WO2024166599A1 - 発泡成形体の製造方法 - Google Patents

発泡成形体の製造方法 Download PDF

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Publication number
WO2024166599A1
WO2024166599A1 PCT/JP2024/000572 JP2024000572W WO2024166599A1 WO 2024166599 A1 WO2024166599 A1 WO 2024166599A1 JP 2024000572 W JP2024000572 W JP 2024000572W WO 2024166599 A1 WO2024166599 A1 WO 2024166599A1
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Prior art keywords
mpa
steam
heating step
movable
drain valve
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English (en)
French (fr)
Japanese (ja)
Inventor
賢明 南田
哲也 梅原
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Kaneka Corp
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Kaneka Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/36—Feeding the material to be shaped
    • B29C44/38—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length
    • B29C44/44—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length in solid form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/60—Measuring, controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products

Definitions

  • the present invention relates to a method for producing a foamed molded article.
  • biodegradable plastics that are decomposed by the action of microorganisms in (a) the sea, soil, and other environments, and (b) landfill sites and compost, have attracted attention.
  • Development of biodegradable plastics is being promoted with the aim of wide-ranging applications to (a) agricultural, forestry, and fishery materials used in the environment, and (b) food containers, packaging materials, sanitary products, garbage bags, etc., which are difficult to recover and reuse after use.
  • foam molded products made of biodegradable plastics are expected to be used in packaging cushioning materials, agricultural product boxes, fish boxes, automotive parts, building materials, civil engineering materials, etc.
  • poly(3-hydroxyalkanoate) (hereinafter sometimes referred to as "P3HA”) is attracting attention as a plastic derived from plant raw materials due to its excellent biodegradability and carbon neutrality.
  • One embodiment of the present invention has been developed in consideration of the above problems, and its purpose is to provide a new method for producing a foamed molded product that can provide a foamed molded product with excellent internal fusion properties.
  • the inventors conducted extensive research to solve the above problems, and as a result, completed the present invention.
  • the manufacturing method of a foamed molded body includes, in order, a filling step of filling a molding space formed by a fixed mold having a fixed-side steam valve and a fixed-side drain valve and a movable mold having a movable-side steam valve and a movable-side drain valve with aliphatic polyester-based resin foamed particles; a one-way heating step of supplying steam at a steam pressure Pf 1 into the molding space through the fixed-side steam valve or the movable-side steam valve with the fixed-side drain valve and the movable-side drain valve closed; a reverse one-way heating step of supplying steam at a steam pressure Pf 2 into the molding space through the steam valve that was not used in the one-way heating step among the fixed-side steam valve and the movable-side steam valve with the fixed-side drain valve and the movable-side drain valve closed; and a double-sided heating step of supplying steam at a steam pressure Pf 3 into the
  • One embodiment of the present invention has the effect of providing a new method for producing a foamed molded article that can provide a foamed molded article with excellent internal fusion properties.
  • FIG. 1 is a schematic diagram showing a molding apparatus for producing a foamed molded article according to one embodiment of the present invention.
  • 1 is a schematic diagram of a foam molded article according to an embodiment of the present invention.
  • the "manufacturing method for a foamed molded article according to one embodiment of the present invention” may be referred to as “the present manufacturing method," and the “aliphatic polyester resin foamed particles” may be referred to as “foamed particles.”
  • the foamed molded article obtained by the present manufacturing method may also be referred to as an "aliphatic polyester resin foamed molded article.”
  • a repeating unit derived from an X monomer may be referred to as an "X unit.”
  • a repeating unit may also be referred to as a constituent unit.
  • the present inventors have conducted intensive research to solve the above problems. That is, the present inventors have conducted intensive research to develop a new method for producing a foamed molded body that can provide a foamed molded body with excellent internal fusion.
  • a process for producing a foamed molded body using a molding machine equipped with a fixed mold and a movable mold a process for supplying steam to only one of the fixed mold and the movable mold through a steam valve equipped in the mold is called a "one-sided heating process”
  • a process for supplying steam to only a mold other than the mold to which steam was supplied in the one-sided heating process through a steam valve equipped in the mold is called a "reverse one-sided heating process”
  • a process for supplying steam to both the fixed mold and the movable mold through the steam valves equipped in each mold is called a "double-sided heating process”.
  • the inventors have surprisingly found a new finding that when such a method is adopted, a foamed molded article with excellent internal fusion can be obtained.
  • This finding is a finding that could not be predicted from the conventional technology in which one-way heating/reverse one-way heating is generally performed with the drain valve of the mold opposite the mold supplying steam open.
  • a method for producing a foamed molded body includes, in order, a filling step of filling a molding space formed by a fixed mold having a fixed-side steam valve and a fixed-side drain valve and a movable mold having a movable-side steam valve and a movable-side drain valve with aliphatic polyester-based resin foamed particles; a one-way heating step of supplying steam at a steam pressure Pf 1 into the molding space through the fixed-side steam valve or the movable-side steam valve while the fixed-side drain valve and the movable-side drain valve are closed; a reverse one-way heating step of supplying steam at a steam pressure Pf 2 into the molding space through the steam valve that was not used in the one-way heating step among the fixed-side steam valve and the movable-side steam valve while the fixed-side drain valve and the movable-side drain valve are closed; and a double-sided heating step of supplying steam at
  • this manufacturing method has the above-mentioned configuration, it has the advantage of being able to provide a foamed molded product with excellent internal fusion properties.
  • this manufacturing method uses aliphatic polyester resin, which is a biodegradable resin, the resulting foamed molded product can suppress soil pollution due to disposal. This can contribute to the achievement of the Sustainable Development Goals (SDGs), such as Goal 12 "Ensure sustainable consumption and production patterns.”
  • SDGs Sustainable Development Goals
  • P3HA-based resin foam particles containing P3HA-based resin, which is marine degradable in addition to soil degradable among aliphatic polyester-based resins the resulting foamed molded product can suppress marine pollution in addition to suppressing soil pollution due to disposal. This can contribute to the achievement of Goal 14 "Conserve and sustainably use the oceans and marine resources for sustainable development” in addition to Goal 12 "Ensure sustainable consumption and production patterns.”
  • the expanded aliphatic polyester resin particles used in the present production method are obtained by expanding the aliphatic polyester resin particles obtained from the aliphatic polyester resin. Further, the expanded molded article is obtained by molding the expanded beads (e.g., in-mold expansion molding). It can also be said that the expanded aliphatic polyester resin particles are obtained by expanding the aliphatic polyester resin particles containing the aliphatic polyester resin.
  • the aliphatic polyester resin particles can be obtained, for example, by the following method: (1) Mixing an aliphatic polyester resin, a bubble adjuster such as talc, and other additives such as an amide to obtain a mixture; (2) The resulting mixture is melt-kneaded while being heated, for example, using an extruder, to obtain a molten resin composition; (3) The resulting resin composition is cooled with water and then cut to obtain aliphatic polyester resin particles.
  • the expanded aliphatic polyester resin particles can be obtained by expanding aliphatic polyester resin particles by, for example, the following method: (1) A dispersion medium such as water, aliphatic polyester resin particles, and, if necessary, a crosslinking agent such as 1,1-di(t-butylperoxy)cyclohexane (TBCH), a dispersing agent such as calcium phosphate tribasic, and a dispersion aid such as sodium alkanesulfonate are mixed in a container; (2) While stirring the obtained mixture with a stirrer or the like, a blowing agent such as carbon dioxide, ethanol, mixed butane (e.g., a mixture of normal butane and isobutane) is added to the container to prepare a dispersion; (3) The temperature of the dispersion is raised to a foaming temperature, and if necessary, pressure is applied to raise the pressure inside the vessel to a foaming pressure; (4) maintaining the temperature and pressure in the vessel at near the foaming temperature and foaming
  • the dispersion liquid (mixture) in the container is continuously stirred, for example, with a stirrer, from the step (2) to the step (5) where the dispersion liquid is completely discharged.
  • the steps (1) and (2) may be collectively referred to as a "dispersion step.”
  • the foamed particles thus obtained may be washed with an aqueous solution of sodium hexametaphosphate, etc., if necessary.
  • the aliphatic polyester resin particles described above may be impregnated with a foaming gas (foaming agent) in a pressure-resistant container, and then the aliphatic polyester resin particles may be placed in a pre-expansion machine and pre-expanded with water vapor or the like to obtain expanded particles.
  • a foaming gas foaming agent
  • the shape of the foamed beads is not particularly limited, but may be, for example, spherical or approximately spherical.
  • the expanded aliphatic polyester resin particles are obtained by expanding aliphatic polyester resin particles containing an aliphatic polyester resin.
  • the expanded aliphatic polyester resin particles contain an aliphatic polyester resin as a resin component.
  • the "resin component" in the expanded beads means the resin component that substantially constitutes the expanded beads, excluding the blowing agent, the cell regulator, and other additives, among the components contained in the expanded beads.
  • the resin component of the aliphatic polyester resin foamed particles contains, for example, more than 50% by weight of aliphatic polyester resin out of 100% by weight of the resin component, more preferably 60% by weight or more, more preferably 70% by weight or more, more preferably 80% by weight or more, even more preferably 90% by weight or more, even more preferably 95% by weight or more, and particularly preferably 100% by weight.
  • the resin component of the aliphatic polyester resin foamed particles is composed only of aliphatic polyester resin. The higher the content of aliphatic polyester resin in the resin component of the aliphatic polyester resin foamed particles, the more advantageous it is that soil pollution due to disposal of the resulting foamed molded article can be suppressed.
  • Aliphatic polyester resins include one or more selected from the group consisting of poly(3-hydroxyalkanoate) resins, polylactic acid, polyethylene succinate, polybutylene succinate, polyethylene adipate, polybutylene adipate, polyhexamethylene adipate polyethylene succinate adipate, polybutylene succinate adipate, polyethylene adipate terephthalate, polybutylene adipate terephthalate, polyethylene succinate terephthalate, polybutylene succinate terephthalate, polybutylene succinate terephthalate, polyethylene oxalate, polybutylene oxalate, polyneopentyl oxalate, polyethylene sebacate, polybutylene sebacate, polyhexamethylene sebacate, and polycaprolactone.
  • poly(3-hydroxyalkanoate) resins polylactic acid, polyethylene succinate, polybutylene succinate, polyethylene adipate, polybutylene
  • poly(3-hydroxyalkanoate) resins which are not only soil degradable but also marine degradable, are preferred.
  • the resin component of the aliphatic polyester resin foam particles preferably contains poly(3-hydroxyalkanoate) resin.
  • the resin component of the aliphatic polyester resin foamed particles preferably contains more than 50% by weight of poly(3-hydroxyalkanoate) resin in 100% by weight of the resin component.
  • foamed particles containing more than 50% by weight of "X" resin in 100% by weight of the resin component may be referred to as X resin foamed particles.
  • foamed particles containing more than 50% by weight of poly(3-hydroxyalkanoate) resin in 100% by weight of the resin component are also referred to as poly(3-hydroxyalkanoate) resin foamed particles.
  • the aliphatic polyester resin foamed particles are preferably poly(3-hydroxyalkanoate) resin foamed particles. This configuration has the advantage of being able to suppress (reduce) soil pollution and marine pollution caused by the disposal of foamed molded bodies.
  • the resin component of the aliphatic polyester resin foamed particles preferably contains 60% by weight or more of poly(3-hydroxyalkanoate) resin, more preferably 70% by weight or more, more preferably 80% by weight or more, even more preferably 90% by weight or more, even more preferably 95% by weight or more, and particularly preferably 100% by weight.
  • the resin component of the aliphatic polyester resin foamed particles is composed only of poly(3-hydroxyalkanoate) resin. The higher the content of poly(3-hydroxyalkanoate) resin in the resin component of the aliphatic polyester resin foamed particles, the more advantageous it is that soil and/or marine pollution due to disposal of the resulting foamed molded article can be suppressed.
  • poly(3-hydroxyalkanoate) resin Poly(3-hydroxyalkanoate) resin
  • the "poly(3-hydroxyalkanoate)-based resin” may be referred to as “poly(3-hydroxyalkanoate)" or "P3HA.” P3HA will be described below.
  • P3HA is a polymer having a 3-hydroxyalkanoate unit as an essential constituent unit (monomer unit).
  • "3-hydroxyalkanoate” may also be referred to as "3HA.”
  • P3HA is preferably a polymer containing a repeating unit represented by the following general formula (1): [-CHR-CH 2 -CO-O-]...(1).
  • R represents an alkyl group represented by C n H 2n+1 , where n represents an integer of 1 to 15.
  • R examples include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, and hexyl.
  • n is preferably 1 to 10, and more preferably 1 to 8.
  • P3HA produced by microorganisms is particularly preferred.
  • P3HA produced by microorganisms is poly[(R)-3HA] in which all 3HA units are (R)-3HA.
  • P3HA preferably contains 3HA units (particularly the repeating units of general formula (1)) in an amount of 50 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more, out of a total of 100 mol% of repeating units in P3HA.
  • the repeating units may be 3HA units only, or may contain, in addition to 3HA units, repeating units derived from monomers other than 3HA (e.g., 4-hydroxyalkanoate units, etc.).
  • 3HA units include 3-hydroxybutyrate units, 3-hydroxyvalerate units, and 3-hydroxyhexanoate units.
  • 3-Hydroxybutyrate has a melting point and tensile strength close to those of propylene. Therefore, it is preferable that the P3HA according to one embodiment of the present invention contains 3-hydroxybutyrate units.
  • "3-hydroxybutyrate” may also be referred to as "3HB.”
  • P3HA preferably contains 80 mol% or more, and more preferably 85 mol% or more, of 100 mol% of all repeating units of P3HA as 3HB units (monomer units).
  • P3HA is preferably a polymer that contains 3HB units and in which all 3HB is (R)-3HB (a polymer produced by a microorganism).
  • the monomer from which the repeating units other than the repeating unit with the highest content are derived is referred to as a comonomer.
  • a "repeating unit derived from a comonomer” may also be referred to as a “comonomer unit.”
  • the comonomer is not particularly limited, but 3-hydroxyhexanoate (hereinafter sometimes referred to as 3HH) or 4-hydroxybutyrate (hereinafter sometimes referred to as 4HB) is preferred.
  • P3HA examples include poly(3-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxypropionate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (hereinafter, sometimes referred to as "P3HB3HV”), poly(3-hydroxybutyrate-co-3-hydroxyvalerate-3-hydroxyhexanoate), and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (hereinafter, sometimes referred to as "P3HB3HH").
  • poly(3-hydroxybutyrate-co-3-hydroxyheptanoate), poly(3-hydroxybutyrate-co-3-hydroxyoctanoate), poly(3-hydroxybutyrate-co-3-hydroxynonanoate), poly(3-hydroxybutyrate-co-3-hydroxydecanoate), poly(3-hydroxybutyrate-co-3-hydroxyundecanoate), poly(3-hydroxybutyrate-co-4-hydroxybutyrate) hereinafter, sometimes referred to as "P3HB4HB").
  • poly(3-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxyhexanoate), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) or poly(3-hydroxybutyrate-co-4-hydroxybutyrate) are preferred.
  • the above-mentioned P3HA may be used alone or in combination of two or more types.
  • P3HA has a 3HB unit as an essential repeating unit (structural unit) and also has a comonomer unit.
  • P3HA is a copolymer having a 3HB unit and a comonomer unit. The case where P3HA has a 3HB unit and a comonomer unit will be described.
  • the ratio of the 3HB unit and the comonomer unit (3HB unit/comonomer unit) in 100 mol% of all repeating units in P3HA is preferably 99/1 (mol%/mol%) to 80/20 (mol%/mol%), more preferably 97/3 (mol%/mol%) to 80/20 (mol%/mol%), and even more preferably 95/5 (mol%/mol%) to 85/15 (mol%/mol%). If the ratio of the comonomer unit to 100 mol% of all repeating units of P3HA is 1 mol% or more, the melt-kneadable temperature range of P3HA and the thermal decomposition temperature range are sufficiently separated, so that the obtained expanded beads have excellent processability.
  • the ratio of the comonomer units to the total repeating units of P3HA (100 mol%) is 20 mol% or less, the P3HA composition crystallizes quickly during melt kneading, and productivity is high.
  • P3HA having such a ratio of each monomer unit can be produced according to a method known to those skilled in the art, for example, the method described in International Publication WO2009/145164.
  • the ratio of each monomer unit in P3HA can be determined by a method known to those skilled in the art, for example, the method described in International Publication WO 2013/147139.
  • the method for producing P3HA is not particularly limited, and may be a production method using chemical synthesis or a production method using microorganisms. Of these, a production method using microorganisms is preferred. Known methods can be applied to the production method for P3HA using microorganisms.
  • bacteria that produce copolymers of 3HB and other hydroxyalkanoates include Aeromonas caviae, which produces P3HB3HV and P3HB3HH, and Alcaligenes eutrophus, which produces P3HB4HB.
  • Aeromonas caviae which produces P3HB3HV and P3HB3HH
  • Alcaligenes eutrophus which produces P3HB4HB.
  • P3HB3HH Alcaligenes eutrophus AC32 (FERM BP-6038) (T. Fukui, Y. Doi, J. Bateriol., 179, p4821-4830 (1997)) is more preferred, as it has been improved in productivity by introducing genes for the P3HA synthase group.
  • microbial cells obtained by culturing microorganisms such as Alcaligenes eutrophus AC32 strain under appropriate conditions and accumulating P3HB3HH within the cells are preferably used.
  • genetically modified microorganisms into which various P3HA synthesis-related genes have been introduced may also be used as copolymer-producing bacteria, depending on the P3HA to be produced.
  • various culture conditions for the microorganisms (bacteria), including the type of substrate, may be optimized depending on the P3HA to be produced.
  • the method for culturing a microorganism that produces P3HA is not particularly limited, and for example, the method described in International Publication No. WO2019/142717 can be used.
  • the resin component of the aliphatic polyester resin foam particles may contain resins other than aliphatic polyester resins.
  • resins other than aliphatic polyester resins include polypropylene, polyethylene, polystyrene, modified starch, and modified cellulose.
  • the expanded particles may contain additives, crystal nucleating agents, bubble regulators, crosslinking agents, crosslinking aids, foaming agents, dispersants, dispersion aids, etc. that can be used during the production of the aliphatic polyester resin particles and/or expanded particles.
  • the expanded particles may contain other components that can be used in addition to these to the extent that they do not impair the effects of one embodiment of the present invention.
  • Examples of other components include colorants such as pigments and dyes, odor absorbers such as activated carbon and zeolite, fragrances such as vanillin and dextrin, plasticizers, antioxidants, antioxidants, weather resistance improvers, ultraviolet absorbers, crystal nucleating agents, lubricants, release agents, water repellents, antibacterial agents, sliding improvers, etc. Only one type of other component may be contained, or two or more types may be contained. The content of these other components can be appropriately set by a person skilled in the art depending on the purpose of use.
  • crosslinking agent for example, an organic peroxide is preferred.
  • a crosslinking agent in the manufacturing process of the aliphatic polyester resin particles and/or the expanded beads, crosslinked expanded beads can be obtained.
  • the aliphatic polyester resin expanded beads are crosslinked by an organic peroxide.
  • the organic peroxide used as the crosslinking agent depends on the type of aliphatic polyester resin used, but is preferably an organic peroxide with a one-hour half-life temperature of 90°C to 160°C, more preferably an organic peroxide with a one-hour half-life temperature of 110°C to 160°C, even more preferably an organic peroxide with a one-hour half-life temperature of 110°C to 125°C, and particularly preferably an organic peroxide with a one-hour half-life temperature of 114°C to 124°C.
  • organic peroxides include benzoyl peroxide (BPO, one-hour half-life temperature: 92°C), t-butylperoxy-2-ethylhexyl carbonate (TBEC, one-hour half-life temperature: 121°C), and 1,1-di(t-butylperoxy)cyclohexane (TBCH, one-hour half-life temperature: 116°C).
  • BPO benzoyl peroxide
  • TBEC t-butylperoxy-2-ethylhexyl carbonate
  • TBCH 1,1-di(t-butylperoxy)cyclohexane
  • a crosslinking agent When a crosslinking agent is used, its amount is not particularly limited.
  • the amount of crosslinking agent used may be set appropriately based on the desired degree of crosslinking and closed cell ratio in the resulting expanded beads.
  • the amount of crosslinking agent used is positively correlated with the gel fraction of the expanded beads, and greatly affects the value of the gel fraction of the expanded beads. Therefore, it is also desirable to strictly set the amount of crosslinking agent used taking into account the gel fraction of the resulting expanded beads.
  • the gel fraction of the aliphatic polyester resin expanded beads is preferably 30% to 85% by weight, more preferably 50% to 80% by weight, and even more preferably 60% to 75% by weight, based on 100% by weight of the expanded beads.
  • the gel fraction of the expanded beads is (a) 30% by weight or more based on 100% by weight of the expanded beads, there is an advantage that the molding temperature range of the expanded beads that can provide good quality expanded molded articles is broadened when molding an expanded molded article, improving productivity, and when (b) 85% by weight or less, there is an advantage that expanded molded articles with excellent internal fusion properties can be easily obtained at low molding pressure.
  • FIG. 1 is a plan view showing an example of a molding device used in this manufacturing method.
  • the molding device 10 shown in FIG. 1 is merely an example, and the molding device used in this manufacturing method is not limited to that shown in FIG. 1.
  • the molding device may be equipped with conventionally known parts and equipment such as a drain restrictor (drain bypass). Specifically, this manufacturing method is carried out through the steps shown below.
  • Fixed side steam valve 12A and movable side steam valve 12B, and fixed side drain valve 13A and movable side drain valve 13B are connected to the fixed mold 11A and movable mold 11B, respectively.
  • the fixed mold 11A and the movable mold 11B are provided with a conventionally known core vent or cut hole for passing steam into the molding space 21, but these are omitted in Figure 1.
  • the movable steam valve 12B is opened, and the fixed steam valve 12A is closed (the fixed drain valve 13A and the movable drain valve 13B are already closed).
  • the air and the foamed particles present among the foamed aliphatic polyester resin particles filled in the molding space 21 are heated (reverse one-way heating step).
  • the steam valves through which the steam passes may be different from each other, and the steam may be supplied through a steam valve reverse to the steam valve described above into the molding space 21.
  • the fixed side steam valve 12A, the fixed side drain valve 13A and the movable side drain valve 13B may be closed, and the steam at a steam pressure Pf 1 may be supplied through the movable side steam valve 12B into the molding space 21, and in the reverse one-way heating step (iv), the fixed side steam valve 12A may be opened, the movable side steam valve 12B may be closed, and the steam at a steam pressure Pf 2 may be supplied through the fixed side steam valve 12A into the molding space 21.
  • the filling step of this manufacturing method is to fill a molding space consisting of a fixed mold to which a fixed steam valve and a fixed drain valve are connected, and a movable mold to which a movable steam valve and a movable drain valve are connected, with fat.
  • the step of filling the molding space with expanded aliphatic polyester resin particles is, for example, carried out by using a filling machine connected to the fixed mold. This is also fine.
  • the fixed mold and the movable mold are closed to provide a molding space, and then the aliphatic polyester resin foam particles are filled.
  • a gap (cracking) large enough to prevent the foam particles from leaking when the mold is closed may be left, and the mold may be completely closed after the foam particles are filled.
  • the foam particles can be filled while discharging the air used during filling from the gap between the fixed mold and the movable mold, which tends to improve the filling property.
  • the gap size (cracking amount) in this case is preferably 1% to 40% of the foam molded body size in the mold opening (mold closing) direction of the foam molded body to be foam-molded in the mold, and more preferably 2% to 35%.
  • the internal pressure of the foam particles may be increased to above atmospheric pressure by a conventionally known method beforehand as necessary, or the foam particles may be used as they are at atmospheric pressure.
  • the foam particles may be filled, for example, by using a filling machine.
  • heating process> In the one-side heating step of the present manufacturing method, with both the fixed-side drain valve and the movable-side drain valve closed, a water vapor pressure Pf is applied through either the fixed-side steam valve or the movable-side steam valve. This is a step of supplying water vapor from step 1 into the molding space. This makes it possible to provide a foamed molded article having excellent internal fusion properties.
  • the value of the water vapor pressure Pf1 is not particularly limited as long as it is greater than 0.
  • the value of the water vapor pressure Pf1 is preferably 0 MPa (G) ⁇ Pf1 ⁇ 0.07 MPa (G), more preferably 0 MPa (G) ⁇ Pf1 ⁇ 0.06 MPa (G), more preferably 0 MPa (G) ⁇ Pf1 ⁇ 0.05 MPa (G), even more preferably 0 MPa (G) ⁇ Pf1 ⁇ 0.04 MPa (G), even more preferably 0.01 MPa (G) ⁇ Pf1 ⁇ 0.03 MPa (G), and particularly preferably 0.02 MPa (G) ⁇ Pf1 ⁇ 0.03 MPa (G).
  • the duration of the heating step is not particularly limited, but is preferably 3 to 20 seconds, more preferably 4 to 15 seconds, even more preferably 5 to 13 seconds, and particularly preferably 5 to 10 seconds.
  • the duration of the heating step is within the above-mentioned range, it has the advantage that the foamed particles can be sufficiently heated. As a result, a foamed molded product with excellent fusion properties on the surface and inside can be obtained.
  • the value of the water vapor pressure Pf2 is not particularly limited as long as it is greater than 0.
  • the value of the water vapor pressure Pf2 is preferably 0 MPa (G) ⁇ Pf2 ⁇ 0.07 MPa (G), more preferably 0 MPa (G) ⁇ Pf2 ⁇ 0.06 MPa (G), more preferably 0 MPa (G) ⁇ Pf2 ⁇ 0.05 MPa (G), even more preferably 0 MPa (G) ⁇ Pf2 ⁇ 0.04 MPa (G), even more preferably 0.01 MPa (G) ⁇ Pf2 ⁇ 0.03 MPa (G), and particularly preferably 0.02 MPa (G) ⁇ Pf2 ⁇ 0.03 MPa (G).
  • the foamed particles on the surface do not fuse at the early stage of molding, so that the foamed particles inside can be heated. As a result, a foamed molded article having better internal fusion properties can be obtained.
  • the water vapor pressure Pf2 is 0.04 MPa (G) or less, it has an advantage that even the internal foamed particles can be heated. As a result, a foamed molded article having better internal fusion properties can be obtained.
  • the water vapor pressure Pf2 is 0.02 MPa (G) or more, it has an advantage that even the internal foamed particles can be heated. As a result, a foamed molded article having better internal fusion properties can be obtained.
  • the water vapor pressures Pf1 and Pf2 may be the same or different.
  • the duration of the reverse one-way heating step is not particularly limited, but is preferably 3 to 20 seconds, more preferably 4 to 15 seconds, even more preferably 5 to 13 seconds, and particularly preferably 5 to 10 seconds.
  • the duration of the one-way heating step is within the above-mentioned range, it has the advantage that the foamed particles can be sufficiently heated. As a result, a foamed molded product with excellent surface and internal fusion properties can be obtained.
  • the duration of the reverse one-way heating step is preferably the same as or shorter than the duration of the one-way heating step.
  • This configuration has the advantage that the foamed particles inside can be sufficiently heated. As a result, a foamed molded product with superior internal fusion properties can be obtained.
  • Double-sided heating process is a process in which steam at a steam pressure Pf 3 is supplied into the molding space through both the fixed-side steam valve and the movable-side steam valve with both the fixed-side drain valve and the movable-side drain valve closed.
  • the value of the water vapor pressure Pf 3 is not particularly limited as long as it is greater than 0.
  • the value of the water vapor pressure Pf 3 is preferably 0.05 MPa (G) ⁇ Pf 3 ⁇ 0.30 MPa (G), more preferably 0.08 MPa (G) ⁇ Pf 3 ⁇ 0.25 MPa (G), even more preferably 0.10 MPa (G) ⁇ Pf 3 ⁇ 0.23 MPa (G), and particularly preferably 0.13 MPa (G) ⁇ Pf 3 ⁇ 0.20 MPa (G).
  • the water vapor pressure Pf 3 is 0.05 MPa (G) or more, it has the advantage that a molded body with excellent fusion properties can be obtained.
  • the water vapor pressure Pf 3 When the water vapor pressure Pf 3 is 0.30 MPa (G) or less, it has the advantage that the surface properties of the obtained molded body are not deteriorated.
  • the water vapor pressure Pf 3 may be the same as or different from Pf 1 and / or Pf 2 .
  • the quotient obtained by dividing the value of the water vapor pressure Pf1 by the value of the water vapor pressure Pf3 is preferably greater than 0 and less than 0.50, more preferably greater than 0 and equal to or less than 0.40, even more preferably 0.05 to 0.30, and particularly preferably 0.10 to 0.25.
  • This configuration has the advantage that even the internal foamed particles can be heated. As a result, a foamed molded product with even better internal fusion properties can be obtained.
  • the quotient obtained by dividing the value of the water vapor pressure Pf2 by the value of the water vapor pressure Pf3 is preferably greater than 0 and less than 0.50, more preferably greater than 0 and equal to or less than 0.40, even more preferably 0.05 to 0.30, and particularly preferably 0.10 to 0.25.
  • This configuration has the advantage that even the internal foamed particles can be heated. As a result, a foamed molded product with even better internal fusion properties can be obtained.
  • the water vapor pressure Pf1 and the water vapor pressure Pf2 were close to the water vapor pressure Pf3 , or the quotient obtained by dividing the values of the water vapor pressures Pf1 and Pf2 by the value of the water vapor pressure Pf3 was at least 0.5 or more.
  • the present inventor independently obtained a new finding in the course of intensive research that, surprisingly, a foamed molded article having superior internal fusion properties can be provided by performing one-way heating and reverse one-way heating with both drain valves closed, and by setting the values of the water vapor pressures Pf1 and Pf2 to values less than half the value of the water vapor pressure Pf3 .
  • the value of the water vapor pressure Pf1 or the water vapor pressure Pf2 can be set low, which has the advantage of keeping production costs low.
  • the duration of the double-sided heating step is not particularly limited, but is preferably 1 to 60 seconds, more preferably 2 to 45 seconds, and even more preferably 3 to 30 seconds. When the duration of the double-sided heating step is 1 second or longer, it has the advantage that a molded product with superior fusion properties is obtained. When the duration of the double-sided heating step is 60 seconds or less, it has the advantage that a molded product with superior fusion properties and surface properties is obtained.
  • the manufacturing method may include a one-sided heating step, an opposite one-sided heating step, a preheating step performed before or after the double-sided heating step, a cooling/removal step, etc.
  • the manufacturing method may include a conventionally known step such as a heat retention step (steaming step) in which the fixed side steam valve and the movable side steam valve are closed after the double-sided heating step.
  • the water vapor pressure and duration of the preheating process, the cooling and removal process, and other processes carried out before and after the double-sided heating process can be determined as appropriate.
  • the water vapor pressure of the preheating process may be 0.01 to 0.04 MPa (G), and the heating time may be 1 to 30 seconds.
  • the temperature of the water sprayed in the cooling and removal process may be 1 to 60°C, and the cooling time may be 1 to 500 seconds.
  • the present manufacturing method it is possible to obtain a foamed molded article (hereinafter, referred to as the present foamed molded article) made from an aliphatic polyester resin as a raw material. Since the present foamed molded article is manufactured according to the present manufacturing method, it has excellent internal fusion properties.
  • the internal fusion property of the foamed molded product can be evaluated by the method described in the Examples below.
  • the internal fusion property of the foamed molded product is preferably greater than 70%, more preferably 75% or more, more preferably 80% or more, even more preferably 85% or more, and particularly preferably 90% or more. There is no particular upper limit to the internal fusion property of the foamed molded product, and it is most preferably 100%.
  • the present foam molded body preferably includes a molded part having a thickness of 40 mm to 500 mm. More preferably, the present foam molded body includes a molded part having a thickness of 50 mm to 500 mm.
  • the present foam molded body may be a foam molded body having an item storage space and a partition part that divides the item storage space.
  • the present foam molded body may be a molded body having a part with a T-shaped cross section.
  • An example of such a foam molded body is a foam molded body 1 having a shape as shown in FIG. 2.
  • FIG. 2 also shows the shape of the foam molded body produced in the examples of the present application.
  • the foam molded body 1 shown in FIG. 2 has a partition part 4, that is, has a part with a T-shaped cross section.
  • a foam molded product including a molded portion having a thickness of 40 mm to 500 mm (sometimes referred to as a "thick portion"), such as the foam molded product 1 shown in Figure 2
  • a sufficient level of internal fusion e.g., a value greater than 70%
  • a foam molded product having excellent internal fusion in the thick portion (bottom portion 3) can be obtained, and the effects of the present manufacturing method can be fully obtained by forming the foam molded product into the shape described above.
  • the foamed molded product may have, for example, one or more handles, or may have additional partitions, ribs, grooves, or irregularities on the inner wall surface.
  • the thickness of the vertical wall, bottom, partition, etc. may be partially changed, and cutouts may be provided on the side or bottom surface, or other known shapes may be used.
  • the foamed molded article can be suitably used for, for example, packaging cushioning materials (e.g., packaging cushioning materials for home appliances such as refrigerators, freezers, air conditioner bodies and their outdoor units, washing machines, air purifiers, humidifiers, rice cookers, microwave ovens, ovens, toasters, electric fans, and battery units; packaging cushioning materials for automobiles such as transmissions, roofs, hoods, doors, batteries, and engines), logistics materials (e.g., agricultural product boxes, fish boxes, etc.), insulation materials, civil engineering and construction components, and automobile components (e.g., tool boxes, bulkheads, seat core materials, bumper core materials, tibia pads, door trims, etc.).
  • packaging cushioning materials e.g., packaging cushioning materials for home appliances such as refrigerators, freezers, air conditioner bodies and their outdoor units, washing machines, air purifiers, humidifiers, rice cookers, microwave ovens, ovens, toasters, electric fans, and battery units
  • packaging cushioning materials for automobiles such as transmissions,
  • One embodiment of the present invention may have the following configuration.
  • a method for producing a foamed molded body comprising the steps of: filling a molding space formed by a fixed mold having a fixed-side steam valve and a fixed-side drain valve, and a movable mold having a movable-side steam valve and a movable-side drain valve, with aliphatic polyester-based resin foamed particles; a one-way heating step of supplying steam at a steam pressure Pf 1 into the molding space through the fixed-side steam valve or the movable-side steam valve while the fixed-side drain valve and the movable-side drain valve are closed; a reverse one-way heating step of supplying steam at a steam pressure Pf 2 into the molding space through one of the fixed-side steam valve and the movable-side steam valve that was not used in the one-way heating step while the fixed-side drain valve and the movable-side drain valve are closed; and a double-sided heating step of supplying steam at a steam pressure Pf 3 into the molding space through the fixed-side steam
  • P3HA (Aliphatic polyester resin) P3HA:
  • the shape of the foam molded article 1 obtained in this example is shown in Figure 2.
  • the foam molded article 1 has a box-like shape with a partition (external dimensions: length 730 mm x width 800 mm x height 110 mm, thickness of the vertical wall 2 and the partition 4 is 20 mm, thickness of the bottom 3 is 50 mm).
  • the fusion property was evaluated according to the following (1) to (4): (1) an incision was made with a cutter in the thickness direction of the bottom 3 (direction perpendicular to the outer bottom surface) on the outer bottom surface of the foam molded body 1, with a length (depth) of 1/20 to 1/10 of the thickness of the bottom 3 (50 mm); (2) the foam molded body was then broken by hand along the incision; (3) the portion excluding the incision (observation surface) of the obtained fracture surface was visually observed, and the portion from the movable mold side surface (the inner surface of the bottom 3, the surface that was in contact with the movable mold, also referred to as the "inner bottom surface") to 10 mm in the thickness direction of the bottom 3 was observed as surface fusion, and the portion from the movable mold side surface to 10 mm in the thickness direction of the bottom 3 was observed as internal fusion.
  • Fusion rate (%) (number of expanded beads broken at other than the interface between the expanded beads within the observation surface/total number of expanded beads present within the observation surface) ⁇ 100.
  • P3HA-based resin expanded particles 100 parts by weight of P3HA resin, 1.0 part by weight of pentaerythritol, 0.50 parts by weight of behenic acid amide, 0.50 parts by weight of erucic acid amide, and 0.10 parts by weight of talc were weighed and dry-blended to prepare a P3HA-based resin composition.
  • the prepared P3HA-based resin composition was fed to a twin-screw extruder (TEM-26SX manufactured by Toshiba Machine Co., Ltd.), and the P3HA-based resin composition was melt-kneaded at a cylinder setting temperature of 130°C to 160°C (melt-kneading process).
  • the melt-kneaded P3HA-based resin composition at 179°C was discharged from the nozzle of the die attached to the tip of the extruder.
  • the discharged P3HA-based resin composition was cooled with water at 50° C. and then cut to obtain cylindrical P3HA-based resin particles each weighing 3.5 mg and having a length/diameter ratio of 2.0 (resin particle molding step).
  • the melting point of the P3HA-based resin particles was 145.0° C.
  • the resulting expanded beads were washed with an aqueous solution of sodium hexametaphosphate and water to remove the dispersant and other substances adhering to the surface of the expanded beads, and then dried at 75° C.
  • the resulting expanded beads had a length/diameter ratio of 1.0 and a spherical or nearly spherical shape.
  • the resulting expanded beads had a gel fraction of 67% by weight and an apparent density of 0.076 g/cm 3 (expansion ratio: 16 times).
  • a mold (fixed mold and movable mold) for obtaining a box-shaped foam molded body 1 having a partition (outside dimensions: length 730 mm ⁇ width 800 mm ⁇ height 110 mm, thickness of vertical wall 2 and partition 4 20 mm, thickness of bottom 3 50 mm) was mounted on a molding machine (DABO DPM-1300).
  • DABO DPM-1300 a molding machine
  • a foam molded body in-mold foam molded body was obtained as follows.
  • the mold was mounted on the molding machine so that the outer bottom surface of the foam molded body 1 was molded by the fixed mold.
  • the mold opening and closing directions of the fixed mold and the movable mold were horizontal to the ground, and the in-mold foam molding was performed so that the height direction of the box-shaped foam molded body 1 was horizontal.
  • the mold consisting of a fixed mold and a movable mold, was opened and then closed until the mold gap in the mold opening and closing direction was 7 mm.
  • a one-way heating step was carried out for 5 seconds using steam from the fixed steam valve at a steam pressure Pf 1 (gauge pressure) shown in Table 1.
  • Pf 1 gauge pressure
  • the open/closed states of the fixed drain valve and the movable drain valve at this time are also shown in Table 1.
  • a double-sided heating step was performed for 15 seconds using steam at a steam pressure Pf of 3 shown in Table 1 through the fixed-side steam valve and the movable-side steam valve.
  • the open/closed states of the fixed-side drain valve and the movable-side drain valve at this time are also shown in Table 1.
  • One embodiment of the present invention can be used effectively for a variety of applications, including food containers, packaging materials, sanitary products, automotive parts (particularly toolboxes, etc.), packaging cushioning materials (particularly for home appliances), agricultural boxes, fish boxes, logistics materials, insulation materials, and civil engineering and construction materials.

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6321133A (ja) * 1986-07-14 1988-01-28 Kanegafuchi Chem Ind Co Ltd ポリオレフイン系樹脂発泡成形における蒸気節減法
JP2012214636A (ja) * 2011-03-31 2012-11-08 Sekisui Plastics Co Ltd ポリエステル系樹脂発泡成形体の製造方法およびポリエステル系樹脂発泡成形体
JP2013176886A (ja) * 2012-02-28 2013-09-09 Sekisui Kaseihin Sakura:Kk 型内発泡成形方法
JP2022102730A (ja) * 2020-12-25 2022-07-07 株式会社カネカ ポリ（３－ヒドロキシアルカノエート）系発泡粒子およびポリ（３－ヒドロキシアルカノエート）系発泡成形体
JP2023143279A (ja) * 2022-03-25 2023-10-06 株式会社カネカ 発泡成形体の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6321133A (ja) * 1986-07-14 1988-01-28 Kanegafuchi Chem Ind Co Ltd ポリオレフイン系樹脂発泡成形における蒸気節減法
JP2012214636A (ja) * 2011-03-31 2012-11-08 Sekisui Plastics Co Ltd ポリエステル系樹脂発泡成形体の製造方法およびポリエステル系樹脂発泡成形体
JP2013176886A (ja) * 2012-02-28 2013-09-09 Sekisui Kaseihin Sakura:Kk 型内発泡成形方法
JP2022102730A (ja) * 2020-12-25 2022-07-07 株式会社カネカ ポリ（３－ヒドロキシアルカノエート）系発泡粒子およびポリ（３－ヒドロキシアルカノエート）系発泡成形体
JP2023143279A (ja) * 2022-03-25 2023-10-06 株式会社カネカ 発泡成形体の製造方法

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