test piece. The porosity of the green body can be calculated from the determined true volume Vc and the external volume Vd using the following formula (3): Porosity (%)=[(Vd-Vc) / Vd]×100...(3)

[0091] The 50% compressive stress (kPa) of the compact was measured using the density (kg / m 3 ) is 7.0 or more (kPa / (kg / m 3 )), and 7.5 (kPa / (kg / m 3 If the value is within this range, the molded article will have excellent rigidity. The ratio of the 25% compressive stress to the 50% compressive stress of the molded article is preferably 0.65 or more, more preferably 0.70 or more, which reduces the change in energy absorption performance over a wide range of strain amounts, making it suitable for use in a variety of applications, such as as an impact absorbing material. The 25% compressive stress and 50% compressive stress of the molded body can be measured in accordance with JIS K6767:1999.

[0092] The foamed bead molding of the present invention can be used as a sound absorbing material, a shock absorbing material, a cushioning material, etc. in various fields such as the field of automobiles and other vehicles, and the field of construction. [Example]

[0093] The present invention will now be described in more detail with reference to examples, although the present invention is not limited to these examples in any way.

[0094] The resins used in the examples and comparative examples, the resulting expanded beads, and the resulting molded articles were subjected to the following physical property measurements and evaluations. The expanded beads were measured and evaluated after conditioning by leaving them at rest for 24 hours under conditions of 50% relative humidity, 23°C, and 1 atm. The physical property measurements and evaluations of the molded articles were also performed using molded articles that had not been cured after molding in a mold. Specifically, the expanded beads were molded in a mold as described below, and the molded articles obtained after demolding were left at rest for 12 hours under conditions of 50% relative humidity, 23°C, and 1 atm to condition, after which the physical properties were measured and evaluated.

[0095] <Polypropylene resin> Table 1 shows various physical properties of the polypropylene resin used in producing the expanded beads.

[0096] [Table 1]

[0097] (Monomer content of polypropylene resin) The content of the monomer component in the polypropylene-based resin (specifically, ethylene-propylene random copolymer, ethylene-propylene-butene random copolymer) was determined by a known method using IR spectroscopy.

[0098] (Flexural modulus of polypropylene resin) A polypropylene resin was heat-pressed at 230°C to produce a 4 mm thick sheet, from which a test piece measuring 80 mm long x 10 mm wide x 4 mm thick was cut. The flexural modulus of this test piece was measured in accordance with JIS K7171:2008. The radius R1 of the indenter and the radius R2 of the support table were both 5 mm, the distance between supports was 64 mm, and the test speed was 2 mm / min.

[0099] (Melting point of polypropylene resin) The melting point of polypropylene resin was determined according to JIS K7121:1987. Specifically, the conditioning method employed was "(2) Measurement of melting temperature after a certain heat treatment." The conditioned specimen was heated from 30 to 200°C at a heating rate of 10°C / min to obtain a DSC curve, and the apex temperature of the melting peak was taken as the melting point. The measurement device used was a heat flux differential scanning calorimeter (manufactured by SII Nanotechnology, Inc., model number: DSC7020).

[0100] (Melt flow rate of polypropylene resin) The melt flow rate (MFR) of polypropylene resin was measured in accordance with JIS K7210-1:2014 at a temperature of 230°C and a load of 2.16 kg.

[0101] Table 2 shows the composition of the obtained multilayer resin particles, the method for producing the multilayer expanded particles, and their physical properties. Table 3 shows the method for producing the obtained molded products, and their physical properties.

[0102] [Table 2]

[0103] [Table 3]

[0104] <Foam particles> (Average hole diameter d of through holes) The average pore size of the through-holes in the expanded beads was determined as follows. 100 expanded beads were randomly selected from the group of expanded beads after conditioning, and cut perpendicular to the penetration direction of the through-holes at a position where the cross-sectional area was approximately maximum. Photographs of the cut surfaces of each expanded bead were taken, and the cross-sectional areas (opening areas) of the through-holes in the cross-sectional photographs were determined. Specifically, the diameters of imaginary circles having the same area as the cross-sectional areas were calculated, and the arithmetic mean of these was taken as the average pore size (d) of the through-holes in the expanded beads.

[0105] (Average outer diameter D) The average outer diameter of the expanded beads was determined as follows. 100 expanded beads were randomly selected from the group of expanded beads after conditioning, and cut perpendicular to the penetration direction of the through-holes at a position where the cross-sectional area was approximately maximum. Photographs of the cut surfaces of each expanded bead were taken, and the cross-sectional area of ​​the expanded bead (including the openings of the through-holes) was determined. Specifically, the diameters of imaginary circles having the same area as the cross-sectional area were calculated, and the arithmetic mean of these was taken as the average outer diameter (D) of the expanded beads.

[0106] (Average wall thickness t) The average wall thickness of the expanded beads was calculated by the following formula (2). Average wall thickness t = (average outer diameter D - average pore diameter d) / 2 (2)

[0107] (bulk density) The bulk density of the expanded beads was determined as follows: Expanded beads were randomly taken from the group of expanded beads after conditioning and placed in a measuring cylinder with a volume of 1 L. A large number of expanded beads were placed up to the 1 L mark so as to form a natural pile. The mass W2 [g] of the placed expanded beads was calculated based on the volume V2 (1000 [cm3]). 3 ]) to obtain (W2 / V2) and convert the unit to obtain the bulk density of the expanded particles.

[0108] (Apparent density) The apparent density of the expanded particles was determined as follows: First, a measuring cylinder containing ethanol at a temperature of 23°C was prepared, and an arbitrary amount of the expanded particles after conditioning (mass W1 [g] of the expanded particles) was submerged in the ethanol in the measuring cylinder using a wire net. Then, taking into account the volume of the wire net, the volume V1 [cm] of the expanded particles was calculated from the rise in the water level. 3 The mass W1 [g] of the expanded particles placed in the measuring cylinder was calculated as the volume V1 [cm 3 The apparent density of the expanded particles was calculated by dividing the measured value by (W1 / V1) and converting it into units.

[0109] (closed cell ratio) The closed cell content of the expanded particles was measured using an air comparison hydrometer in accordance with ASTM-D2856-70 Procedure C. Specifically, it was determined as follows: Bulk volume after conditioning: about 20 cm 3 The expanded beads were used as measurement samples, and their apparent volumes (Va) were accurately measured by the ethanol immersion method as described below. After measuring the apparent volumes (Va), the measurement samples were thoroughly dried, and then the true volumes (Vx) of the measurement samples were measured using an Accupyc II 1340 (Shimadzu Corporation) in accordance with Procedure C described in ASTM-D2856-70. The measurement pressure was 5 kPa (G). Based on these volume values ​​(Va) and (Vx), the closed cell ratio was calculated using the following formula (1), and the arithmetic mean value of five samples (N=5) was taken as the closed cell ratio of the expanded beads. Closed cell ratio (%)=(Vx-W / ρ)×100 / (Va-W / ρ) (1) however, Vx: The true volume of the expanded beads measured by the above method, i.e., the sum of the volume of the resin constituting the expanded beads and the total volume of the closed cells in the expanded beads (unit: cm 3 ) Va: The apparent volume (unit: cm) of the foamed particles measured from the rise in the water level when the foamed particles are submerged in a measuring cylinder containing ethanol. 3 ) W: Weight of the sample for measuring foam particles (unit: g) ρ: Density of the resin that makes up the foamed particles (unit: g / cm 3 )

[0110] (High temperature peak heat quantity) After the conditioning, one expanded bead was sampled from the group of expanded beads. This expanded bead was used as a test specimen, and a DSC curve was obtained by heating the specimen from 23°C to 200°C at a heating rate of 10°C / min using a heat flux differential scanning calorimeter (manufactured by SII Nanotechnology, Inc., model number: DSC7020). The area of ​​the high-temperature peak in the DSC curve was determined, and this was taken as the high-temperature peak heat quantity. This measurement was carried out for five expanded beads, and the arithmetic mean values ​​are shown in Table 2.

[0111] (average bubble diameter La) The average cell diameter La of expanded beads was measured as follows. Each expanded bead was cut perpendicular to the penetration direction of the through-holes at a position where the cross-sectional area was approximately maximum. One of the cut sections of the expanded bead was photographed, and four lines were drawn at equal angles (i.e., 45°) on the vertical cross-sectional photograph, from the outermost surface of the expanded bead through the center of the through-hole to the outermost surface on the opposite side. The number of cells intersecting each line was then counted. The total length of the line segments intersecting the cells being measured was then divided by the total number of cells counted to determine the cell diameter of the expanded beads. This measurement was performed on 50 expanded beads, and the arithmetic mean value of the measured values ​​was taken as the average cell diameter La.

[0112] (Average bubble diameter Li in the inner layer) The average cell diameter Li of the inner surface layer was measured as follows. The expanded beads were cut perpendicular to the penetration direction of the through holes at a position where the cross-section area was approximately maximum. A photograph of one of the cut expanded beads was taken, and four lines were drawn at equal angles (i.e., 45°) on the perpendicular cross section from the outermost surface of the expanded beads through the center of the through holes to the outermost surface on the opposite side. The number of bubbles intersecting each line within 300 μm from the outer periphery of the through hole (i.e., the portion of each line extending from the outer periphery of the through hole toward the outer surface of the expanded beads within a length of 300 μm) was counted. The cell diameter of the inner surface layer was calculated by dividing the total length of the line segments intersecting with the bubbles being measured by the total number of bubbles counted. This measurement was performed on 50 expanded beads, and the arithmetic mean value of each measurement was taken as the average cell diameter Li of the inner surface layer.

[0113] <Foamed bead molding> (Molded object density) Molded body density (kg / m 3 ) was calculated by dividing the weight of the molded body by the volume determined from the outer dimensions of the molded body and converting the result into units.

[0114] (25% compressive stress and 50% compressive stress) Test pieces measuring 50 mm long x 50 mm wide x 25 mm thick were cut out from the center of the molded body so that the skin layer on the surface of the molded body was not included in the test piece. Based on JIS K6767:1999, a compression test was conducted at a compression rate of 10 mm / min to determine the 25% compressive stress and 50% compressive stress of the molded body. The densities of the test pieces used to measure the 25% compressive stress and 50% compressive stress were determined using the same method as in the measurement of the molded body density, and are shown in Table 2 as "cut-out density."

[0115] (porosity) The porosity of the green body was measured by cutting a rectangular parallelepiped test piece (20 mm long x 100 mm wide x 20 mm high) from the center of the green body. Next, this test piece was submerged in a measuring cylinder containing ethanol, and the true volume Vc [L] of the test piece was calculated from the rise in the ethanol liquid level. In addition, the external volume Vd [L] was calculated from the external dimensions of the test piece. The porosity of the green body was calculated from the calculated true volume Vc and external volume Vd using the following formula (3). Porosity (%)=[(Vd-Vc) / Vd]×100...(3)

[0116] (exterior) The surface of the molded article was visually observed, and the appearance of the molded article was evaluated based on the following criteria. A+: The surface of the molded article has extremely few interparticle gaps and the irregularities caused by the through holes are barely noticeable, showing an extremely good surface condition. A: The surface of the molded article has sufficiently small interparticle gaps and shows a good surface condition with little visible irregularities caused by through holes. B: Some irregularities due to interparticle gaps and / or through holes are observed on the surface of the molded body. C: Significant irregularities due to interparticle gaps and / or through holes are observed on the surface of the molded article.

[0117] (molding cycle) In the production of the molded body described below, after heating was completed, the molded body in the mold was cooled with water, the pressure inside the mold was released, and the time required for the value of the surface pressure gauge attached to the inner surface of the mold to fall to 0.04 MPa (G) (i.e., the water cooling time) was measured, and the mold was evaluated based on the measured water cooling time according to the following criteria. A: Water cooling time is 50 seconds or less B: Water cooling time is over 50 seconds and up to 120 seconds C: Water cooling time is over 120 seconds

[0118] (Non-cultivative formability) The evaluation of formability without curing was carried out as follows. After the molded body was released from the molding die, it was left to stand for a predetermined time in a high-temperature atmosphere adjusted to a temperature of about 60 to 80°C, and the evaluation of the fusion property and recovery property of the molded body was carried out without curing. Specifically, in the production of the molded body described below, the molded body was left to stand for 12 hours at 23°C after release from the mold, and the evaluation of the fusion property and recovery property described below was carried out using the molded body. When the evaluation results of both the fusion property and the recovery property were acceptable, the molded body was evaluated as "good: ○", and otherwise it was evaluated as "poor: ×". Note that for Comparative Examples 2 and 3, the evaluation of formability without curing was not carried out because the appearance was poor.

[0119] (Fusing ability) The molded body was bent and broken, and the number of foamed particles present on the fracture surface C1 and the number of broken foamed particles C2 were determined. The ratio of the number of broken foamed particles to the number of foamed particles present on the fracture surface (material failure rate) was calculated using the formula C2 / C1 x 100. This measurement was performed five times using different test pieces, and the material failure rate was calculated for each. An arithmetic mean value of the material failure rate of 90% or more was considered a pass, and a ratio of less than 90% was considered a fail.

[0120] (Recoverability) The thickness of the molded body obtained using a flat mold measuring 300 mm in length, 250 mm in width, and 60 mm in thickness was measured near the four corners (specifically, 10 mm inward from the corners toward the center) and at the center (the part dividing the body into two equal parts in both the length and width directions). Next, the ratio (unit: %) of the thickness of the thinnest part to the thickness of the thickest part among the measured parts was calculated. A thickness ratio of 95% or more was considered to be acceptable, and a thickness ratio of less than 95% was considered to be unacceptable.

[0121] In Examples 1 to 4 and Comparative Examples 1 to 3, the expanded beads and their molded articles were produced as follows. Example 1 <Production of Polypropylene-Based Multilayer Resin Particles> A polypropylene-based resin (abbreviated as PP1) was melt-kneaded in an extruder for forming a core layer at a maximum set temperature of 245°C to obtain a resin melt for forming a core layer. A polypropylene-based resin (abbreviated as PP4) was melt-kneaded in an extruder for forming a coating layer at a maximum set temperature of 245°C to obtain a resin melt for forming a coating layer. These resin melts were then introduced into a co-extrusion die, where they merged in a sheath-core configuration, with the resin melt for forming the core layer forming the core layer and the resin melt for forming the coating layer forming the sheath layer. This sheath-core resin melt was then extruded from the co-extrusion die into a tubular strand, which was water-cooled while being withdrawn and then cut into pieces with a pelletizer to a mass of approximately 1.5 mg. In this way, multilayer resin particles were obtained, each consisting of a cylindrical core layer with through holes and a coating layer covering the outer surface of the core layer. In producing the multilayer resin particles, zinc borate was supplied as a cell adjusting agent to the extruder for forming the core layer, and 500 ppm by mass of zinc borate was contained in the polypropylene resin. The through holes of the multilayer resin particles were formed as follows: When the sheath-core shaped resin melt was extruded from a die, a die was used in which a metal fitting provided at the flow path at the tip of the die formed a flow path having a cross-sectional shape capable of forming the cross-sectional shape of the multilayer resin particles having through holes, and the sheath-core shaped resin melt was passed through the flow path to form the through holes.

[0122] In order to produce multilayer resin particles having through holes, die 1 was used in the production of resin particles in Examples 1, 2, and 3, die 2 was used in Example 4, die 3 was used in Comparative Example 1, and die 4 was used in Comparative Examples 2 and 3. Die 1 is a die designed to produce expanded beads having a small average pore diameter d of through holes and an inner surface layer made of fine bubbles, die 2 is a die designed to produce resin beads having a small average pore diameter d of through holes, die 3 is a die designed to produce resin beads having no through holes, and die 4 is a die designed to produce resin beads having a large average pore diameter d of through holes.

[0123] Die 1 is designed so that the length in the extrusion direction of the through-hole-forming metal fittings provided in the flow paths on the die tip side (the distance from the upstream end of the through-hole-forming metal fittings to the die tip, i.e., the outlet of the resin melt) is long. Specifically, the length in the extrusion direction of the through-hole-forming metal fittings provided in the flow paths on the die tip side is 1.4 times the length in the extrusion direction of the through-hole-forming metal fittings provided in the flow paths on the die tip side of dies 2 and 4. Die 1 is designed so that the resin particles are more strongly oriented on the through-hole side than dies 2 and 4, which are conventionally used to produce resin particles with through holes.

[0124] <Production of polypropylene-based multilayer foam beads> 1 kg of the multilayer resin particles was placed in a 5 L sealed container together with 3 L of water as a dispersion medium. Furthermore, 0.3 parts by mass of kaolin as a dispersant and 0.004 parts by mass of a surfactant (sodium alkylbenzene sulfonate) were added to the sealed container relative to 100 parts by mass of the multilayer resin particles. Carbon dioxide as a blowing agent was added to the sealed container, after which the sealed container was sealed and heated to the temperature listed in the "Expansion Temperature" column in Table 2 while stirring. The pressure inside the container (blowing agent impregnation pressure, carbon dioxide pressure) at this time was the value listed in Table 2. After maintaining this expansion temperature for 15 minutes, the contents of the container were released to atmospheric pressure to obtain multilayer expanded particles. The multilayer expanded particles were dried at 23°C for 24 hours.

[0125] <Production of Molded Product> To produce the molded articles, the multi-layer foamed beads were dried at 23°C for 24 hours and then subjected to internal pressure before molding. Specifically, the multi-layer foamed beads were placed in a sealed container and pressurized with compressed air to apply the internal pressures shown in Table 3 to the multi-layer foamed beads before molding. The internal pressure of the multilayer foamed beads was measured as follows. The weight of the multilayer foamed beads in an elevated internal pressure state immediately before filling the mold was defined as Q (g), and the weight of the multilayer foamed beads after 48 hours was defined as U (g). The difference between Q (g) and U (g) was defined as the increased air volume W (g). The internal pressure P (MPa (G)) of the multilayer foamed beads was calculated using the formula P = (W ÷ M) × R × T ÷ V. In this formula, M is the molecular weight of air, R is the gas constant, T is the absolute temperature, and V is the volume (L) obtained by subtracting the volume of the base resin in the foamed beads from the apparent volume of the multilayer foamed beads. In this example, M = 28.8 (g / mol), R = 0.0083 (MPa L / (K mol)), and T = 296 (K).

[0126] Next, the multilayer foamed particles were filled into a flat mold measuring 300 mm in length, 250 mm in width, and 60 mm in thickness, with the cracking amount adjusted to the amount listed in Table 3. The mold was then clamped and subjected to an exhaust process in which steam was supplied from both sides of the mold for 5 seconds to preheat. One-sided heating was then performed by supplying steam from one side of the mold until a pressure 0.08 MPa (G) lower than the specified molding pressure was reached. Next, one-sided heating was performed by supplying steam from the other side of the mold until a pressure 0.04 MPa (G) lower than the specified molding pressure was reached, followed by heating (main heating) until the molding pressure listed in Table 3 was reached. After heating was completed, the pressure was released and the molded product was water-cooled until the surface pressure due to the foaming force of the molded product reached 0.04 MPa (G), after which it was demolded from the mold to obtain a molded product.

[0127] Example 2 Multilayer expanded beads were produced in the same manner as in Example 1, except that polypropylene resin 2 (abbreviated as PP2) was used as the base resin constituting the foamed core layer, and the foaming temperature and the foaming agent impregnation pressure were changed to the values ​​shown in Table 2. Using the obtained multilayer expanded beads, an expanded bead molding was produced in the same manner as in Example 1, except that the molding conditions shown in Table 3 were used.

[0128] Example 3 Multilayer expanded beads were produced in the same manner as in Example 1, except that polypropylene resin 3 (abbreviated as PP3) was used as the base resin constituting the foamed core layer and the foaming temperature and the foaming agent impregnation pressure were changed to the values ​​shown in Table 2. Using the obtained multilayer expanded beads, an expanded bead molding was produced in the same manner as in Example 1.

[0129] Example 4 Multilayer expanded beads were produced in the same manner as in Example 1, except that die 2 was used. Furthermore, a molded article was produced in the same manner as in Example 1 using the obtained multilayer expanded beads. The die 2 has the same shape as the die 1, except that the distance from the die tip to the metal fitting provided at the tip of the die for forming the through-hole is shorter than that of the die 1.

[0130] (Comparative Example 1) Multilayer resin beads having no through holes were produced using die 3, and multilayer expanded beads were obtained in the same manner as in Example 1, except that the expansion temperature and the blowing agent impregnation pressure were changed to the values ​​shown in Table 2. In addition, using the obtained multilayer expanded beads, expanded bead moldings were produced in the same manner as in Example 1, except that the molding conditions shown in Table 3 were used.

[0131] (Comparative Example 2) Multilayer expanded beads were obtained in the same manner as in Example 1, except that die 4 was used during the production of multilayer resin beads and the expansion temperature and the blowing agent impregnation pressure were changed to the values ​​shown in Table 2. In addition, using the obtained multilayer expanded beads, an expanded bead molding was produced in the same manner as in Example 1, except that the molding conditions shown in Table 2 were used. Die 4 has the same shape as die 1, except that the distance from the metal fittings at the tip of the die to the tip of the die is shorter than that of die 1, and the inner diameter of the small holes in the die has been changed so that the diameter of the through holes in the resulting resin particles is larger.

[0132] (Comparative Example 3) Using the same expanded beads as in Comparative Example 2, the molding conditions in the molding step were changed to those shown in Table 3 to obtain an expanded bead molded article.

[0133] Fig. 2 shows a photograph of a cross section perpendicular to the penetration direction of the through-holes of the expanded beads of Example 1. Fig. 3 shows a photograph of a cross section cut along the penetration direction of the expanded beads of Example 1. As shown in Figs. 2 and 3, an inner surface layer having fine bubbles is formed on the inner peripheral surface of the expanded beads (i.e., on the outer peripheral edge of the through-holes). As can be seen from Table 3, according to Examples 1 to 4, even if the curing step is omitted, a molded article having a desired shape and excellent appearance and rigidity can be produced. In Example 4, the average cell diameter Li of the inner surface layer of the expanded beads was slightly larger than that of Example 1 (Table 2). Therefore, the appearance and compressive strength of the molded article were slightly inferior to those of the molded article of Example 1.

[0134] On the other hand, as can be seen from Tables 2 and 3, in Comparative Example 1, a molded article was produced using multilayer foamed beads without through holes, so that the molded article underwent significant shrinkage and deformation (failed recovery) and a good molded article could not be obtained without further processing. In addition, the molding cycle was significantly longer. In Comparative Example 2, the molded article was produced using multilayer foamed beads in which the average pore diameter d of the through holes was too large and the average cell diameter of the inner layer was too large, resulting in a poor appearance of the molded article and reduced rigidity. Comparative Example 3 is an example in which the molding conditions were changed from those of Comparative Example 2 to improve the appearance and rigidity of the molded body. In Comparative Example 3, the appearance was improved but not sufficiently, and the molding cycle was lengthened. [Explanation of symbols]

[0135] 1. Foam particles 11 Through hole

Claims

1. A polypropylene-based resin expanded particle having through holes, The through holes have an average diameter d of 1 mm or less, The foamed beads have a closed cell rate of 85% or more, The average cell diameter La of the expanded beads is 50 μm or more and 300 μm or less, The polypropylene-based resin expanded beads are characterized in that the average cell diameter Li of the inner surface layer on the inner surface side of the expanded beads is 5 μm or more and 150 μm or less, and the average cell diameter Li of the inner surface layer is smaller than the average cell diameter La of the expanded beads.

2. The expanded polypropylene resin particles according to claim 1, wherein the average cell diameter Li of the inner surface layer is 30 μm or more and 100 μm or less.

3. 3. The expanded polypropylene resin beads according to claim 1, wherein the ratio Li / La of the average cell diameter Li of the inner surface layer to the average cell diameter La of the expanded beads is 0.65 or less.

4. 3. The expanded polypropylene resin beads according to claim 1, wherein a ratio d / D of an average pore diameter d of the through-holes of the expanded beads to an average outer diameter D of the expanded beads is 0.4 or less.

5. The apparent density of the expanded beads is 10 kg / m ３ More than 150kg / m ３ 3. The expanded polypropylene resin particles according to claim 1 or 2, wherein:

6. 3. The expanded polypropylene-based resin beads according to claim 1, wherein the expanded beads are multi-layered expanded beads having an expanded polypropylene-based resin core layer and a polyolefin-based resin coating layer covering the expanded core layer.

7. 3. A polypropylene resin expanded bead molded article obtained by molding the polypropylene resin expanded bead according to claim 1 or 2 in a mold.

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