Polypropylene resin foam particles, polypropylene resin foam molded body, and method for manufacturing polypropylene resin foam particles
By combining polypropylene random copolymer and propylene homopolymer or block copolymer with specific properties, the method addresses the inefficiency in molding cycle time for foamed molded articles, achieving rapid production with high-quality results.
Patent Information
- Application Number
- PCT/JP2025/011813
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2024-03-26
- Filing Date
- 2025-03-25
- Publication Date
- 2025-10-02
AI Technical Summary
Conventional methods for producing foamed molded articles using foamed beads are inefficient in terms of molding cycle time, and there is a need for improved techniques to shorten this process.
The production of expanded polypropylene resin beads involves a combination of polypropylene random copolymer and propylene homopolymer or block copolymer, with specific melting points and melt flow rates, followed by an expansion process to create beads that can be molded into articles in a shorter cycle.
The described method allows for the production of expanded polypropylene resin molded articles in a significantly reduced molding cycle time, while maintaining excellent surface aesthetics and properties.
Smart Images

Figure JPOXMLDOC01-APPB-T000001 
Figure JPOXMLDOC01-APPB-T000002 
Figure JPOXMLDOC01-APPB-T000003
Abstract
Description
Polypropylene-based resin expanded beads, polypropylene-based resin expanded molded article, and method for producing polypropylene-based resin expanded beads
[0001] The present invention relates to expanded polypropylene resin beads, expanded molded polypropylene resin articles, and a method for producing expanded polypropylene resin beads.
[0002] Polypropylene-based resin foam molded articles are used in a variety of applications, such as cushioning packaging materials, returnable boxes, and automotive components (see, for example, Patent Documents 1 and 2).
[0003] JP 2011-137172 A International Publication No. WO2023 / 190441
[0004] However, the above-mentioned conventional techniques are not sufficient from the viewpoint of the molding cycle in the production of foamed molded articles using foamed beads, and there is room for further improvement.
[0005] One embodiment of the present invention has been made in consideration of the above-mentioned problems, and its object is to provide novel expanded polypropylene resin beads that can provide expanded polypropylene resin molded articles in a short molding cycle, and a expanded polypropylene resin molded article obtained by molding the expanded polypropylene resin beads.
[0006] The present inventors have conducted extensive research to solve the above problems and have completed the present invention.
[0007] That is, the expanded polypropylene resin beads according to one embodiment of the present invention are expanded polypropylene resin beads obtained by expanding polypropylene resin beads, wherein the polypropylene resin particles contain a polypropylene random copolymer (A) having a melting point of 140.0°C or more and less than 155.0°C, and a propylene homopolymer (B1) and / or a polypropylene block copolymer (B2), wherein the melting point of the mixture of the propylene homopolymer (B1) and the polypropylene block copolymer (B2) is 155.0°C or more and less than 165.0°C, and the melt flow rate (MFR) of the polypropylene random copolymer (A) at 230°C and a load of 2160 g is 155.0°C or more and less than 165.0°C. A) of the mixture of the propylene homopolymer (B1) and the polypropylene block copolymer (B2) at 230°C and a load of 2160 g (MFR B ) ratio (MFR B / MFR A ) is 2.0 to 30.0.
[0008] Further, a method for producing expanded polypropylene-based resin beads according to one embodiment of the present invention comprises: an extrusion step of melt-kneading a mixed resin containing a polypropylene-based random copolymer (A) having a melting point of 140.0°C or more and less than 155.0°C, and a propylene homopolymer (B1) and / or a polypropylene block copolymer (B2) to obtain polypropylene-based resin beads; and an expansion step of expanding the polypropylene-based resin beads obtained in the extrusion step, wherein the melting point of the mixture of the propylene homopolymer (B1) and the polypropylene block copolymer (B2) is 155.0°C or more and less than 165.0°C, and the melt flow rate (MFR) of the polypropylene random copolymer (A) at 230°C and a load of 2,160 g is 155.0°C or more and less than 165.0°C. A ) of the mixture of the propylene homopolymer (B1) and the polypropylene block copolymer (B2) at 230°C and a load of 2160 g (MFR B ) ratio (MFR B / MFR A ) is 2.0 to 30.0.
[0009] According to one embodiment of the present invention, it is possible to provide novel expanded polypropylene-based resin beads that can provide expanded polypropylene-based resin molded articles in a short molding cycle, and a novel method for producing the expanded polypropylene-based resin beads.
[0010] An embodiment of the present invention will be described below, but the present invention is not limited thereto. The present invention is not limited to the respective configurations described below, and various modifications are possible within the scope of the claims. Furthermore, embodiments or examples obtained by combining the technical means disclosed in different embodiments or examples are also included in the technical scope of the present invention. Furthermore, new technical features can be formed by combining the technical means disclosed in each embodiment. All academic literature and patent documents described in this specification are incorporated herein by reference. Furthermore, unless otherwise specified in this specification, the term "A to B" representing a numerical range means "greater than or equal to A (including and greater than A) and less than or equal to B (including and less than B)."
[0011] In this specification, a "structural unit derived from an X monomer" contained in a polymer, copolymer, or resin may be referred to as an "X unit."
[0012] Unless otherwise specified in this specification, the structural unit is X 1 Unit, X 2 Units, ... and X n A copolymer containing units (n is an integer of 2 or more) is referred to as "X 1 / X 2 / ・・・ / X n Also referred to as "copolymer". X 1 / X 2 / ・・・ / X n Unless otherwise specified, the polymerization mode of the copolymer is not particularly limited, and the copolymer may be a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer.
[0013] In this specification, "polypropylene-based resin particles" may be referred to as "resin particles," "expanded polypropylene-based resin particles" may be referred to as "expanded particles," "expanded polypropylene-based resin particles according to one embodiment of the present invention" may be referred to as "the present expanded particles," "polypropylene-based resin foam molded body" may be referred to as "foam molded body," and "polypropylene-based resin foam molded body according to one embodiment of the present invention" may be referred to as "the present foam molded body." In this specification, "method for producing expanded polypropylene-based resin particles" may be referred to as "production method," and "method for producing expanded polypropylene-based resin particles according to one embodiment of the present invention" may be referred to as "the present production method."
[0014] [1. Technical Concept of One Embodiment of the Present Invention] A polypropylene-based random copolymer can generally be used as a raw material for a polypropylene-based resin foam molded article. On the other hand, a polypropylene-based block copolymer can also be used as a raw material for a polypropylene-based resin foam molded article. For example, this can be done when the impact resistance of the polypropylene-based resin foam molded article is to be increased or when recycled resin is used to reduce the environmental impact.
[0015] As a recycled polypropylene resin, polypropylene block copolymers are distributed in much larger quantities than polypropylene random copolymers.
[0016] Propylene homopolymers may also be used as a raw material for polypropylene-based resin foam molded articles, for example, when the purpose is to improve the dimensional stability of the polypropylene-based resin foam molded articles.
[0017] Motivated by the above, the present inventors have conducted extensive research into the following: providing expanded polypropylene resin particles, which are a raw material for polypropylene resin expansion moldings, by using a combination of a polypropylene random copolymer and a propylene homopolymer and / or a polypropylene block copolymer.
[0018] Through intensive research, the present inventors independently obtained the following novel finding: when resin particles obtained by using a combination of a polypropylene random copolymer and a propylene homopolymer and / or a polypropylene block copolymer are expanded, and the expanded particles are then molded to obtain a foamed molded article, the molding cycle may be lengthened in some cases.
[0019] Therefore, the present inventors have conducted further intensive research with the following objective: to provide expanded beads that can provide expanded molded articles in a short molding cycle even when a polypropylene random copolymer is used in combination with a propylene homopolymer and / or a polypropylene block copolymer.
[0020] As a result, the present inventors independently found the following novel finding, which led to the completion of the present invention: the finding that the following expanded beads, or expanded beads obtained by the following production method, can surprisingly provide an expanded molded article in a short molding cycle: expanded polypropylene resin beads obtained by expanding polypropylene resin beads, wherein the polypropylene resin beads contain a polypropylene random copolymer (A) having a melting point of 140.0°C or more and less than 155.0°C, and a propylene homopolymer (B1) and / or a polypropylene block copolymer (B2), the melting point of the mixture of the propylene homopolymer (B1) and the polypropylene block copolymer (B2) being 155.0°C or more and less than 165.0°C, and the melt flow rate (MFR) of the polypropylene random copolymer (A) at 230°C and a load of 2,160 g is 155.0°C or more and less than 165.0°C, A ) of the mixture of the propylene homopolymer (B1) and the polypropylene block copolymer (B2) at 230°C and a load of 2160 g (MFR B ) ratio (MFR B / MFR Aand a polypropylene-based resin expanded particle, the polypropylene-based resin expanded particle comprising: an extrusion step of melt-kneading a mixed resin containing a polypropylene-based random copolymer (A) having a melting point of 140.0°C or more and less than 155.0°C, and a propylene homopolymer (B1) and / or a polypropylene block copolymer (B2) to obtain polypropylene-based resin particles; and an expansion step of expanding the polypropylene-based resin particles obtained in the extrusion step, wherein the melting point of the mixture of the propylene homopolymer (B1) and the polypropylene block copolymer (B2) is 155.0°C or more and less than 165.0°C, and the melt flow rate (MFR) of the polypropylene-based random copolymer (A) at 230°C and a load of 2160 g is 2.0 to 30.0. A ) of the mixture of the propylene homopolymer (B1) and the polypropylene block copolymer (B2) at 230°C and a load of 2160 g (MFR B ) ratio (MFR B / MFR A ) is 2.0 to 30.0.
[0021] [2. Expanded Polypropylene Resin Beads] Expanded polypropylene resin beads according to one embodiment of the present invention are polypropylene resin beads obtained by expanding polypropylene resin beads, the polypropylene resin particles comprising a polypropylene random copolymer (A) having a melting point of 140.0°C or more and less than 155.0°C, and a propylene homopolymer (B1) and / or a polypropylene block copolymer (B2), the melting point of the mixture of the propylene homopolymer (B1) and the polypropylene block copolymer (B2) being 155.0°C or more and less than 165.0°C, the melt flow rate (MFR) of the polypropylene random copolymer (A) at 230°C and a load of 2160 g being 155.0°C or more and less than 165.0°C, and the melt flow rate (MFR) of the polypropylene random copolymer (A) being 155.0°C or more and less than 165.0°C. A ) of the mixture of the propylene homopolymer (B1) and the polypropylene block copolymer (B2) at 230°C and a load of 2160 g (MFR B ) ratio (MFR B / MFR AIn this specification, the structure in which "the melting point of the mixture of the propylene homopolymer (B1) and the polypropylene block copolymer (B2) is 155.0°C or higher and lower than 165.0°C" may be referred to as "structure A", and the melt flow rate (MFR) of the polypropylene random copolymer (A) at 230°C and a load of 2160 g may be referred to as "structure B". A ) of the mixture of the propylene homopolymer (B1) and the polypropylene block copolymer (B2) at 230°C and a load of 2160 g (MFR B ) ratio (MFR B / MFR A ) is 2.0 to 30.0" is sometimes referred to as "Configuration B."
[0022] The present expanded beads have the above-mentioned configurations (particularly, configurations A and B), and therefore have the advantage of being able to provide foamed molded articles in a short molding cycle. Furthermore, the present expanded beads have the above-mentioned configurations and therefore have the advantage of being able to provide foamed molded articles with excellent surface aesthetics. The molding cycle and methods for measuring and evaluating the surface aesthetics of foamed molded articles will be described in detail in the Examples below.
[0023] <Components> (Polypropylene Resin Particles) (Resin Components) The polypropylene random copolymer (A), propylene homopolymer (B1), and polypropylene block copolymer (B2) can also be considered as resin components in the resin particles and expanded beads. In other words, the resin particles and the present expanded beads contain at least the polypropylene random copolymer (A) and the propylene homopolymer (B1) and / or the polypropylene block copolymer (B2) as resin components. In this specification, "components that substantially constitute the resin particles" and "components that substantially constitute the expanded beads" are both also referred to as "base resin." In other words, the resin particles contain a base resin, and the base resin contains the polypropylene random copolymer (A) and the propylene homopolymer (B1) and / or the polypropylene block copolymer (B2). In other words, the present expanded beads contain a base resin, and the base resin contains the polypropylene random copolymer (A) and the propylene homopolymer (B1) and / or the polypropylene block copolymer (B2).
[0024] The polypropylene random copolymer (A), the propylene homopolymer (B1) and the polypropylene block copolymer (B2) are all polypropylene resins.
[0025] In this specification, the term "polypropylene resin" refers to a resin having the highest content of propylene units among all the structural units constituting the resin. For example, the polypropylene resin contains 50 mol % or more of propylene units out of 100 mol % of all structural units.
[0026] (Polypropylene Random Copolymer (A)) The polypropylene random copolymer (A) has, in addition to propylene units, one or more constituent units derived from a monomer other than a propylene monomer.
[0027] In this specification, the "structural units other than propylene units" contained in the polypropylene resin may be referred to as "comonomer units." In other words, the polypropylene random copolymer (A) contains at least propylene units and comonomer units. In the polypropylene random copolymer (A), the bonding order of the propylene units and the comonomer units is random.
[0028] Comonomers include α-olefins having 2 or 4 to 12 carbon atoms, such as ethylene, 1-butene, isobutene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3,4-dimethyl-1-butene, 1-heptene, 3-methyl-1-hexene, 1-octene, and 1-decene.
[0029] The heating temperature of the expanded beads when they are molded (for example, in-mold foam molding) is sometimes referred to as the "molding temperature." From the viewpoint of lowering the molding temperature, the polypropylene random copolymer (A) preferably contains an ethylene unit as a comonomer unit. For example, the polypropylene random copolymer (A) is preferably a propylene / ethylene random copolymer containing a propylene unit and an ethylene unit.
[0030] The polypropylene random copolymer (A) is not limited to a propylene / ethylene random copolymer. Examples of the polypropylene random copolymer (A) other than a propylene / ethylene random copolymer include a propylene / 1-butene random copolymer, a propylene / ethylene / 1-butene random copolymer, a propylene / chlorinated vinyl random copolymer, and a propylene / maleic anhydride random copolymer. Note that the 1-butene is synonymous with butene-1.
[0031] The polypropylene random copolymer (A) may be a combination of a propylene / ethylene random copolymer and one or more polypropylene random copolymers other than the propylene / ethylene random copolymer.
[0032] The melting point of the polypropylene random copolymer (A) is 140.0° C. or higher but lower than 155.0° C., preferably 140.0° C. or higher but lower than 153.0° C., more preferably 140.0° C. or higher but lower than 150.0° C., and even more preferably 142.0° C. or higher but lower than 149.0° C. When the polypropylene random copolymer (A) has a melting point of (i) 140.0° C. or higher, the expanded molded article obtained from the expanded beads has excellent heat resistance, and when it has a melting point of (ii) lower than 155.0° C., it is advantageous in that it becomes easier to increase the expansion ratio of the expanded beads in the production of the expanded beads.
[0033] In this specification, the melting points of the polypropylene random copolymer (A), the propylene homopolymer (B1) described below, and the polypropylene block copolymer (B2) are values measured by differential scanning calorimetry (hereinafter referred to as "DSC method"). Specific operating procedures are as described in the examples described below. As the differential scanning calorimeter, for example, a DSC7020 model manufactured by Seiko Instruments Inc. can be used.
[0034] The melt flow rate (MFR) of the polypropylene random copolymer (A) at 230°C and a load of 2160 g A ) is not particularly limited as long as it satisfies the constitution B. MFR of the polypropylene random copolymer (A) at 230°C and a load of 2160 g A The MFR of the polypropylene random copolymer (A) at 230°C and a load of 2160 g is preferably 3.0 g / 10 min to 30.0 g / 10 min, more preferably 3.0 g / 10 min to 25.0 g / 10 min, more preferably 4.0 g / 10 min to 20.0 g / 10 min, and even more preferably 5.0 g / 10 min to 18.0 g / 10 min. A Within the above range, there is an advantage that expanded beads having a relatively large expansion ratio can be easily obtained. Furthermore, in this case, there are also advantages that the surface appearance of the expanded molded article obtained from the expanded beads is excellent and the shrinkage rate of the expanded molded article is small.
[0035] In this specification, the MFR at 230°C and a load of 2160 g of the polypropylene random copolymer (A), the propylene homopolymer (B1), the polypropylene block copolymer (B2), the mixture of the propylene homopolymer (B1) and the polypropylene block copolymer (B2), and the polypropylene resin particles described below is a value determined using a melt mass-flow rate measuring device as described in JIS-K7210. Specific operating procedures are as described in the examples described below.
[0036] The polypropylene random copolymer (A) may be a newly produced one (non-recycled polypropylene random copolymer) produced by a known method, or a recycled polypropylene random copolymer derived from recycled materials. In other words, a recycled material containing a recycled polypropylene random copolymer may be used as the polypropylene random copolymer (A). The polypropylene random copolymer (A) may contain a recycled polypropylene random copolymer. When only recycled materials are used as the polypropylene random copolymer (A), the content of the polypropylene random copolymer (A) in the expanded beads is the product obtained by multiplying the amount of recycled material used (blended amount) by the content ratio of the recycled polypropylene random copolymer in the recycled material. The polypropylene random copolymer (A) may be a mixture of a recycled polypropylene random copolymer and a non-recycled polypropylene random copolymer.
[0037] The proportion of polypropylene random copolymers derived from recycled materials (i.e., recycled polypropylene random copolymers) in 100% by weight of the polypropylene random copolymer (A) may be 50% or more, 70% or more, 80% or more, or even 100%. The polypropylene random copolymer (A) may be composed solely of recycled polypropylene random copolymers. The higher the proportion of polypropylene random copolymers derived from recycled materials (i.e., recycled polypropylene random copolymers) in the polypropylene random copolymer (A), the more advantageously the environmental load can be reduced.
[0038] As used herein, the term "recycled material" refers to (a) a resin composition (or pellets) obtained by reusing a resin product that has been used and / or discarded after being converted into a resin composition (or pellets) by any means (e.g., crushing, shredding, melting, or a combination thereof) from a resin product (e.g., foam particles; foam molded products; films; food trays; packaging containers such as bags and bottles; medical containers such as IV drip packs and syringes; clothing cases; miscellaneous goods such as clear files; home appliances; automobile parts; fishing gear such as fishing nets, ropes, and floats); and (b) a resin composition obtained by reusing waste generated during the production of a resin product after being reusable into a resin composition (or pellets) by any means (e.g., crushing, shredding, melting, or a combination thereof). Resin product recovery is often performed by collecting resin products for each intended use and / or by collecting the raw materials used for the resin product. Therefore, recycled materials may primarily contain resins of the same or substantially the same composition (e.g., polypropylene-based resins and polyethylene-based resins). On the other hand, in the recovery of resin products, the resin product to be recovered may be mixed with other resin products for different purposes and / or made from different raw materials. Therefore, the recycled material may contain, in addition to the resin that is the main component, resins with compositions other than the resin in question.
[0039] In this specification, the resin contained in the recycled material may be referred to as a "recycled resin." For example, a recycled material obtained by (a) converting a resin product obtained primarily from a polypropylene-based resin into a resin composition by any means, and / or (b) converting waste generated during the production process of a resin product using a polypropylene-based resin as a primary raw material into a resin composition by any means, contains a recycled polypropylene-based resin as the recycled resin. A recycled material containing primarily recycled polypropylene-based resin as the resin may contain recycled polyethylene-based resin as the recycled resin in an amount less than the amount of recycled polypropylene-based resin.
[0040] The recycled material may contain additives used in the manufacturing process of the resin product (for example, various additives described in the section (Additives) below, such as foam nucleating agents (e.g., talc, calcium carbonate, silica, kaolin, barium sulfate, calcium hydroxide, aluminum hydroxide, aluminum oxide, titanium oxide, zinc borate, etc.) and colorants).
[0041] In this specification, the origin of the recycled material is not particularly limited. The recycled material may be derived from a foam such as foam particles and foam molded products. The recycled material may also be derived from a non-foamed material (for example, films; food trays; packaging containers such as bags and bottle containers; medical containers such as intravenous packs and syringes; clothing cases; miscellaneous goods such as clear files; home appliances; automobile parts; fishing gear such as fishing nets, ropes, and floats).
[0042] In this specification, a resin that has never been in the form of a resin product may also be referred to as a “non-recycled resin.” For example, a polypropylene-based resin that has never been in the form of a resin product is also referred to as a “non-recycled polypropylene-based resin.”
[0043] The case where the resin particles contain multiple polypropylene random copolymers that differ in composition, physical properties, and / or origin (whether recycled or not, etc.) will be described. In this case, the mixture consisting of all the polypropylene random copolymers contained in the resin particles is regarded as "polypropylene random copolymer (A)." Furthermore, the physical properties (e.g., melting point and MFR) of the mixture consisting of all the polypropylene random copolymers contained in the resin particles are also considered to be the same. A etc.) and the physical properties (e.g., melting point and MFR) of the polypropylene random copolymer (A). A For example, when the resin particles contain only two polypropylene random copolymers, a polypropylene random copolymer having a melting point of 139°C and a polypropylene random copolymer having a melting point of 150°C, the melting point of the mixture consisting of the entire amount of the polypropylene random copolymer having a melting point of 139°C and the entire amount of the polypropylene random copolymer having a melting point of 150°C contained in the resin particles is regarded as the melting point of the polypropylene random copolymer (A).
[0044] (Propylene homopolymer (B1)) The melting point of the propylene homopolymer (B1) is not particularly limited as long as it satisfies the structure A. The melting point of the propylene homopolymer (B1) is preferably 155.0°C or higher and lower than 165.0°C, more preferably 155.0°C or higher and 163.0°C or lower, more preferably 155.0°C or higher and 160.0°C or lower, and even more preferably 155.0°C or higher and 158.0°C or lower. When the melting point of the propylene homopolymer (B1) is (i) 155.0°C or higher, there is an advantage that a foamed molded article having excellent heat resistance can be obtained, and (ii) when it is lower than 165.0°C, there is an advantage that the foaming temperature and molding temperature can be lowered.
[0045] The melt flow rate (MFR) of the propylene homopolymer (B1) at 230°C and a load of 2160 g is not particularly limited as long as it satisfies the requirement B. The MFR of the propylene homopolymer (B1) at 230°C and a load of 2160 g is preferably 6 g / 10 min to 350 g / 10 min, more preferably 10 g / 10 min to 300 g / 10 min, even more preferably 15 g / 10 min to 280 g / 10 min, and particularly preferably 20 g / 10 min to 250 g / 10 min. When the MFR of the propylene homopolymer (B1) at 230°C and a load of 2160 g falls within the above range, it has the advantage of easily obtaining expanded beads having a relatively high expansion ratio. Furthermore, in this case, it also has the advantage that the surface beauty of the expanded molded article obtained from the expanded beads is excellent and the shrinkage rate of the expanded molded article is low. The upper limit of the MFR of the propylene homopolymer (B1) at 230°C under a load of 2160 g may be 200 g / 10 min or less, 150 g / 10 min or less, or 100 g / min or less.
[0046] When the resin particles contain a polypropylene random copolymer (A) and a propylene homopolymer (B1), the content of the propylene homopolymer (B1) in the resin particles is preferably less than 95 parts by weight, more preferably 10 parts by weight or more and 50 parts by weight or less, even more preferably 10 parts by weight or more and 40 parts by weight or less, and particularly preferably 10 parts by weight or more and 30 parts by weight or less, per 100 parts by weight of the total of the polypropylene random copolymer (A) and the propylene homopolymer (B1). This configuration has the advantage of allowing the foaming temperature and molding temperature to be lowered.
[0047] When the resin particles contain a propylene homopolymer (B1), the ratio of the content of the polypropylene random copolymer (A) to the content of the propylene homopolymer (B1) in the resin particles (content (parts by weight) of the polypropylene random copolymer (A):content (parts by weight) of the propylene homopolymer (B1)) is preferably 90:10 to 50:50, more preferably 85:15 to 50:50, even more preferably 80:20 to 60:40, and particularly preferably 75:25 to 70:30. This configuration has the advantages of (i) being able to lower the foaming temperature and molding temperature, and (ii) the resulting foamed molded article having excellent heat resistance.
[0048] The propylene homopolymer (B1) may be a newly produced propylene homopolymer (non-recycled propylene homopolymer) produced by a known method, or a recycled propylene homopolymer derived from a recycled material. In other words, a recycled material containing a recycled propylene homopolymer may be used as the propylene homopolymer (B1). The propylene homopolymer (B1) may contain a recycled propylene homopolymer. When a recycled material is used, the content of the propylene homopolymer (B1) in the expanded beads is the product obtained by multiplying the amount (blended amount) of the recycled material used by the content ratio of the propylene homopolymer (B1) in the recycled material. The propylene homopolymer (B1) may be a mixture of a recycled propylene homopolymer and a non-recycled propylene homopolymer.
[0049] From the viewpoint of reducing the environmental load, the proportion of propylene homopolymers derived from recycled materials (i.e., recycled propylene homopolymers) in 100% by weight of the propylene homopolymer (B1) is preferably 50% or more, more preferably 70% or more, even more preferably 80% or more, and particularly preferably 100%. That is, it is particularly preferable that the propylene homopolymer (B1) is composed solely of recycled propylene homopolymers.
[0050] The propylene homopolymer (B1) may contain structural units derived from isoprene and structural units derived from conjugated dienes, but preferably does not contain any of them. The total content of structural units derived from isoprene and structural units derived from conjugated dienes in 100% by weight of the propylene homopolymer (B1) is preferably 20% by weight or less, more preferably 10% by weight or less, even more preferably 5% by weight or less, and most preferably 0% by weight.
[0051] The case where the resin particles contain multiple types of propylene homopolymers that differ in composition, physical properties, and / or origin (whether recycled or not, etc.) will be described. In this case, the mixture of all propylene homopolymers contained in the resin particles is regarded as "propylene homopolymer (B1)." Furthermore, the physical properties (e.g., melting point, MFR, etc.) of the mixture of all propylene homopolymers contained in the resin particles are regarded as the physical properties (e.g., melting point, MFR, etc.) of the propylene homopolymer (B1).
[0052] (Polypropylene Block Copolymer (B2)) The polypropylene block copolymer (B2) has, in addition to propylene units, one or more structural units derived from a monomer other than a propylene monomer. In other words, the polypropylene block copolymer (B2) contains at least propylene units and comonomer units. More specifically, the polypropylene block copolymer (B2) contains a propylene block composed of propylene units and a comonomer block composed of comonomer units. Specific examples of the comonomer units are the same as those explained above in the section (Polypropylene Random Copolymer (A)), and therefore, the explanation therefor is omitted here.
[0053] From the viewpoint of lowering the molding temperature, the polypropylene-based block copolymer (B2) preferably contains an ethylene unit as a comonomer unit, for example, the polypropylene-based block copolymer (B2) is preferably a propylene / ethylene block copolymer containing a propylene block composed of propylene units and an ethylene block composed of ethylene units.
[0054] The polypropylene-based block copolymer (B2) is not limited to a propylene / ethylene block copolymer. Examples of the polypropylene-based block copolymer (B2) other than a propylene / ethylene block copolymer include a propylene / 1-butene block copolymer, a propylene / ethylene / 1-butene block copolymer, a propylene / vinyl chloride block copolymer, and a propylene / maleic anhydride block copolymer.
[0055] The polypropylene-based block copolymer (B2) includes substances that are considered to be polypropylene-based block copolymers in the technical field of polypropylene-based resins. For example, a propylene / ethylene block copolymer includes a homopolypropylene matrix and a polyethylene layer covered with an ethylene / propylene elastic copolymer as a domain, and is sometimes called an impact copolymer.
[0056] The polypropylene-based block copolymer (B2) may be a combination of a propylene / ethylene block copolymer and one or more polypropylene-based block copolymers (B2) other than a propylene / ethylene block copolymer.
[0057] The melting point of the polypropylene block copolymer (B2) is not particularly limited as long as it satisfies the structure A. The melting point of the polypropylene block copolymer (B2) is preferably 155.0°C or higher and lower than 165.0°C, more preferably 155.0°C or higher and lower than 164.0°C, more preferably 156.0°C or higher and lower than 163.0°C, more preferably 156.0°C or higher and lower than 162.0°C, and even more preferably 156.0°C or higher and lower than 161.0°C. When the melting point of the polypropylene block copolymer (B2) is (i) 155.0°C or higher, it has the advantage that a foamed molded article having excellent heat resistance can be obtained, and (ii) when it is lower than 165.0°C, it has the advantage that the moldability is excellent.
[0058] The melt flow rate (MFR) of the polypropylene block copolymer (B2) at 230°C and a load of 2160 g is not particularly limited as long as it satisfies the requirement B. The MFR of the polypropylene block copolymer (B2) at 230°C and a load of 2160 g is preferably 6 g / 10 min to 350 g / 10 min, more preferably 10 g / 10 min to 300 g / 10 min, more preferably 15 g / 10 min to 280 g / 10 min, and even more preferably 20 g / 10 min to 250 g / 10 min. When the MFR of the polypropylene block copolymer (B2) at 230°C and a load of 2160 g is within the above range, it has the advantage of easily obtaining expanded beads having a relatively high expansion ratio. Furthermore, in this case, it also has the advantage that the surface beauty of the expanded molded article obtained from the expanded beads is excellent and the shrinkage rate of the expanded molded article is low.
[0059] When the resin particles contain a polypropylene block copolymer (B2), the ratio of the content of the polypropylene random copolymer (A) in the resin particles to the content of the polypropylene block copolymer (B2) (content (parts by weight) of the polypropylene random copolymer (A):content (parts by weight) of the polypropylene block copolymer (B2)) is preferably 90:10 to 40:60, more preferably 85:15 to 55:45, even more preferably 80:20 to 60:40, and particularly preferably 75:25 to 65:35. This configuration has the advantages of (i) being able to lower the foaming temperature and molding temperature, and (ii) the resulting foamed molded article having excellent heat resistance.
[0060] The polypropylene-based block copolymer (B2) may be a newly produced polypropylene-based block copolymer (non-recycled polypropylene-based block copolymer) produced by a known method, or a recycled polypropylene-based block copolymer derived from a recycled material. In other words, a recycled material containing a recycled polypropylene-based block copolymer may be used as the polypropylene-based block copolymer (B2). The polypropylene-based block copolymer (B2) may contain a recycled polypropylene-based block copolymer. When a recycled material is used, the content of the polypropylene-based block copolymer (B2) in the expanded beads is the product obtained by multiplying the amount (blended amount) of the recycled material used by the content ratio of the polypropylene-based block copolymer (B2) in the recycled material. The polypropylene-based block copolymer (B2) may be a mixture of a recycled polypropylene-based block copolymer and a non-recycled polypropylene-based block copolymer. The polypropylene-based block copolymer (B2) preferably contains a recycled polypropylene-based block copolymer derived from a recycled material. As described above, the circulation volume of polypropylene-based block copolymers as recycled polypropylene-based resins is greater than the circulation volume of polypropylene-based random copolymers. Therefore, recycled polypropylene-based block copolymer resins are relatively easy to obtain.
[0061] From the viewpoint of reducing the environmental load, the proportion of recycled polypropylene block copolymers derived from recycled materials (i.e., recycled polypropylene block copolymers) in 100% by weight of the polypropylene block copolymer (B2) is preferably 50% or more, more preferably 70% or more, even more preferably 80% or more, and particularly preferably 100%. That is, it is particularly preferred that the polypropylene block copolymer (B2) is composed solely of recycled polypropylene block copolymers.
[0062] The polypropylene block copolymer (B2) may contain, but preferably does not contain, structural units derived from isoprene and structural units derived from conjugated dienes. In 100% by weight of the polypropylene block copolymer (B2), the total content of structural units derived from isoprene and structural units derived from conjugated dienes is preferably 20% by weight or less, more preferably 10% by weight or less, even more preferably 5% by weight or less, and most preferably 0% by weight.
[0063] The following describes a case where resin particles contain multiple polypropylene-based block copolymers with different compositions, physical properties, and / or origins (e.g., whether recycled or not). In this case, the mixture of all polypropylene-based block copolymers contained in the resin particles is considered to be the "polypropylene-based block copolymer (B2)." Furthermore, the physical properties (e.g., melting point, MFR, etc.) of the mixture of all polypropylene-based block copolymers contained in the resin particles are considered to be the physical properties (e.g., melting point, MFR, etc.) of the polypropylene-based block copolymer (B2).
[0064] At least one of the polypropylene random copolymer (A), the propylene homopolymer (B1), and the polypropylene block copolymer (B2) preferably contains a recycled resin derived from recycled materials. Using recycled resin not only reduces environmental pollution, but also significantly reduces the amount of plastic waste generated and the amount of plastic used in production. Therefore, embodiments using recycled resin as all or part of the resin have the advantage of contributing to the achievement of Sustainable Development Goals (SDGs), such as Goal 12 "Ensure sustainable consumption and production patterns" and Goal 14 "Conserve and sustainably use the oceans and marine resources for sustainable development."
[0065] (Mixture of Propylene Homopolymer (B1) and Polypropylene-Based Block Copolymer (B2)) The melting point of the mixture of propylene homopolymer (B1) and polypropylene-based block copolymer (B2) is 155°C or higher and lower than 165°C, more preferably 155°C or higher and lower than 164°C, more preferably 155°C or higher and lower than 163°C, more preferably 155°C or higher and lower than 162°C, more preferably 155°C or higher and lower than 161°C, more preferably 155°C or higher and lower than 160°C, and even more preferably 155°C or higher and lower than 158°C. This configuration has the advantage that the expanded beads can provide a foamed molded article in a short molding cycle. Furthermore, when the melting point of the mixture of propylene homopolymer (B1) and polypropylene-based block copolymer (B2) is (i) 155°C or higher, it has the advantage that a foamed molded article having excellent heat resistance can be obtained, and (ii) when it is lower than 165°C, it has the advantage that the foaming temperature and molding temperature can be lowered and the molding processability is excellent.
[0066] The melt flow rate (MFR) of the mixture of propylene homopolymer (B1) and polypropylene block copolymer (B2) at 230°C and a load of 2160 g was B ) is not particularly limited as long as it satisfies the constitution B. The MFR of the mixture of the propylene homopolymer (B1) and the polypropylene block copolymer (B2) at 230°C and a load of 2160 g B The MFR of the mixture of the propylene homopolymer (B1) and the polypropylene block copolymer (B2) at 230°C and a load of 2160 g is preferably 6 g / 10 min to 350 g / 10 min, more preferably 10 g / 10 min to 300 g / 10 min, still more preferably 15 g / 10 min to 280 g / 10 min, and particularly preferably 20 g / 10 min to 250 g / 10 min. B Within the above range, there is an advantage that expanded beads having a relatively large expansion ratio can be easily obtained. Furthermore, in this case, there are also advantages that the surface appearance of the expanded molded article obtained from the expanded beads is excellent and the shrinkage rate of the expanded molded article is small.
[0067] In one embodiment of the present invention, the resin particles may (i) contain a propylene homopolymer (B1) and not contain a polypropylene-based block copolymer (B2), (ii) contain a polypropylene-based block copolymer (B2) and not contain a propylene homopolymer (B1), or (iii) contain both a propylene homopolymer (B1) and a polypropylene-based block copolymer (B2). Therefore, the "melting point and MFR of a mixture of a propylene homopolymer (B1) and a polypropylene-based block copolymer (B2)" is not limited to the above. B " respectively means (i) the melting point and MFR of the propylene homopolymer (B1) when the resin particles contain a propylene homopolymer (B1) but do not contain a polypropylene-based block copolymer (B2); (ii) the melting point and MFR of the polypropylene-based block copolymer (B2) when the resin particles contain a polypropylene-based block copolymer (B2) but do not contain a propylene homopolymer (B1); and (iii) the melting point and MFR of the mixture of the propylene homopolymer (B1) and the polypropylene-based block copolymer (B2) when the resin particles contain both the propylene homopolymer (B1) and the polypropylene-based block copolymer (B2).
[0068] In the resin particles, it is preferred that, based on a total of 100 parts by weight of the polypropylene random copolymer (A), the propylene homopolymer (B1), and the polypropylene block copolymer (B2), (a) the content of the polypropylene random copolymer (A) is 70 to 95 parts by weight, and the total content of the propylene homopolymer (B1) and the polypropylene block copolymer (B2) is 5 to 30 parts by weight; (b) the content of the polypropylene random copolymer (A) is 70 to 90 parts by weight, and the total content of the propylene homopolymer (B1) and the polypropylene block copolymer (B2) is 10 to 30 parts by weight; and (c) the content of the polypropylene random copolymer (A) is 70 to 80 parts by weight, and the total content of the propylene homopolymer (B1) and the polypropylene block copolymer (B2) is 20 to 30 parts by weight. When the contents of the polypropylene random copolymer (A), the propylene homopolymer (B1), and the polypropylene block copolymer (B2) in the resin particles are within the above-mentioned ranges, the expanded beads have the advantage of being superior in productivity for producing polypropylene resin expansion molded articles. The term "total content of the propylene homopolymer (B1) and the polypropylene block copolymer (B2)" refers to (i) the content of the propylene homopolymer (B1) when the resin particles contain the propylene homopolymer (B1) but not the polypropylene block copolymer (B2), (ii) the content of the polypropylene block copolymer (B2) when the resin particles contain the polypropylene block copolymer (B2) but not the propylene homopolymer (B1), and (iii) the total content of the propylene homopolymer (B1) and the polypropylene block copolymer (B2) when the resin particles contain both the propylene homopolymer (B1) and the polypropylene block copolymer (B2).
[0069] (MFR B / MFR A The melt flow rate (MFR) of the polypropylene random copolymer (A) at 230°C and a load of 2160 g A) of the mixture of propylene homopolymer (B1) and polypropylene block copolymer (B2) at 230 ° C. and a load of 2160 g (MFR B ) ratio (MFR B / MFR A ) is 2.0 to 30.0, preferably 4.0 to 30.0, and more preferably 5.0 to 30.0. This configuration has the advantage that the expanded beads can provide a foamed molded article in a short molding cycle. This configuration also has the advantage that a foamed molded article with excellent surface beauty can be provided.
[0070] The resin particles may further contain, as a resin component, a resin other than the polypropylene random copolymer (A), the propylene homopolymer (B1), and the polypropylene block copolymer (B2) (sometimes referred to as "other resins, etc.") to the extent that the effects of one embodiment of the present invention are not impaired. Examples of the other resins include: (a) polypropylene resins other than polypropylene random copolymers, propylene homopolymers, and polypropylene block copolymers having a melting point of less than 140.0°C or 155.0°C or more; (b) ethylene resins such as high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, linear very low-density polyethylene, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, and ethylene / methacrylic acid copolymer; (c) styrene resins such as polystyrene, styrene / maleic anhydride copolymer, and styrene / ethylene copolymer; (d) polyolefin waxes such as propylene-α-olefin wax; and (e) olefin rubbers such as ethylene / propylene rubber, ethylene / butene rubber, ethylene / hexene rubber, and ethylene / octene rubber. The content of other resins in the resin particles is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, per 100 parts by weight of the total of the polypropylene random copolymer (A), the propylene homopolymer (B1), and the polypropylene block copolymer (B2).
[0071] (Additives) In addition to the resin components described above, the resin particles may further contain optional additives. Examples of the additives include colorants, water-absorbing substances (e.g., (i) polyols such as glycerin and diglycerin, (ii) polyethers such as polyethylene glycol and polyethylene oxide, and (iii) metal borates such as borax and zinc borate), foam nucleating agents (e.g., inorganic substances such as talc, calcium carbonate, silica, kaolin, barium sulfate, calcium hydroxide, aluminum hydroxide, aluminum oxide, and titanium oxide), antistatic agents (e.g., glycerin monostearate, glycerin monodistearate), and flame retardants (e.g., hydroxybenzoates). Examples of suitable additives include hindered amine flame retardants, bromine flame retardants, phosphate ester flame retardants, and melamine flame retardants, antioxidants (e.g., hindered phenol antioxidants), heat stabilizers (e.g., phosphorus-based heat stabilizers and sulfur-based heat stabilizers), light stabilizers (e.g., benzotriazole UV absorbers, triazine UV absorbers, HALS and / or hindered amine light stabilizers), nucleating agents, conductive agents (e.g., carbon, carbon nanotubes, and metal fillers), lubricants, acid scavengers, antiblocking agents, metal chelating agents (e.g., IRGANOX® MD1024 and ADK STAB® CDA-1), lubricants, antibacterial agents, organic peroxides, and MFR adjusters. The resin particles may also contain an additive for recycled materials containing any one or a combination of two or more of these additives. A "metal chelating agent" is sometimes referred to as a "metal deactivator." Such additives may be added directly to the mixed resin or polypropylene resin composition described below in the production of polypropylene resin particles.
[0072] Examples of colorants include chromatic pigments and carbon black. Chromatic pigments include (i) blue pigments such as copper phthalocyanine blue, ultramarine, cobalt blue, and Prussian blue; (ii) red pigments such as perylene red, quinacridone red, and cadmium red; (iii) yellow pigments such as condensed azo yellow, cadmium yellow, and barium chromate; (iv) green pigments obtained by blending blue and yellow pigments; (v) orange pigments obtained by blending red and yellow pigments; and (vi) purple pigments such as cobalt violet and pigments obtained by blending blue and red pigments. The resin particles may contain carbon black.
[0073] <Physical Properties> The physical properties of the resin particles and the present expanded beads will be described below.
[0074] (MFR of Polypropylene-Based Resin Particles) The MFR of the polypropylene-based resin particles at 230°C and a load of 2160 g is preferably 7.0 g / 10 min to 30.0 g / 10 min, more preferably 10.0 g / 10 min to 28.0 g / 10 min, and even more preferably 13.0 g / 10 min to 26.0 g / 10 min or more. This configuration has the advantage that the expanded beads can provide a foamed molded article in a short molding cycle. This configuration also has the advantage that a foamed molded article having excellent internal fusion properties and / or surface beauty can be provided.
[0075] (DSC Ratio of Expanded Polypropylene Resin Beads) The expanded beads preferably have at least two melting peaks in a DSC curve obtained by a differential scanning calorimeter (differential scanning calorimetry) described below. The heat of fusion determined from the higher-temperature peak among the melting peaks is referred to as the "high-temperature heat of fusion (Q h ) and the heat of fusion calculated from the melting peak on the low temperature side is called the "low temperature heat of fusion (Q l In addition, when there are three or more melting peaks, the heat of fusion calculated from the highest melting peak is called the "high-temperature heat of fusion (Q h ) and the heat of fusion calculated from the other melting peaks is called the "low-temperature heat of fusion (Q lThe ratio of the heat of fusion on the higher temperature side to the total heat of fusion, more specifically, the ratio of the heat of fusion on the higher temperature side to the total heat of fusion (100%), is also referred to as the "DSC ratio". The DSC ratio can be calculated using the following formula: DSC ratio (%) = Q h / (Q l +Q h ) x 100.
[0076] The ratio of the heat of fusion on the higher temperature side to the total heat of fusion of the expanded beads (100%), i.e., the DSC ratio, is not particularly limited. The DSC ratio of the expanded beads is preferably 30.0% to 50.0%, more preferably 30.0% to 40.0%, and even more preferably 30.0% to 35.0%. When the DSC ratio of the expanded beads is 30.0% or more, the expanded beads have the advantage of being able to provide a foamed molded article with sufficient strength. On the other hand, when the DSC ratio of the expanded beads is 50.0% or less, the expanded beads have the advantage of being able to be molded at a relatively low temperature (molding temperature) to provide a foamed molded article. The method for measuring the DSC ratio of the expanded beads will be described in detail in the Examples below.
[0077] The DSC ratio of the expanded beads is also a measure of the amount of high-melting-point crystals contained in the expanded beads. That is, a DSC ratio of 30.0% to 50.0% indicates that the expanded beads contain a relatively large amount of high-melting-point crystals. Furthermore, the DSC ratio of the expanded beads is significantly related to the viscoelasticity of the resin particles and the expanded beads when they are foamed and expanded. That is, when the DSC ratio of the expanded beads is 30.0% to 50.0%, the resin particles and the expanded beads can exhibit excellent foamability and expansion properties, respectively, when they are foamed and when they are molded. As a result, the expanded beads have the advantage that they can produce foamed molded articles with excellent internal fusion properties and excellent mechanical strength, such as compressive strength, even at low molding pressures.
[0078] In the present expanded beads, examples of a method for controlling the DSC ratio within a predetermined range include a method for adjusting the conditions during production of the present expanded beads (particularly, the foaming temperature, foaming pressure, holding time, and the temperature of the region (space) from which the dispersion is released, etc.) In terms of ease of adjustment, a method for controlling the DSC ratio within a predetermined range by adjusting the foaming temperature, foaming pressure, and / or holding time is preferred.
[0079] For example, increasing the foaming temperature tends to decrease the DSC ratio, while decreasing the foaming temperature tends to increase the DSC ratio. This is because the amount of unmelted crystals varies depending on the foaming temperature. Increasing the foaming pressure also tends to decrease the DSC ratio, while decreasing the foaming pressure also tends to increase the DSC ratio. This is because the degree of plasticization varies depending on the foaming pressure, thereby changing the amount of unmelted crystals. In addition, the DSC ratio tends to increase as the holding time increases. This is because the amount of growth of unmelted crystals varies depending on the holding time.
[0080] (Expansion Ratio of Expanded Polypropylene Resin Beads) The expanded beads preferably have an expansion ratio of 10 to 50, more preferably 18 to 40, and even more preferably 18 to 30. If the expansion ratio of the expanded beads is (i) 10 or more, a lightweight expanded molded article can be obtained efficiently, and if (ii) 50 or less, there is no risk of the strength of the resulting expanded molded article being insufficient. The method for calculating the expansion ratio of the expanded beads will be described in detail in the Examples below.
[0081] (Average Cell Diameter of Expanded Polypropylene Resin Beads) The average cell diameter of the expanded beads is not particularly limited. The average cell diameter of the expanded beads is preferably 80 μm to 500 μm, more preferably 85 μm to 400 μm, even more preferably 90 μm to 300 μm, and particularly preferably 95 μm to 250 μm. When the average cell diameter of the expanded beads is (i) 80 μm or more, the expanded beads can provide a polypropylene resin foam molded article having excellent compressive strength, and (ii) when the average cell diameter is 500 μm or less, there is no risk of the molding cycle becoming longer, which has the advantage of improving productivity. The method for measuring the average cell diameter of the expanded beads will be described in detail in the Examples below.
[0082] (Molding Pressure) The present expanded beads have the advantage that they can be used to obtain a foamed molded article having an excellent fusion rate (for example, a fusion rate of 80% or more) at a low molding pressure. In other words, the present expanded beads have the advantage that a foamed molded article having an excellent fusion rate can be provided at a molding pressure equivalent to that of foamed beads obtained using only a polypropylene-based random copolymer as the base resin.
[0083] In this specification, the minimum molding pressure that can provide a foamed molded article having an excellent fusion rate (e.g., a fusion rate of 80% or more) in the production of a foamed molded article using the expanded beads is also referred to as the "minimum molding pressure." The expanded beads also have the advantage of a low minimum molding pressure. In other words, the minimum molding pressure of the expanded beads can be equivalent to that of expanded beads obtained using only a polypropylene-based random copolymer as the base resin.
[0084] The molding pressure of the present expanded beads is not particularly limited, but is preferably 0.34 MPa (gauge pressure) or less, more preferably 0.32 MPa (gauge pressure) or less, and even more preferably 0.30 MPa (gauge pressure) or less. The lower limit of the molding pressure is not particularly limited, but may be, for example, 0.15 MPa (gauge pressure) or more. When the minimum molding pressure is within the above-mentioned range, there is an advantage that a foamed molded article can be provided with a small economic burden.
[0085] [3. Method for producing expanded polypropylene-based resin beads] A method for producing expanded polypropylene-based resin beads according to one embodiment of the present invention comprises an extrusion step of melt-kneading a mixed resin containing a polypropylene-based random copolymer (A) having a melting point of 140.0°C or more and less than 155.0°C, and a propylene homopolymer (B1) and / or a polypropylene block copolymer (B2) to obtain polypropylene-based resin beads, and an expansion step of expanding the polypropylene-based resin beads obtained in the extrusion step, wherein the melting point of the mixture of the propylene homopolymer (B1) and the polypropylene block copolymer (B2) is 155.0°C or more and less than 165.0°C, and the melt flow rate (MFR) of the polypropylene random copolymer (A) at 230°C and a load of 2,160 g is 155.0°C or more and less than 165.0°C. A ) of the mixture of the propylene homopolymer (B1) and the polypropylene block copolymer (B2) at 230°C and a load of 2160 g (MFR B ) ratio (MFR B / MFR A ) is 2.0 to 30.0.
[0086] Because the present production method includes the above-described configuration, it has the advantage of being able to provide expanded beads that can provide expanded molded articles in a short molding cycle. Furthermore, because the present production method includes the above-described configuration, it has the advantage of being able to provide expanded beads that can provide expanded molded articles with excellent internal fusion properties and / or surface aesthetics. Furthermore, because the present production method includes the above-described configuration, it is possible to provide expanded beads that can provide expanded molded articles with excellent internal fusion properties and / or surface aesthetics using a smaller amount of steam than conventional methods, despite the use of a propylene homopolymer and / or a polypropylene-based block copolymer. In other words, because the present production method includes the above-described configuration, it also has the advantage of low energy consumption (energy saving). As described above, the present production method also has Configuration A and Configuration B.
[0087] (Extrusion Step) In the extrusion step, a mixed resin containing the polypropylene random copolymer (A) and the propylene homopolymer (B1) and / or the polypropylene block copolymer (B2) is melt-kneaded.
[0088] The specific embodiment of the extrusion step is not particularly limited. For example, a method for obtaining resin particles can be a method using an extruder. Specifically, for example, resin particles can be produced by the following methods (1) to (5): (1) blending a polypropylene random copolymer (A), a propylene homopolymer (B1), and / or a polypropylene block copolymer (B2), and, if necessary, one or more selected from the group consisting of other resins and additives to produce a mixed resin; (2) feeding the mixed resin into an extruder and melt-kneading the mixed resin to prepare a polypropylene resin composition; (3) extruding the polypropylene resin composition through a die equipped in the extruder; (4) solidifying the extruded polypropylene resin composition by cooling it, for example, by passing it through water; (5) then cutting the solidified polypropylene resin composition into desired shapes such as a cylindrical, elliptical, spherical, cubic, rectangular, hollow cylinder, polygonal prism, etc., using a cutter. Alternatively, in (3), the melt-mixed polypropylene resin composition may be directly extruded into water through a die provided in an extruder, and immediately after extrusion, the polypropylene resin composition may be cut into particles, cooled, and solidified. By melt-mixing the mixed resin in this manner, more uniform resin particles can be obtained. The extrusion step may also include a peroxide treatment step in which the mixed resin is treated with a peroxide.
[0089] The weight per particle of the resin particles obtained as described above is preferably 0.2 mg / particle to 10.0 mg / particle, more preferably 0.5 mg / particle to 6.0 mg / particle. When the weight per particle of the resin particles is (a) 0.2 mg / particle or more, the handleability of the resin particles tends to be improved and the shrinkage rate of the foamed molded article obtained by molding the obtained foamed beads tends to be small. When the weight per particle of the resin particles is (b) 10.0 mg / particle or less, the mold filling property in the in-mold foam molding step tends to be improved.
[0090] (Peroxide Treatment Step) The present production method preferably includes a peroxide treatment step in which a propylene homopolymer (B1') and / or a polypropylene-based block copolymer (B2') is treated with a peroxide to obtain the propylene homopolymer (B1) and / or the polypropylene-based block copolymer (B2). For example, by melt-kneading an organic peroxide with (i) the propylene homopolymer (B1'), (ii) the polypropylene-based block copolymer (B2'), or (iii) a mixture of the propylene homopolymer (B1') and the polypropylene-based block copolymer (B2') in an extruder, these resins can be treated with the peroxide, and the resulting polymers can be used as (i) the propylene homopolymer (B1), (ii) the polypropylene-based block copolymer (B2), or (iii) a mixture of the propylene homopolymer (B1) and the polypropylene-based block copolymer (B2), respectively. In other words, in this production method, the propylene homopolymer (B1) and / or polypropylene-based block copolymer (B2) may be treated with peroxide. Even if the MFR at 230°C and a load of 2160 g of the mixture of propylene homopolymer and polypropylene-based block copolymer prepared as raw materials is low and does not satisfy the structure B according to one embodiment of the present invention, the MFR of the mixture can be increased by treating the propylene homopolymer and / or polypropylene-based block copolymer with peroxide, thereby making the mixture satisfy the structure B. A propylene homopolymer and a polypropylene-based block copolymer that satisfy the structure B can be respectively referred to as the propylene homopolymer (B1) and the polypropylene-based block copolymer (B2) according to one embodiment of the present invention. In other words, the propylene homopolymer (B1') and the polypropylene-based block copolymer (B2') respectively refer to a propylene homopolymer and a polypropylene-based block copolymer that do not satisfy the structure B. The specific embodiment of the peroxide treatment step is not particularly limited as long as the structure B is satisfied.
[0091] In the present production method, (i) when a propylene homopolymer (B1) is used but a polypropylene-based block copolymer (B2) is not used, only the propylene homopolymer (B1') needs to be treated with a peroxide in the peroxide treatment step; (ii) when a polypropylene-based block copolymer (B2) is used but a propylene homopolymer (B1) is not used, only the polypropylene-based block copolymer (B2') needs to be treated with a peroxide in the peroxide treatment step; (iii) when both the propylene homopolymer (B1) and the polypropylene-based block copolymer (B2) are used, in the peroxide treatment step, (iii-1) only the propylene homopolymer (B1') may be treated with a peroxide, (iii-2) only the polypropylene-based block copolymer (B2') may be treated with a peroxide, or (iii-3) both the propylene homopolymer (B1') and the polypropylene-based block copolymer (B2') may be treated with a peroxide.
[0092] The propylene homopolymer (B1') and the polypropylene block copolymer (B2') may have the same configuration as the propylene homopolymer (B1) and the polypropylene block copolymer (B2), respectively, except that the MFR of a mixture of the propylene homopolymer (B1') and the polypropylene block copolymer (B2') does not satisfy the structure B. That is, for each configuration of the propylene homopolymer (B1') and the polypropylene block copolymer (B2'), the descriptions in the above sections (Propylene homopolymer (B1)) and (Polypropylene block copolymer (B2)) can be appropriately cited.
[0093] In the peroxide treatment step, the amount of peroxide used is preferably 0.01 to 1.00 parts by weight, more preferably 0.05 to 0.50 parts by weight, and even more preferably 0.10 to 0.40 parts by weight, per 100 parts by weight of the total of the propylene homopolymer (B1') and the polypropylene block copolymer (B2').
[0094] Examples of peroxides that can be used include 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, t-butylperoxylaurate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxybenzoate, dicumyl peroxide, 1,3-bis(t-butylperoxyisopropyl)benzene, t-butylperoxyisopropyl monocarbonate, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,1-di(t-butylperoxy)cyclohexane, n-butyl-4,4-di(t-butylperoxy)valerate, α,α'-di(t-butylperoxy)diisopropylbenzene, and 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3.
[0095] In this production method, in addition to the peroxide treatment step described above, the extrusion step may further include a step of treating the mixed resin with a peroxide.
[0096] (Foaming step) The foaming step in the present production method is not particularly limited, but may include, for example, an embodiment having: (i) a dispersing step of dispersing polypropylene-based resin particles, an aqueous dispersion medium, and a foaming agent in a container to obtain a dispersion, (ii) a heating step of heating the dispersion to a temperature equal to or higher than the softening temperature of the polypropylene-based resin particles, (iii) a pressurizing step of increasing the pressure in the container, and (iv) a releasing step of opening one end of the container and releasing the dispersion in the container into a region with a pressure lower than the pressure in the container. Hereinafter, an example of the foaming step will be described using an example in which the foaming step includes the dispersing step, the heating step, the pressurizing step, and the releasing step.
[0097] (Dispersion step) The container used in the dispersion step is not particularly limited. Examples of the container include a pressure-resistant container and an autoclave-type pressure-resistant container (pressure-resistant autoclave). The container may be equipped with a stirrer inside the container.
[0098] The aqueous dispersion medium is not particularly limited as long as it contains water. In terms of enabling stable production of expanded beads, it is preferable to use pure water such as RO water (water purified by a reverse osmosis membrane method), distilled water, deionized water (water purified by an ion exchange resin), or ultrapure water as the aqueous dispersion medium.
[0099] Examples of blowing agents include (a) (a-1) inorganic blowing agents such as inorganic gases such as nitrogen, carbon dioxide, and air (a mixture of oxygen, nitrogen, and carbon dioxide), and (a-2) water; and (b) organic blowing agents. From the viewpoint of reducing the environmental load and reducing the risk of combustion, the blowing agent is preferably an inorganic blowing agent, more preferably an inorganic gas and / or water, and even more preferably carbon dioxide and / or water. The water used as the aqueous dispersion medium can also be used as the blowing agent. In this case, both the aqueous dispersion medium and the blowing agent in the dispersion step can be water.
[0100] In this production method, it is preferable to use a dispersant (e.g., inorganic dispersant such as tricalcium phosphate, trimagnesium phosphate, basic magnesium carbonate, calcium carbonate, barium sulfate, kaolin, talc, clay, etc.) and a dispersing aid (e.g., sodium dodecylbenzenesulfonate, sodium alkanesulfonate, sodium alkylsulfonate, sodium alkyldiphenyletherdisulfonate, sodium α-olefinsulfonate, etc.). This configuration can reduce adhesion of resin particles (sometimes referred to as blocking) and improve the stability of the dispersion in the container. As a result, it has the advantage of enabling stable production of expanded beads.
[0101] (Heating step) In this specification, the "softening temperature of the polypropylene-based resin particles" means the melting point of the resin with the highest melting point among the non-recycled polypropylene-based resin contained in the base resin constituting the polypropylene-based resin particles and the resin components contained in the recycled material -10.0°C.
[0102] In this specification, "a temperature equal to or higher than the softening temperature of the polypropylene-based resin particles" may be referred to as "foaming temperature." In other words, the heating step can be said to be a step of heating the temperature of the dispersion to the foaming temperature. The foaming temperature in the heating step is not particularly limited as long as it is equal to or higher than the softening temperature of the polypropylene-based resin particles. In the heating step, the temperature to which the dispersion is heated, i.e., the upper limit of the foaming temperature, is not particularly limited. The foaming temperature is preferably equal to or lower than the softening temperature of the polypropylene-based resin particles + 20.0°C, more preferably equal to or lower than the softening temperature of the polypropylene-based resin particles + 15.0°C, and even more preferably equal to or lower than the softening temperature of the polypropylene-based resin particles + 10.0°C. This configuration has the advantage that there is no risk of the polypropylene-based resin particles adhering to each other in the container.
[0103] (Pressurizing Step) In this specification, the pressure (constant pressure) after being pressurized in the pressurizing step may be referred to as the “foaming pressure.” In other words, in the pressurizing step, the pressure inside the container is increased to the foaming pressure.
[0104] In the pressurizing step, the pressure inside the container, i.e., the expansion pressure, is not particularly limited. The expansion pressure in the pressurizing step is preferably (i) 1.0 MPa (gauge pressure) to 10.0 MPa (gauge pressure), more preferably (ii) 1.5 MPa (gauge pressure) to 5.0 MPa (gauge pressure), and even more preferably (iii) 1.5 MPa (gauge pressure) to 3.5 MPa (gauge pressure). When the expansion pressure is 1.0 MPa (gauge pressure) or more, expanded beads with a suitable density can be obtained.
[0105] The heating step and the pressure applying step may be carried out in any order, or may be carried out simultaneously.
[0106] (Holding Step) The present production method may further include a holding step, after the heating step and the pressurizing step and before the releasing step, of holding the temperature inside the container at the foaming temperature and the pressure inside the container at (or near) the foaming pressure.
[0107] In the holding step, the time (holding time) for holding the temperature of the dispersion at the foaming temperature and the pressure inside the container at (near) the foaming pressure is not particularly limited. The holding time is preferably 10 to 60 minutes, more preferably 12 to 55 minutes, and even more preferably 15 to 50 minutes. A holding time of 10 minutes or longer has the advantage that a sufficient amount of unmelted crystals (crystals of the base resin) are present, thereby reducing shrinkage and / or an increase in the open cell ratio of the resulting expanded beads. On the other hand, a holding time of 60 minutes or shorter has the advantage that an excessive amount of unmelted crystals are not present, allowing the expanded beads to be molded at a low molding temperature.
[0108] (Releasing Step) The releasing step can be carried out after the heating step and the pressurizing step (a) when the holding step is not carried out, or after the holding step (b) when the holding step is carried out. The releasing step can expand the resin particles, resulting in expanded particles.
[0109] In the releasing step, the "region under a pressure lower than the pressure inside the container" refers to a "region under a pressure lower than the pressure inside the container" or a "space under a pressure lower than the pressure inside the container", and can also be referred to as "an atmosphere under a pressure lower than the pressure inside the container". The region under a pressure lower than the pressure inside the container can also be referred to as a region under a pressure lower than the foaming pressure, and may be, for example, a region under atmospheric pressure. The low-pressure region is, for example, a gas phase. Furthermore, in order to improve foaming properties, the low-pressure region (space) may be filled with saturated water vapor.
[0110] In the discharging step, when the dispersion is discharged into a region having a pressure lower than the pressure inside the container, the dispersion can also be discharged through an orifice having a diameter of 1 mm to 5 mm for the purposes of adjusting the flow rate of the dispersion and reducing variation in the expansion ratio of the resulting expanded beads.
[0111] As described above, the process of producing expanded beads from resin beads is called the "first-stage expansion process," and the resulting expanded beads are called "first-stage expanded beads." In order to obtain expanded beads with a high expansion ratio, the first-stage expanded beads obtained in the first-stage expansion process may be expanded again. The process of increasing the expansion ratio of the first-stage expanded beads is called the "second-stage expansion process," and the polypropylene resin expanded beads obtained by the second-stage expansion process are called "second-stage expanded beads." The specific method for the second-stage expansion process is not particularly limited, and any known method can be used.
[0112] [4. Polypropylene-based resin foam molded article] A polypropylene-based resin foam molded article according to one embodiment of the present invention is a foam molded article obtained by molding the polypropylene-based resin foam beads described in Section [2. Polypropylene-based resin foam beads]. The polypropylene-based resin foam molded article according to one embodiment of the present invention may be a foam molded article obtained by molding the polypropylene-based resin foam beads obtained by the production method described in Section [3. Production method for polypropylene-based resin foam beads]. It can also be said that the polypropylene-based resin foam molded article according to one embodiment of the present invention comprises the polypropylene-based resin foam beads described in Section [2. Polypropylene-based resin foam beads] or the polypropylene-based resin foam beads obtained by the production method described in Section [3. Production method for polypropylene-based resin foam beads].
[0113] In this specification, the "polypropylene resin foam molded article according to one embodiment of the present invention" may be referred to as the "present foam molded article."
[0114] The foamed molded article of the present invention has the above-mentioned structure and therefore has the advantage of excellent internal fusion and / or surface beauty.
[0115] (Internal fusion property) In this specification, the internal fusion property of the present foamed molded article is evaluated by the number of all foamed beads present and the number of foamed beads broken at other than particle interfaces on the fracture surface of the foamed molded article. The greater the number of foamed beads broken at other than particle interfaces among all foamed beads present, in other words, the higher the internal fusion rate, the better the internal fusion property.
[0116] The internal fusion rate of the foamed molded article is preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, and particularly preferably 90% or more.
[0117] (Surface aesthetics) In this specification, the surface aesthetics of the present foamed molded article is evaluated based on the degree of gaps between the foam particles (hereinafter sometimes referred to as "intergranular gaps") on the surface of the foamed molded article and the wrinkles on the surface of the foamed molded article. The smaller the size and number of intergranular gaps on the surface of the foamed molded article, the better the surface aesthetics of the foamed molded article. Furthermore, the fewer wrinkles on the surface of the foamed molded article, the better the surface aesthetics of the foamed molded article.
[0118] (Molding cycle) In this specification, the length of the molding cycle of the present foam molded article is evaluated by the time (seconds) until the cooling (water cooling) of the molded article is completed. The completion time of the cooling (water cooling) of the molded article was defined as the time when the mold was opened and demolded when the surface pressure measured by a pressure gauge attached to the surface of the Planck mold decreased to 0.01 MPa (gauge pressure).
[0119] An embodiment of the present invention may have the following configuration.
[0120] [1] Expanded polypropylene resin particles obtained by expanding polypropylene resin particles, wherein the polypropylene resin particles contain a polypropylene random copolymer (A) having a melting point of 140.0°C or more and less than 155.0°C, and a propylene homopolymer (B1) and / or a polypropylene block copolymer (B2), wherein the melting point of the mixture of the propylene homopolymer (B1) and the polypropylene block copolymer (B2) is 155.0°C or more and less than 165.0°C, and the melt flow rate (MFR) of the polypropylene random copolymer (A) at 230°C and a load of 2160 g is 155.0°C or more and less than 165.0°C. A ) of the mixture of the propylene homopolymer (B1) and the polypropylene block copolymer (B2) at 230°C and a load of 2160 g (MFR B ) ratio (MFR B / MFR A) is 2.0 to 30.0.
[0121] [2] The expanded polypropylene resin particles according to [1], wherein, in the polypropylene resin particles, the content of the polypropylene random copolymer (A) is 70 to 95 parts by weight, and the total content of the propylene homopolymer (B1) and the polypropylene block copolymer (B2) is 5 to 30 parts by weight, based on 100 parts by weight of the polypropylene random copolymer (A), the propylene homopolymer (B1), and the polypropylene block copolymer (B2).
[0122] [3] The expanded polypropylene resin particles according to [1] or [2], which have two or more melting peaks in a DSC curve obtained by measurement using a differential scanning calorimeter.
[0123] [4] The expanded polypropylene resin particles according to any one of [1] to [3], wherein the DSC ratio is 30.0% to 50.0%.
[0124] [5] The expanded polypropylene resin particles according to any one of [1] to [4], wherein at least one of the polypropylene random copolymer (A), the propylene homopolymer (B1), and the polypropylene block copolymer (B2) contains a recycled resin.
[0125] [6] The polypropylene-based resin expanded particles according to any one of [1] to [5], wherein the polypropylene-based resin particles have a melt flow rate (MFR) of 7.0 g / 10 min to 30.0 g / 10 min at 230 ° C and a load of 2160 g.
[0126] [7] The expanded polypropylene resin particles according to any one of [1] to [6], wherein the polypropylene random copolymer (A) is at least one selected from the group consisting of a propylene / ethylene random copolymer, a propylene / 1-butene random copolymer, a propylene / ethylene / 1-butene random copolymer, a propylene / vinyl chloride random copolymer, and a propylene / maleic anhydride random copolymer.
[0127] [8] The melt flow rate (MFR) of the polypropylene random copolymer (A) at 230°C and a load of 2160 g A ) is 3.0 g / 10 min to 30.0 g / 10 min. The expanded polypropylene resin particles according to any one of [1] to [7].
[0128] [9] The polypropylene-based random copolymer (A) includes a recycled polypropylene-based random copolymer, [1] to [8]. The expanded polypropylene-based resin particles.
[0129]
[10] The expanded polypropylene resin particles according to [9], wherein the proportion of the recycled polypropylene random copolymer in 100% by weight of the polypropylene random copolymer (A) is 50% or more.
[0130]
[11] The expanded polypropylene resin particles according to any one of [1] to
[10] , wherein the melting point of the propylene homopolymer (B1) is 155.0°C or higher and lower than 165.0°C.
[0131]
[12] The expanded polypropylene resin particles according to any one of [1] to
[11] , wherein the propylene homopolymer (B1) has a melt flow rate of 6 g / 10 min to 350 g / 10 min at 230 ° C. under a load of 2160 g.
[0132]
[13] The expanded polypropylene resin particles according to any one of [1] to
[12] , wherein when the polypropylene resin particles contain the propylene homopolymer (B1), the ratio of the content of the polypropylene random copolymer (A) in the polypropylene resin particles to the content of the propylene homopolymer (B1) (the content (parts by weight) of the polypropylene random copolymer (A):the content (parts by weight) of the propylene homopolymer (B1)) is 90:10 to 50:50.
[0133]
[14] The expanded polypropylene resin particles according to any one of [1] to
[13] , wherein the total content of structural units derived from isoprene and structural units derived from conjugated dienes is 20% by weight or less, based on 100% by weight of the propylene homopolymer (B1).
[0134]
[15] The expanded polypropylene resin particles according to any one of [1] to
[14] , wherein the polypropylene block copolymer (B2) is at least one selected from the group consisting of a propylene / ethylene block copolymer, a propylene / 1-butene block copolymer, a propylene / ethylene / 1-butene block copolymer, a propylene / vinyl chloride block copolymer, and a propylene / maleic anhydride block copolymer.
[0135]
[16] The expanded polypropylene resin particles according to any one of [1] to
[15] , wherein the melting point of the polypropylene block copolymer (B2) is 155.0°C or higher and lower than 165.0°C.
[0136]
[17] The expanded polypropylene resin particles according to any one of [1] to
[16] , wherein the polypropylene block copolymer (B2) has a melt flow rate of 6 g / 10 min to 350 g / 10 min at 230°C under a load of 2160 g.
[0137]
[18] The expanded polypropylene resin particles according to any one of [1] to
[17] , wherein when the polypropylene resin particles contain the polypropylene block copolymer (B2), the ratio of the content of the polypropylene random copolymer (A) in the polypropylene resin particles to the content of the polypropylene block copolymer (B2) (the content (parts by weight) of the polypropylene random copolymer (A):the content (parts by weight) of the polypropylene block copolymer (B2)) is 90:10 to 40:60.
[0138]
[19] The expanded polypropylene resin particles according to any one of [1] to
[18] , wherein the polypropylene block copolymer (B2) includes a recycled polypropylene block copolymer.
[0139]
[20] The expanded polypropylene resin particles according to any one of [1] to
[19] , wherein the proportion of the recycled polypropylene block copolymer in 100% by weight of the polypropylene block copolymer (B2) is 50% or more.
[0140]
[21] The expanded polypropylene resin particles according to any one of [1] to
[20] , wherein the total content of structural units derived from isoprene and structural units derived from conjugated dienes is 20% by weight or less in 100% by weight of the polypropylene block copolymer (B2).
[0141]
[22] The melt flow rate (MFR) of the mixture of the propylene homopolymer (B1) and the polypropylene block copolymer (B2) at 230°C and a load of 2160 g B ) is 6 g / 10 min to 350 g / 10 min. The expanded polypropylene resin particles according to any one of [1] to
[21] .
[0142]
[23] The expanded polypropylene resin particles according to any one of [1] to
[22] , wherein the polypropylene resin particles contain carbon black.
[0143]
[24] The expanded polypropylene resin particles according to any one of [1] to
[23] , wherein the expansion ratio is 10 to 50 times.
[0144]
[25] The expanded polypropylene resin particles according to any one of [1] to
[24] , wherein the average cell diameter is 80 μm to 500 μm.
[0145]
[26] A polypropylene resin foam molded article obtained by molding the expanded polypropylene resin beads according to any one of [1] to
[25] .
[0146]
[27] The polypropylene resin foam molded article according to
[26] , wherein the internal fusion rate is 60% or more.
[0147]
[28] A method for producing polypropylene-based resin particles, comprising: an extrusion step of melt-kneading a mixed resin containing a polypropylene-based random copolymer (A) having a melting point of 140.0°C or more and less than 155.0°C, and a propylene homopolymer (B1) and / or a polypropylene-based block copolymer (B2) to obtain polypropylene-based resin particles; and an expansion step of expanding the polypropylene-based resin particles obtained in the extrusion step, wherein the melting point of the mixture of the propylene homopolymer (B1) and the polypropylene-based block copolymer (B2) is 155.0°C or more and less than 165.0°C, and the melt flow rate (MFR) of the polypropylene-based random copolymer (A) at 230°C and a load of 2160 g is 155.0°C or more and less than 165.0°C. A ) of the mixture of the propylene homopolymer (B1) and the polypropylene block copolymer (B2) at 230°C and a load of 2160 g (MFR B ) ratio (MFR B / MFR A ) is 2.0 to 30.0.
[0148]
[29] A method for producing expanded polypropylene-based resin beads according to
[28] , comprising a peroxide treatment step of treating a propylene homopolymer (B1') and / or a polypropylene-based block copolymer (B2') with a peroxide to obtain the propylene homopolymer (B1) and / or the polypropylene-based block copolymer (B2).
[0149]
[30] The method for producing expanded polypropylene resin beads according to
[28] or
[29] , wherein the amount of the peroxide used in the peroxide treatment step is 0.01 to 1.00 parts by weight per 100 parts by weight of the total of the propylene homopolymer (B1') and the polypropylene block copolymer (B2').
[0150]
[31] The polypropylene-based resin particles have a melt flow rate (MFR) of 7.0 g / 10 min to 30.0 g / 10 min at 230 ° C. and a load of 2160 g.
[28] -
[30] The method for producing expanded polypropylene-based resin particles.
[0151]
[32] The method for producing expanded polypropylene resin beads according to any one of
[28] to
[31] , wherein in the extrusion step, the amount of the polypropylene random copolymer (A) used is 70 to 95 parts by weight, and the total amount of the propylene homopolymer (B1) and the polypropylene block copolymer (B2) used is 5 to 30 parts by weight, based on a total of 100 parts by weight of the polypropylene random copolymer (A), the propylene homopolymer (B1), and the polypropylene block copolymer (B2).
[0152]
[33] The expanded polypropylene resin beads have two or more melting peaks in a DSC curve obtained by measurement using a differential scanning calorimeter.
[28] -
[32] The method for producing expanded polypropylene resin beads.
[0153]
[34] The method for producing expanded polypropylene resin beads according to any one of
[28] to
[33] , wherein the DSC ratio of the expanded polypropylene resin beads is 30.0% to 50.0%.
[0154]
[35] The method for producing expanded polypropylene resin beads according to any one of
[28] to
[34] , wherein at least one of the polypropylene random copolymer (A), the propylene homopolymer (B1), and the polypropylene block copolymer (B2) contains a recycled resin.
[0155]
[36] The method for producing expanded polypropylene resin beads according to any one of
[28] to
[35] , wherein the polypropylene random copolymer (A) is at least one selected from the group consisting of a propylene / ethylene random copolymer, a propylene / 1-butene random copolymer, a propylene / ethylene / 1-butene random copolymer, a propylene / vinyl chloride random copolymer, and a propylene / maleic anhydride random copolymer.
[0156]
[37] The melt flow rate (MFR) of the polypropylene random copolymer (A) at 230°C and a load of 2160 g A) is 3.0 g / 10 min to 30.0 g / 10 min. The method for producing expanded polypropylene resin beads according to any one of
[28] to
[36] .
[0157]
[38] The method for producing expanded polypropylene resin beads according to any one of
[28] to
[37] , wherein the polypropylene random copolymer (A) includes a recycled polypropylene random copolymer.
[0158]
[39] The method for producing expanded polypropylene resin beads according to
[38] , wherein the proportion of the recycled polypropylene random copolymer in 100% by weight of the polypropylene random copolymer (A) is 50% or more.
[0159]
[40] The method for producing expanded polypropylene resin beads according to any one of
[28] to
[39] , wherein the melting point of the propylene homopolymer (B1) is 155.0°C or higher and lower than 165.0°C.
[0160]
[41] The method for producing expanded polypropylene resin beads according to any one of
[28] to
[40] , wherein the propylene homopolymer (B1) has a melt flow rate of 6 g / 10 min to 350 g / 10 min at 230°C under a load of 2160 g.
[0161]
[42] The method for producing expanded polypropylene resin beads according to any one of
[28] to
[41] , wherein, when the propylene homopolymer (B1) is used in the extrusion step, the ratio of the amount of the polypropylene random copolymer (A) used in the extrusion step to the amount of the propylene homopolymer (B1) used (parts by weight of the polypropylene random copolymer (A) : amount of the propylene homopolymer (B1) used (parts by weight)) is 90:10 to 50:50.
[0162]
[43] The method for producing expanded polypropylene resin beads according to any one of
[28] to
[42] , wherein the total content of structural units derived from isoprene and structural units derived from conjugated dienes is 20% by weight or less, based on 100% by weight of the propylene homopolymer (B1).
[0163]
[44] The method for producing expanded polypropylene-based resin beads according to any one of
[28] to
[43] , wherein the polypropylene-based block copolymer (B2) is at least one selected from the group consisting of a propylene / ethylene block copolymer, a propylene / 1-butene block copolymer, a propylene / ethylene / 1-butene block copolymer, a propylene / chlorinated vinyl block copolymer, and a propylene / maleic anhydride block copolymer.
[0164]
[45] The method for producing expanded polypropylene resin beads according to any one of
[28] to
[44] , wherein the melting point of the polypropylene block copolymer (B2) is 155.0°C or higher and lower than 165.0°C.
[0165]
[46] The method for producing expanded polypropylene resin beads according to any one of
[28] to
[45] , wherein the polypropylene block copolymer (B2) has a melt flow rate of 6 g / 10 min to 350 g / 10 min at 230°C and a load of 2160 g.
[0166]
[47] The method for producing expanded polypropylene resin beads according to any one of
[28] to
[46] , wherein, when the polypropylene block copolymer (B2) is used in the extrusion step, the ratio of the amount of the polypropylene random copolymer (A) used in the extrusion step to the amount of the polypropylene block copolymer (B2) used (amount of the polypropylene random copolymer (A) used (parts by weight):amount of the polypropylene block copolymer (B2) used (parts by weight)) is 90:10 to 40:60.
[0167]
[48] The method for producing expanded polypropylene resin beads according to any one of
[28] to
[47] , wherein the polypropylene block copolymer (B2) includes a recycled polypropylene block copolymer.
[0168]
[49] The method for producing expanded polypropylene resin beads according to any one of
[28] to
[48] , wherein the proportion of the recycled polypropylene block copolymer in 100% by weight of the polypropylene block copolymer (B2) is 50% or more.
[0169]
[50] The method for producing expanded polypropylene resin beads according to any one of
[28] to
[49] , wherein the total content of structural units derived from isoprene and structural units derived from conjugated diene is 20% by weight or less in 100% by weight of the polypropylene block copolymer (B2).
[0170]
[51] The melt flow rate (MFR) of the mixture of the propylene homopolymer (B1) and the polypropylene block copolymer (B2) at 230°C and a load of 2160 g B ) is 6 g / 10 min to 350 g / 10 min.
[0171]
[52] The method for producing expanded polypropylene resin beads according to any one of
[28] to
[51] , wherein the mixed resin contains carbon black.
[0172]
[53] The method for producing expanded polypropylene resin beads according to any one of
[28] to
[52] , wherein the expansion ratio of the expanded polypropylene resin beads is 10 to 50 times.
[0173]
[54] The method for producing expanded polypropylene resin beads according to any one of
[28] to
[53] , wherein the expanded polypropylene resin beads have an average cell diameter of 80 μm to 500 μm.
[0174]
[55] A method for producing a polypropylene-based resin foam molded article, comprising a step of molding expanded polypropylene-based resin beads produced by the method for producing expanded polypropylene-based resin beads according to any one of
[28] to
[54] .
[0175]
[56] The method for producing a polypropylene-based resin foam molded article according to
[55] , wherein the polypropylene-based resin foam molded article has an internal fusion rate of 60% or more.
[0176] Hereinafter, one embodiment of the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.
[0177] [Materials] <Base resin> (Polypropylene-based random copolymer (A)) A-1, A-2 [non-recycled resin; manufactured by Prime Polymer Co., Ltd., propylene / ethylene random copolymer] A-3 [non-recycled resin; manufactured by Prime Polymer Co., Ltd., propylene / ethylene / 1-butene random copolymer] A-4 [recycled material; a foamed molded article containing A-3 as the base resin was pulverized, and the pulverized material was melt-kneaded to obtain a resin composition in the form of pellets. The resulting resin composition in pellet form was used as a recycled material.] (Propylene homopolymer (B1)) B1-1 [Non-recycled resin; manufactured by Prime Polymer Co., Ltd., propylene homopolymer] B1-2, B1-3 [Non-recycled resin; resin obtained by treating B1-1 with peroxide] B1-4 [Non-recycled resin; manufactured by Prime Polymer Co., Ltd., propylene homopolymer] B1-5 [Non-recycled resin; resin obtained by treating B1-4 with peroxide] (Polypropylene block copolymer (B2)) B2-1 [Non-recycled resin; manufactured by Prime Polymer Co., Ltd., propylene / ethylene block copolymer] B2-2 [Non-recycled resin; resin obtained by treating B2-1 with peroxide] B2-3 [Non-recycled resin; manufactured by Prime Polymer Co., Ltd., propylene / ethylene block copolymer] B2-4, B2-5 [Non-recycled resin; resin obtained by treating B2-3 with peroxide] B2-6 [Non-recycled resin; propylene / ethylene block copolymer manufactured by Prime Polymer Co., Ltd.] B2-7, B2-8 [Non-recycled resin; resin obtained by treating B2-6 with peroxide] B2-9 [Recycled material; automotive parts containing a propylene / ethylene block copolymer as a base resin were pulverized, and the pulverized material was melt-kneaded to obtain a resin composition in pellet form. The resulting resin composition in pellet form was used as the recycled material] B2-10 to B2-12 [Recycled material; material obtained by treating B2-9 with peroxide] B2-13 [Recycled material; foamed sheet containing a propylene / ethylene block copolymer as a base resin was pulverized, and the pulverized material was melt-kneaded to obtain a resin composition in pellet form.The resulting pellet-shaped resin composition was used as a recycled material.] B2-14, B2-15 [recycled material; material obtained by treating B2-13 with peroxide] (peroxides) Peroxide [NOF Corp., Perbutyl I] Peroxide [NOF Corp., Perhexa 25B-40] (Adjustment of MFR of polypropylene resin and recycled material (peroxide treatment step)) B1-2 and B1-3 were obtained by dry-blending B1-1 with the peroxides shown in Table 1 using a blender, melt-kneading the mixture at a resin temperature of 220°C using a twin-screw extruder (Toshiba Machine Co., Ltd., TEM26-SX), and water-cooling the extruded strands in a 2 m-long water tank and then cutting them to obtain strands (approximately 5 mg / grain). Similarly, B2-2 was obtained by treating B2-1, B1-5 by treating B1-4, B2-4 and B2-5 by treating B2-3, B2-7 and B2-8 by treating B2-6, B2-10 to B2-12 by treating B2-9, and B2-14 and B2-15 by treating B2-13 with the peroxides shown in Table 1. The amount of peroxide (parts by weight) in Table 1 is the amount of peroxide used per 100 parts by weight of non-recycled resin or recycled material.
[0178] Table 1 shows the composition of the non-recycled resin used, the composition of the recycled polypropylene resin contained in the recycled material, and the peroxide treatment. The melting point, MFR, number-average molecular weight (Mn), weight-average molecular weight (Mw), and z-average molecular weight (Mz) of the non-recycled resin and recycled material used were measured using the methods described below. The carbon black content and ash content of the recycled material used were measured using the methods described below. The results are shown in Table 2. In Table 2, resins marked with "-" in the "Carbon Black (wt%)" column indicate that they contain no carbon black (0 wt%). Similarly, recycled materials marked with "-" in the "Ash Content (wt%)" column indicate that they contain no ash (0.00 wt% or more and 0.05 wt% or less). In Table 2, the content of recycled polypropylene resin contained in the recycled material is calculated by subtracting the carbon black content and ash content listed in Table 2 from 100 wt% of the recycled material.
[0179] <Resin particle additives> Talc [Talc Powder PK-S, manufactured by Hayashi Kasei Co., Ltd.] Glycerin [Purified Glycerin D, manufactured by Lion Corporation] Zinc borate [Zinc borate 2335, manufactured by Tomita Pharmaceutical Co., Ltd.] Carbon black masterbatch [a mixture obtained by mixing 40 parts by weight of carbon black and 60 parts by weight of polypropylene resin (MFR at 230°C = 7.5 g / 10 min)].
[0180] [Measurement Methods] The evaluation methods used in the examples and comparative examples are described below.
[0181] <Measurement of Melting Point of Polypropylene-Based Resin and Recycled Material> The melting points of the polypropylene-based resin and recycled material were measured using a differential scanning calorimeter (DSC7020, manufactured by Hitachi High-Tech Science Corporation). The specific measurement method was as follows (1) to (3): (1) 5 to 6 mg of the sample to be measured was heated from 40°C to 220°C at a heating rate of 10°C / min to melt; (2) Then, the temperature was lowered from 220°C to 40°C at a heating rate of 10°C / min to crystallize; (3) The temperature was further increased from 40°C to 220°C at a heating rate of 10°C / min. The temperature of the peak (melting peak) of the DSC curve obtained during the second heating (i.e., during (3)) was taken as the melting point of the polypropylene-based resin and recycled material. In addition, when there are multiple peaks (melting peaks) in the DSC curves of the polypropylene-based resin and the recycled material obtained by the second temperature increase using the above-mentioned method, the temperature of the peak (melting peak) with the largest heat of fusion was taken as the melting point of the polypropylene-based resin and the recycled material.
[0182] <Measurement of MFR of Polypropylene Resin and Recycled Material> The MFR of the polypropylene resin and recycled material was measured using a melt mass-flow rate measuring device described in JIS K7210 under the following conditions: orifice 2.0959±0.005 mmφ, orifice length 8.000±0.025 mm, load 2160 g, and temperature 230±0.2°C.
[0183] <GPC Measurement of Polypropylene Resin and Recycled Material> The number average molecular weight (Mn), weight average molecular weight (Mw) and z average molecular weight (Mz) of the polypropylene resin and recycled material were measured as polystyrene equivalent values by gel permeation chromatography (GPC). The GPC measurement conditions for measuring the molecular weights of the polypropylene resin and recycled material were as follows.
[0184] 20 mg of the polypropylene resin and recycled material to be measured were completely dissolved in 20 mL of o-dichlorobenzene at 145 ° C., and the resulting solution was hot-filtered through a sintered filter with a pore size of 1.0 μm, and the filtrate was used as an analytical sample. Measurement equipment: HLC-8321 GPC / HT type high-temperature gel permeation chromatograph (manufactured by Tosoh Corporation) Analysis equipment: Data processing software Empower 3 (manufactured by Waters Japan) Columns: 2 TSKgel GMH6-HT, 2 TSKgel GMH6-HTL (inner diameter 7.5 mm x length 300 mm, manufactured by Tosoh Corporation) Mobile phase: o-dichlorobenzene (containing 0.025% BHT) Column temperature: 140 ° C Detector: differential refractometer Flow rate: 1.0 mL / min Injection volume: 1.0 mL / min.
[0185] The recycled materials used in the examples and comparative examples did not contain any resins other than the polypropylene-based resins listed in the "Composition of Recycled Polypropylene-Based Resins Contained in the Recycled Material" column, but only contained carbon black and ash. Carbon black and ash do not affect the melting point, MFR, number-average molecular weight (Mn), weight-average molecular weight (Mw), and z-average molecular weight (Mz). Therefore, the melting point, MFR, number-average molecular weight (Mn), weight-average molecular weight (Mw), and z-average molecular weight (Mz) of the recycled materials can be considered to be the melting point, MFR, number-average molecular weight (Mn), weight-average molecular weight (Mw), and z-average molecular weight (Mz) of the polypropylene-based resins listed in the "Composition of Recycled Polypropylene-Based Resins Contained in the Recycled Material" column, respectively.
[0186] <Quantitative Determination of Carbon Black in Recycled Materials> The carbon black content in recycled materials was measured using a thermogravimetric and differential thermal analyzer (STA200RV, manufactured by Hitachi High-Tech Science Corp.). The specific operating procedures were as follows: (1) 6 to 8 mg of the sample to be measured was weighed into a Pt measuring vessel; (2) The temperature of the sample was increased to 600°C at 10°C / min in a nitrogen atmosphere, then cooled to 400°C at 10°C / min, and then the sample was placed in a simulated air (oxygen:nitrogen = 21%:79%) atmosphere and heated to 800°C at 10°C / min; (3) In the TG weight loss curve obtained in step (2), the weight loss rate (wt%) at 400°C in the step of increasing the temperature from 400°C to 800°C and the weight loss rate (wt%) at 800°C were used to calculate the weight ratio (wt%) of carbon black.
[0187] <Quantitative Determination of Ash Content in Recycled Materials> The ash content in the recycled materials was determined from the weight of the recycled materials and the weight of the residue after burning the recycled materials. The specific operating procedures were as follows: (1) The recycled materials were heated at 150°C for 1 hour to completely remove moisture from the recycled materials; (2) 1 g to 2 g of recycled materials were placed in a crucible and held at 300°C in an electric furnace for 30 minutes or more, and then burned at 750°C for 1 hour or more; (3) The crucible was removed from the electric furnace and cooled in a desiccator at 23°C for 1 hour; (4) The ash content in the recycled materials was calculated using the following formula: W1: weight of crucible (g); W2: weight of crucible + recycled materials before burning (g); W3: weight of crucible + recycled materials after burning (g); Ash content in recycled materials (wt%) = {(W3 - W1) * 100} / (W2 - W1).
[0188] <Measurement of MFR of polypropylene-based resin particles> The method for measuring the MFR of polypropylene-based resin particles is the same as the method described in the section <Measurement of MFR of polypropylene-based resin and recycled material> above, except that the sample is polypropylene-based resin particles. Therefore, the description therein is incorporated by reference and will not be described again here.
[0189] <Measurement of DSC Ratio of Expanded Polypropylene Resin Beads> The DSC ratio was measured using a differential scanning calorimeter (DSC7020, manufactured by Hitachi High-Tech Science Corporation). Specifically, the area of the melting peak on the low-temperature side of the DSC curve obtained during the first temperature rise when 5 to 6 mg of expanded polypropylene resin beads was heated from 40°C to 220°C at a heating rate of 10°C / min was determined as Q l The melting peak area on the high temperature side is Q h The DSC ratio was calculated using the following formula: DSC ratio (%) = Q h / (Q l +Q h ) x 100.
[0190] Strictly speaking, the procedure was as follows: A line segment was drawn connecting the maximum point between the low-temperature melting peak and the high-temperature melting peak and the point on the curve at a temperature of 100°C. L The melting peak and line segment on the low temperature side L The area of the part enclosed by and is Q l In addition, a line was drawn from the maximum point between the melting peak on the low temperature side and the melting peak on the high temperature side to the melting end baseline. H The melting peak and line segment on the high temperature side H The area of the part enclosed by and is Q h In addition, the temperature at the top of the melting peak on the higher side and the temperature at the top of the melting peak on the lower side were read.
[0191] <Measurement of Expansion Ratio of Expanded Polypropylene Resin Beads> The expansion ratio of expanded beads was measured by the following methods (1) to (4): (1) Approximately 3 g to 10 g of expanded polypropylene resin beads were taken, dried at 60°C for 6 hours, and then conditioned in a room at 23°C and 50% humidity, and the weight w 1 (2) The expanded particles used for the weight measurement were submerged in a measuring cylinder containing ethanol, and the volume v (cm) was measured by the amount of rise in the water level in the measuring cylinder (submersion method). 3 (3) The true specific gravity ρ of the expanded polypropylene resin particles was measured. b =w 1 / v was calculated; (4) Density ρ of polypropylene resin particles before foaming r The true specific gravity ρ of the polypropylene resin foam particlesb The value obtained was used as the expansion ratio of the expanded polypropylene resin beads. In the examples and comparative examples shown below, the density ρ of the polypropylene resin beads before expansion (polypropylene resin beads) was r are all 0.9 g / cm 3 It was.
[0192] <Average Cell Diameter of Expanded Polypropylene Resin Beads> The average cell diameter of expanded polypropylene resin beads was measured by the following methods (1) to (5): (1) Using a razor (high-stainless double-edged blade, manufactured by Feather Corporation), the expanded beads were cut so as to pass through the center of the expanded beads, while being careful not to destroy the cell membranes (cell membranes) of the expanded beads; (2) The cut surface of the expanded beads obtained was observed using a microscope (manufactured by Hirox Co., Ltd., RH-2000), and an image of the observed surface was taken; (3) On the obtained image, a line segment corresponding to a length of 2000 μm was drawn at any part of the expanded beads except for the surface layer part; (4) The number n of cells through which the line segment passed was measured, and the cell diameter was calculated from the formula (cell diameter = 2000 / n (μm)); (5) The same procedure was performed on 10 expanded beads, and the arithmetic mean value of the calculated cell diameters was taken as the average cell diameter of the expanded polypropylene resin beads.
[0193] <Internal Fusion Property of Polypropylene-Based Resin Foam Molded Articles> The internal fusion property of polypropylene-based resin foam molded articles was evaluated by determining the internal fusion rate of the molded article. The internal fusion rate of polypropylene-based resin foam molded articles was measured as follows (1) to (4): (1) A cutter was used to make a 5 mm long incision on any one surface of the foam molded article in a direction perpendicular to the surface; (2) The foam molded article was then manually broken along the incision; (3) The area of the resulting fracture surface excluding the incision was visually observed to count the total number of foamed beads present in the area and the number of foamed beads that had broken in the area other than at the particle interface (i.e., the foamed beads that had broken themselves); (4) The internal fusion rate was calculated according to the following formula: Internal fusion rate (%) = (number of foamed beads that had broken in the area other than at the particle interface / total number of foamed beads present in the area) × 100. The values listed in the "Internal Fusion Property" column of Tables 3 to 5 are the internal fusion rate (%) values.
[0194] <Surface Beauty of Polypropylene-Based Resin Foam Molded Article> A 350 mm long x 450 mm wide surface of the obtained polypropylene-based resin foam molded article was visually observed, and the surface beauty was judged according to the following criteria. Interparticle gaps (gaps between polypropylene-based resin foam particles), which are one of the evaluation indices for surface beauty, were judged by visually counting the number of gaps present in a 50 mm square area at the center of the surface of the molded article. 4 (Beautiful surface appearance): No wrinkles and 0 to 1 interparticle gap. 3 (Good surface appearance): No wrinkles and 2 to 3 interparticle gaps. 2 (Acceptable surface appearance): Wrinkles are observed or 4 to 5 interparticle gaps are present. 1 (Failure in surface appearance): Wrinkles are observed or 6 or more interparticle gaps are present.
[0195] <Molding Cycle of Polypropylene-Based Resin Foam Molded Articles> The molding cycle in the manufacturing method for polypropylene-based resin foam molded articles was measured from the start of molding to the end of molding, when the molded article was demolded. The start of molding was the point at which the polypropylene-based resin foam beads began to be filled into the mold. A mold capable of forming a molding space measuring 370 mm long, 320 mm wide, and 50 mm thick was used. Next, with the drain valve of the drain line of the molding machine open, steam at 0.10 MPa (gauge pressure) was pumped into the mold for 3 seconds to heat the foamed beads and expel air from the mold (preheating step). Next, steam was flowed from the fixed mold side to the movable mold side for 6 seconds (one-way heating step), and then steam was flowed from the movable mold side to the fixed mold side for 3 seconds (reverse one-way heating step) to expel air and heat the foamed beads. Next, with the drain valve of the drain line of the molding machine closed, steam at 0.30 MPa (gauge pressure) was pumped into the mold for 9 seconds to heat the foamed beads (double-sided heating step), fusing them to form a foam molded article. Next, the foam molded article in the mold was water-cooled. Subsequently, the mold was opened when the surface pressure measured by a surface pressure gauge attached to the surface of the Planck mold had dropped to 0.01 MPa (gauge pressure), and molding was completed when the mold was released. The evaluation criteria for molding cycle (productivity) were as follows: 3 (excellent): molding cycle was 180 seconds or less. 2 (poor): molding cycle was more than 180 seconds and less than 210 seconds. 1 (very poor): molding cycle was more than 210 seconds.
[0196] The methods for producing polypropylene resin particles, expanded polypropylene resin particles, and expanded molded polypropylene resin articles in Examples and Comparative Examples will be described below.
[0197] Example 1 [Preparation of Polypropylene-Based Resin Particles] 75 parts by weight of A-3 as the polypropylene-based random copolymer (A), 25 parts by weight of B1-2 as the propylene homopolymer (B1), 0.2 parts by weight of talc, and 0.2 parts by weight of glycerin were weighed and dry-blended using a blender to obtain a mixed resin. The obtained mixed resin was melt-kneaded at a resin temperature of 220°C using a twin-screw extruder (TEM26-SX, manufactured by Toshiba Machine Co., Ltd.), and the extruded strand was water-cooled in a 2-m-long water tank and then cut to produce polypropylene-based resin particles (1.2 mg / particle) (extrusion step).
[0198] [Preparation of expanded polypropylene resin particles (expansion step)] 100 parts by weight (2.4 kg) of the polypropylene resin particles obtained as described above, 200 parts by weight of water, 0.3 parts by weight of kaolin (manufactured by BASF, ASP170) as a water-insoluble inorganic compound, and 0.06 parts by weight of sodium dodecylbenzenesulfonate (manufactured by Kao Corporation, Neopelex G-15) as a surfactant were charged into a 10 L pressure-resistant autoclave, and then 5 parts by weight of carbon dioxide was added as a foaming agent under stirring (dispersion step). The contents of the autoclave were heated to a foaming temperature of 160 ° C. (heating step), and maintained for 10 minutes. After that, carbon dioxide was additionally injected to increase the internal pressure of the autoclave to a foaming pressure of 2.80 MPa (gauge pressure) (pressurization step). After maintaining the foaming temperature and foaming pressure for 20 minutes (maintaining step), the valve at the bottom of the autoclave was opened, and the foam was released through a 3.6 mm diameter orifice to atmospheric pressure to obtain expanded polypropylene resin beads with an expansion ratio of 18 (releasing step). During this release, carbon dioxide was injected to maintain the pressure in the container so that it would not decrease. The expanded polypropylene resin beads had two peaks in the DSC curve: a high-temperature melting peak at 169 ° C and a low-temperature melting peak at 150 ° C, a DSC ratio of 30.1%, and an average cell diameter of 280 μm.
[0199] [Preparation of Polypropylene-Based Resin Foam Molded Article] The obtained polypropylene-based resin foamed beads were dried at 80°C. The dried polypropylene-based resin foamed beads were placed in a pressure-resistant container and impregnated with pressurized air to adjust the internal pressure of the polypropylene-based resin foamed beads to 0.20 MPa (absolute pressure). Next, the pressurized polypropylene-based resin foamed beads were filled into a mold measuring 370 mm in length, 320 mm in width, and 50 mm in thickness. The mold chamber was then heated with steam at 0.30 MPa (gauge pressure) (molding pressure) to fuse the foamed beads together. After water-cooling the inside of the mold and the surface of the molded article, the molded article was released from the mold to obtain a polypropylene-based resin foamed molded article. The obtained foamed molded article was left to stand at 23°C for 2 hours and then aged at 75°C for 16 hours.
[0200] (Examples 2 to 20, Comparative Examples 1 to 8) In [Preparation of Polypropylene-Based Resin Particles], polypropylene-based resin particles were prepared by the same procedure as in Example 1, except that the formulation of the base resin was changed as shown in Tables 3 to 5. For example, in Example 12, polypropylene-based resin particles were prepared by the same procedure as in Example 1, except for the following: 75 parts by weight of A-3 as the polypropylene-based random copolymer (A), 25 parts by weight of B2-12- as the propylene homopolymer (B1), 0.2 parts by weight of talc, 0.2 parts by weight of glycerin, and 7.5 parts by weight of the carbon black masterbatch were weighed out and dry-blended using a blender to obtain a mixed resin. For example, in Example 13, polypropylene-based resin particles were prepared in the same manner as in Example 1, except for the following: 75 parts by weight of A-3 as the polypropylene-based random copolymer (A), 25 parts by weight of B2-12- as the propylene homopolymer (B1), 0.05 parts by weight of zinc borate, and 7.5 parts by weight of a carbon black masterbatch were weighed and dry-blended using a blender to obtain a mixed resin. Next, polypropylene-based resin expanded beads and polypropylene-based resin foam molded articles were prepared in the same manner as in Example 1, except that the foaming conditions in [Preparation of Expanded Polypropylene-Based Resin Beads] were changed as shown in Tables 3 to 5. The formulation conditions of the base resin, the foaming conditions, and the evaluation results of the obtained expanded polypropylene-based resin beads and expanded polypropylene-based resin foam molded articles are shown in Tables 3 to 5.
[0201] In Examples 1 to 20, the compositions contained a polypropylene random copolymer (A) and a propylene homopolymer (B1) and / or a polypropylene block copolymer (B2), and had an MFR B / MFR AIt was found that, as long as the polypropylene-based resin particles have a molecular weight of 2.0 to 30.0, even when a recycled polypropylene-based random copolymer (A), or a propylene homopolymer (B1) and / or a polypropylene-based block copolymer (B2) is used as in Examples 8 to 20, a foamed molded article can be obtained in a short molding cycle, and a foamed molded article having excellent surface beauty can be obtained.
[0202] It was found that in Comparative Examples 1 to 8, when either the configuration A or the configuration B was not satisfied, the molding cycle was poor and there was room for improvement in the surface aesthetics.
[0203] According to one embodiment of the present invention, novel polypropylene-based resin particles capable of producing a polypropylene-based resin foam molded article in a short molding cycle can be provided, which can be used in a variety of applications, including automotive interior components, core materials for automotive bumpers, heat insulating materials, cushioning packaging materials, and returnable containers.
Claims
1. Polypropylene-based resin expanded particles obtained by expanding polypropylene-based resin particles, wherein the polypropylene-based resin particles contain a polypropylene-based random copolymer (A) having a melting point of 140.0°C or more but less than 155.0°C, and a propylene homopolymer (B1) and / or a polypropylene block copolymer (B2), wherein the melting point of the mixture of the propylene homopolymer (B1) and the polypropylene block copolymer (B2) is 155.0°C or more but less than 165.0°C, and the melt flow rate (MFR) of the polypropylene random copolymer (A) at 230°C and a load of 2160 g is A ) of the mixture of the propylene homopolymer (B1) and the polypropylene block copolymer (B2) at 230°C and a load of 2160 g (MFR B ) ratio (MFR B / MFR A ) is 2.0 to 30.
0.
2. The expanded polypropylene resin particles according to claim 1, wherein, in the polypropylene resin particles, the content of the polypropylene random copolymer (A) is 70 to 95 parts by weight, and the total content of the propylene homopolymer (B1) and the polypropylene block copolymer (B2) is 5 to 30 parts by weight, based on a total of 100 parts by weight of the polypropylene random copolymer (A), the propylene homopolymer (B1), and the polypropylene block copolymer (B2).
3. The expanded polypropylene resin particles according to claim 1, which have two or more melting peaks in a DSC curve obtained by measurement using a differential scanning calorimeter.
4. The expanded polypropylene resin particles according to claim 1, wherein the DSC ratio is 30.0% to 50.0%.
5. The polypropylene-based resin expanded particles according to claim 1, wherein at least one of the polypropylene-based random copolymer (A), the propylene homopolymer (B1), and the polypropylene-based block copolymer (B2) contains a recycled resin.
6. The expanded polypropylene resin particles according to claim 1, wherein the melt flow rate (MFR) of the polypropylene resin particles at 230°C under a load of 2160 g is 7.0 g / 10 min to 30.0 g / 10 min.
7. The expanded polypropylene resin particles according to claim 1, wherein the propylene homopolymer (B1) has a melt flow rate of 6 g / 10 min to 350 g / 10 min at 230°C under a load of 2160 g, and the polypropylene block copolymer (B2) has a melt flow rate of 6 g / 10 min to 350 g / 10 min at 230°C under a load of 2160 g.
8. The expanded polypropylene resin particles according to claim 1, wherein the polypropylene resin particles contain carbon black.
9. A polypropylene resin foam molded article obtained by molding the polypropylene resin foam beads according to any one of claims 1 to 8.
10. A method for producing polypropylene-based resin particles, comprising: an extrusion step of melt-kneading a mixed resin containing a polypropylene-based random copolymer (A) having a melting point of 140.0°C or more and less than 155.0°C, and a propylene homopolymer (B1) and / or a polypropylene-based block copolymer (B2) to obtain polypropylene-based resin particles; and an expansion step of expanding the polypropylene-based resin particles obtained in the extrusion step, wherein the melting point of the mixture of the propylene homopolymer (B1) and the polypropylene-based block copolymer (B2) is 155.0°C or more and less than 165.0°C, and the melt flow rate (MFR) of the polypropylene-based random copolymer (A) at 230°C and a load of 2,160 g is 155.0°C or more and less than 165.0°C. A ) of the mixture of the propylene homopolymer (B1) and the polypropylene block copolymer (B2) at 230°C and a load of 2160 g (MFR B ) ratio (MFR B / MFR A ) is 2.0 to 30.
0.
11. A method for producing expanded polypropylene resin beads according to claim 10, comprising a peroxide treatment step of treating a propylene homopolymer (B1') and / or a polypropylene block copolymer (B2') with a peroxide to obtain the propylene homopolymer (B1) and / or the polypropylene block copolymer (B2).
12. The method for producing expanded polypropylene resin beads according to claim 10 or 11, wherein the melt flow rate (MFR) of the polypropylene resin beads at 230°C under a load of 2160 g is 7.0 g / 10 min to 30.0 g / 10 min.
13. The method for producing expanded polypropylene resin beads according to claim 11, wherein the amount of peroxide used in the peroxide treatment step is 0.01 to 1.00 parts by weight per 100 parts by weight of the total of the propylene homopolymer (B1') and the polypropylene block copolymer (B2').
Citation Information
Patent Citations
Polypropylene-based resin pre-foamed pellets and polypropylene-based resin internal mold foamed molded article obtained from the polypropylene-based resin pre-foamed pellets
JP2009256460A
Manufacturing method of pre-expanded particle of polypropylene resin, and pre-expanded particle of polypropylene resin
JP2010043209A
Polypropylene resin foam particle, polypropylene resin in-mold foam molded body and manufacturing method therefor
JP2017179281A
Composite foam sheet and molding
JP2020163756A
Polypropylene resin foam particles, polypropylene resin foam molded body, and method for manufacturing polypropylene resin foam particles
WO2023190441A1