WO2025094876A1 - 被覆再生材及びその製造方法 - Google Patents

被覆再生材及びその製造方法 Download PDF

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Publication number
WO2025094876A1
WO2025094876A1 PCT/JP2024/038296 JP2024038296W WO2025094876A1 WO 2025094876 A1 WO2025094876 A1 WO 2025094876A1 JP 2024038296 W JP2024038296 W JP 2024038296W WO 2025094876 A1 WO2025094876 A1 WO 2025094876A1
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Prior art keywords
recycled material
antioxidant
mass
elastomer
parts
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English (en)
French (fr)
Japanese (ja)
Inventor
竜也 金塚
雅季 伊藤
暁斗 渡邉
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Polyplastics Co Ltd
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Polyplastics Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/04—Disintegrating plastics, e.g. by milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/16—Auxiliary treatment of granules
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/02—Polythioethers; Polythioether-ethers

Definitions

  • the present invention relates to a coated recycled material and a method for producing the same.
  • Patent Document 1 In order to build a sustainable recycling-based society, technologies for recycling and utilizing plastic waste are being considered (for example, Patent Document 1).
  • Polyarylene sulfide resins are excellent in heat resistance, mechanical properties, chemical resistance, dimensional stability, and flame retardancy, and are therefore widely used in electrical and electronic equipment part materials, automotive part materials, chemical equipment part materials, etc. Therefore, recycling and utilizing materials containing polyarylene sulfide resins can help build a sustainable recycling-based society.
  • recycled products When recycling materials containing polyarylene sulfide resin, molded products and parts other than molded products discharged during molding (hereinafter collectively referred to as "recycled products") are crushed, and then, as necessary, molded using recycled materials that have been pelletized again.
  • the recycled materials may have decomposition of the matrix polymer, deterioration of additives, and fineness of fillers due to shearing when crushing the recycled products, heat history due to having been through one or more molding processes, and heat history during the re-pellet process. In that case, there may be changes in fluidity, crystallinity, polarity, etc. compared to virgin materials that have not been through a molding process.
  • the objective of this disclosure is to provide a recycled coating material that reduces mold contamination during molding and a method for producing the same.
  • the present invention has the following aspects.
  • ⁇ 1> A method for producing a coated recycled material (Z), Preparing a recycled material (z1) of an article comprising 100 parts by mass of a polyarylene sulfide resin (P) and 1 to 20 parts by mass of an elastomer (Q); and Coating at least a portion of a surface of the recycled material (z1) with an antioxidant (A); Including, In the coating, the coating amount of the antioxidant (A) is 0.025 to 0.25 parts by mass per part by mass of the elastomer (Q) contained in the recycled material (z1).
  • the coated recycled material (Z) has a coating amount of the antioxidant (A) of 0.025 to 0.25 parts by mass per part by mass of the elastomer (Q) contained in the recycled material (z1).
  • the present invention provides a recycled coating material that causes minimal mold contamination during molding, and a method for producing the same.
  • FIG. 1 is a schematic diagram of a molded body used when evaluating mold deposits, with the upper side being a top view and the lower side being a cross-sectional view.
  • the manufacturing method according to this embodiment is a manufacturing method of the coated recycled material (Z), (1) preparing a recycled material (z1) of an article comprising 100 parts by mass of a polyarylene sulfide resin (P) and 1 to 20 parts by mass of an elastomer (Q); and (2) coating at least a portion of a surface of the recycled material (z1) with an antioxidant (A); Including, In the coating, the coating amount of the antioxidant (A) is 0.025 to 0.25 parts by mass per part by mass of the elastomer (Q) contained in the recycled material (z1).
  • recycled materials often have changes in fluidity, crystallinity, polarity, etc. compared to virgin materials.
  • the changes in physical properties tend to be greater. For this reason, it is difficult to predict the effect of adding even well-known additives to recycled materials.
  • additives may cause mold deposits during molding, so additives to be added to recycled materials must be selected carefully.
  • the inventor therefore considered using recycled materials that already contained antioxidants as the recycled products in order to suppress mold deposits during recycling.
  • the expected effect of suppressing mold fouling was not obtained.
  • the inventor discovered that by coating the recycled material with a specified amount of antioxidant, mold fouling can be suppressed when the resulting coated recycled material is injection molded, and this led to the completion of the present disclosure.
  • recycling means crushing an article such as a molded body (a recycled product) and regenerating it as a raw material for use in manufacturing a molded body
  • recycled material means the recycled material.
  • the recycled material may be crushed material of the recycled product, or may be pellets obtained by melting and kneading the crushed material.
  • Pelletized recycled material is sometimes called "recycled pellets.”
  • Articles such as molded products that are recycled products are materials (raw materials) for regeneration, and are sometimes called “raw materials for recycling.”
  • raw materials that have not been used to produce molded bodies are called “virgin materials”
  • pellets of virgin materials are called “virgin pellets”
  • virgin materials of polyarylene sulfide resins are called “virgin polyarylene sulfide resins”.
  • Coated recycled material means recycled material with at least a portion of its surface coated with a certain compound (here, antioxidant (A)).
  • “coated” means that at least a portion of the surface of the recycled material is covered with antioxidant (A), and can include antioxidant (A) adhering and/or adhering to a portion of the surface of the recycled material, as well as antioxidant (A) spreading in a layer to cover a portion of the surface.
  • Adhering and/or adhering can include a state in which solid (e.g., powdered) antioxidant (A) is adhered by electrostatic force or the like, or a state in which part of the solid antioxidant (A) is melted and the remaining part remains solid, with the melted part adhering to the surface of the recycled material.
  • solid antioxidant (A) e.g., powdered
  • part of the solid antioxidant (A) is melted and the remaining part remains solid, with the melted part adhering to the surface of the recycled material.
  • a recycled material (z1) of an article containing 100 parts by mass of a polyarylene sulfide resin (P) and 1 to 20 parts by mass of an elastomer (Q) is prepared.
  • the "article” referred to here is an article to be recycled (recyclable article), and may be a molded article, or may be an article discharged after being retained in a cylinder for a long time during molding.
  • examples include defective products generated during the manufacturing process of molded articles, parts other than the product obtained during injection molding (e.g., runners, sprues, etc.), unused products, and chunks of polyethylene sulfide resin material used as a purge during molding and discharged, and it is preferable to include one or more selected from these.
  • the recycled molded article may be an injection molded article.
  • the polyarylene sulfide resin (P) may be a virgin polyarylene sulfide resin, or may be a recycled polyarylene sulfide resin that has been reused at least once.
  • the polyarylene sulfide resin (P) preferably contains a virgin polyarylene sulfide resin. By using an article containing a virgin polyarylene sulfide resin as a raw material for recycling, it is possible to reduce mold contamination during molding.
  • the polyarylene sulfide resin (P) preferably contains a recycled polyarylene sulfide resin. By using an article containing a recycled polyarylene sulfide resin as a raw material for recycling, it is easier to form a sustainable recycling-based society.
  • the polyarylene sulfide resin is a resin having a repeating unit represented by the following general formula (I). -(Ar-S)-...(I) (wherein Ar represents an arylene group).
  • the arylene group is not particularly limited, but examples thereof include p-phenylene group, m-phenylene group, o-phenylene group, substituted phenylene group, p,p'-diphenylenesulfone group, p,p'-biphenylene group, p,p'-diphenylene ether group, p,p'-diphenylenecarbonyl group, and naphthalene group.
  • Polyarylene sulfide resins can be homopolymers using the same repeating units among the repeating units represented by the above general formula (I), as well as copolymers containing different types of repeating units.
  • homopolymers those having p-phenylene sulfide groups as repeating units, which have p-phenylene groups as arylene groups, are preferred. This is because homopolymers having p-phenylene sulfide groups as repeating units have extremely high heat resistance, and exhibit high strength, high rigidity, and high dimensional stability over a wide temperature range. By using such homopolymers, molded articles with extremely excellent physical properties can be obtained.
  • a combination of two or more different arylene sulfide groups among the above-mentioned arylene group-containing arylene sulfide groups can be used.
  • a combination containing a p-phenylene sulfide group and an m-phenylene sulfide group is preferred from the viewpoint of obtaining a molded product with high physical properties such as heat resistance, moldability, and mechanical properties.
  • a polymer containing 70 to 100 mol% of p-phenylene sulfide groups is more preferred, and a polymer containing 80 to 100 mol% is even more preferred.
  • the polyarylene sulfide resin having phenylene sulfide groups is a polyphenylene sulfide resin (PPS resin).
  • Polyarylene sulfide resins are generally known to have a substantially linear molecular structure with no branching or crosslinking, and a structure with branching or crosslinking, depending on the manufacturing method. In one embodiment, from the viewpoint of improving the toughness of the molded product, it is more preferable that the resin does not contain a structure with a crosslinking structure.
  • the content of the polyarylene sulfide resin (P) in the recycled material (z1) is preferably 30 to 99 mass%, more preferably 50 to 95 mass%, based on the total amount of the recycled material (z1). In one embodiment, the total content of the polyarylene sulfide resin (P) and the elastomer (Q) in the resin components contained in the recycled material (z1) is preferably 80 to 100 mass%, more preferably 90 to 100 mass%, based on the total amount of the resin components. In one embodiment, the resin components contained in the recycled material (z1) may consist of the polyarylene sulfide resin (P) and the elastomer (Q).
  • elastomer (Q) examples include olefin-based elastomers, styrene-based elastomers, polyester-based elastomers, etc., which may be grafted, and it is preferable to include at least one selected from these, and for example, it may include an olefin-based elastomer. Even when the recycled material (z1) includes an elastomer, it is possible to suppress mold contamination when molding the resulting coated recycled material (Z).
  • the elastomer (Q) may be an elastomer having a reactive functional group, such as an acid-modified elastomer modified with an acid or an acid anhydride, such as (meth)acrylic acid or maleic anhydride; an elastomer using a copolymerizable monomer having a glycidyl group or an epoxy group (such as glycidyl (meth)acrylate); or an epoxy-modified elastomer obtained by epoxidizing the unsaturated bond of an elastomer.
  • a reactive functional group such as an acid-modified elastomer modified with an acid or an acid anhydride, such as (meth)acrylic acid or maleic anhydride
  • an elastomer using a copolymerizable monomer having a glycidyl group or an epoxy group such as glycidyl (meth)acrylate
  • Olefin-based elastomers include copolymers of ⁇ -olefins and copolymerizable monomers.
  • the ⁇ -olefin is preferably one or more selected from ⁇ -olefins having 2 to 13 carbon atoms (e.g., ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, etc.).
  • copolymers of ⁇ -olefins and copolymerizable monomers include, but are not limited to, ⁇ -olefin-unsaturated carboxylic acid alkyl ester copolymers, and olefin-based copolymers containing structural units derived from ⁇ -olefins and structural units derived from glycidyl esters of ⁇ , ⁇ -unsaturated acids.
  • glycidyl esters of ⁇ , ⁇ -unsaturated acids include, but are not limited to, glycidyl esters of acrylic acid, glycidyl esters of methacrylic acid, and glycidyl esters of ethacrylic acid.
  • the olefin-based copolymer may further include structural units derived from (meth)acrylic acid esters.
  • Preferred specific examples of olefin-based elastomers include ethylene propylene rubber (EPR), ethylene-glycidyl methacrylate copolymer (E-GMA), ethylene-glycidyl methacrylate-methyl acrylate copolymer (E-GMA-MA), etc.
  • EPR ethylene propylene rubber
  • E-GMA ethylene-glycidyl methacrylate copolymer
  • E-GMA-MA ethylene-glycidyl methacrylate-methyl acrylate copolymer
  • the olefin-based elastomer may be contained alone or in combination of two or more kinds.
  • the styrene-based elastomer may be a block copolymer consisting of a polymer block mainly made of a vinyl aromatic compound such as styrene and a polymer block mainly made of a non-hydrogenated and/or hydrogenated conjugated diene compound.
  • Specific examples of preferred styrene-based elastomers include styrene-butadiene rubber (SBR) and styrene-ethylene-butylene-styrene block copolymer (SEBS).
  • SBR styrene-butadiene rubber
  • SEBS styrene-ethylene-butylene-styrene block copolymer
  • the styrene-based elastomer may also be a modified copolymer into which a functional group (epoxy group, carboxy group, acid anhydride group, etc.) has been introduced.
  • modified copolymers include epoxidized styrene-diene copolymers in which the unsaturated bond of the diene has been epoxidized (e.g., epoxidized styrene-diene-styrene block copolymers or hydrogenated polymers thereof).
  • the styrene-based elastomer may be contained alone or in combination of two or more types.
  • polyester-based elastomers include block copolymers in which aromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate serve as hard segments, and polyethers such as polyethylene glycol and polytetramethylene glycol, or aliphatic polyesters such as polyethylene adipate, polybutylene adipate, and polycaprolactone serve as soft segments.
  • aromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate
  • polyethers such as polyethylene glycol and polytetramethylene glycol
  • aliphatic polyesters such as polyethylene adipate, polybutylene adipate, and polycaprolactone serve as soft segments.
  • the polyester-based elastomers may be used alone or in combination of two or more types.
  • the elastomer (Q) When the elastomer (Q) has a reactive functional group, it can provide the virgin material with the effects of increasing impact resistance and high- and low-temperature impact properties, and of imparting toughness, but when recycled, mold deposits are more likely to occur and mold fouling is more likely to occur.
  • the manufacturing method of the coated recycled material (Z) according to this embodiment even when the recycled material (z1) contains the elastomer (Q) having a reactive functional group, mold fouling during molding can be reduced.
  • the elastomer (Q) may have a reactive functional group.
  • the method for producing the coated recycled material (Z) may include preparing the recycled material (z1) of an article including the elastomer (Q) having a reactive functional group.
  • reactive functional group means a functional group that can react with an end group of a polyarylene sulfide resin to form a chemical bond at the melting temperature of the resin.
  • reactive functional groups include glycidyl groups, epoxy groups, carboxy groups, hydroxyl groups, acid anhydride groups, salts of carboxy groups, carboxylate groups, amide groups, and amino groups, isocyanate groups, isothiocyanate groups, acetoxy groups, silanol groups, alkoxysilane groups, alkynyl groups, oxazoline groups, thiol groups, and sulfonic acid groups.
  • the elastomer (Q) may include an olefin-based elastomer, a styrene-based elastomer, or a polyester-based elastomer that includes one or more groups selected from a glycidyl group, an epoxy group, a carboxy group, a hydroxyl group, an acid anhydride group, a salt of a carboxy group, a carboxylate ester group, an amide group, and an amino group, an isocyanate group, an isothiocyanate group, an acetoxy group, a silanol group, an alkoxysilane group, an alkynyl group, an oxazoline group, a thiol group, and a sulfonic acid group.
  • a glycidyl group an epoxy group, a carboxy group, a hydroxyl group, an acid anhydride group, a salt of a carboxy group, a carboxylate ester group, an
  • the elastomer (Q) may include at least one selected from an olefin-based elastomer including a constitutional unit derived from an ⁇ -olefin and a constitutional unit derived from a glycidyl ester of an ⁇ , ⁇ -unsaturated acid, and a styrene-based elastomer including an epoxidized styrene-diene copolymer in which an unsaturated bond of a diene has been epoxidized.
  • the elastomer (Q) may include an elastomer (Q) containing constitutional units derived from an ⁇ -olefin and constitutional units derived from a glycidyl ester of an ⁇ , ⁇ -unsaturated acid.
  • the method for producing the coated recycled material (Z) may include preparing a recycled material (z1) of an article containing an elastomer (Q) containing constitutional units derived from an ⁇ -olefin and constitutional units derived from a glycidyl ester of an ⁇ , ⁇ -unsaturated acid.
  • the content of the reactive functional group may be 0.1 to 10 mass% of the total amount of the elastomer, or may be 0.5 to 8 mass%.
  • the content of the reactive functional group can be calculated from the manufacturer's catalog value of the copolymer composition and the molecular weight of the functional group.
  • the content of the elastomer (Q) in the recycled material (z1) is 1 to 20 parts by mass, preferably 2 to 15 parts by mass, more preferably 3 to 10 parts by mass, and even more preferably 3 to 8.5 parts by mass, per 100 parts by mass of the polyarylene sulfide resin (P).
  • the content of the elastomer (Q) in the pulverized material (X) may be 6.2 parts by mass per 100 parts by mass of the polyarylene sulfide resin (P). In all aspects, these values may be combined to form the upper or lower limit of the numerical range.
  • the elastomer content may be the manufacturer's catalog value for the article. The elastomer content may also be measured by thermogravimetry.
  • the recycled material (z1) may contain 1 to 20 mass %, 2 to 18 mass %, or 3 to 16 mass % of an elastomer having a reactive functional group based on the total amount of the recycled material (z1).
  • the recycled material (z1) may contain other components contained in the recycled molded product in addition to the above-mentioned polyarylene sulfide resin (P) and elastomer (Q).
  • other components that the recycled material (z1) may contain include organic or inorganic fillers, and other additives that are generally added to thermoplastic resins (e.g., flame retardants, colorants such as dyes and pigments, stabilizers such as ultraviolet absorbers, lubricants, crystallization accelerators, crystal nucleating agents, etc.).
  • Organic or inorganic fillers include fibrous fillers such as high-melting point organic fibrous substances such as glass fiber, carbon fiber, zinc oxide fiber, titanium oxide fiber, wollastonite, silica fiber, silica-alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, stainless steel fiber, aluminum fiber, titanium fiber, copper fiber, brass fiber, polyamide, high molecular weight polyethylene, aramid, fluororesin, polyester resin, and acrylic resin; carbon black, graphite, silica, quartz powder, and glass beads.
  • fibrous fillers such as high-melting point organic fibrous substances such as glass fiber, carbon fiber, zinc oxide fiber, titanium oxide fiber, wollastonite, silica fiber, silica-alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, stainless steel fiber, aluminum
  • milled glass fiber glass balloons, glass powder, talc (granular), silicates such as calcium silicate, aluminum silicate, diatomaceous earth, metal oxides such as iron oxide, titanium oxide, zinc oxide, alumina (granular), metal carbonates such as calcium carbonate, magnesium carbonate, metal sulfates such as calcium sulfate, barium sulfate, and other powdered and granular fillers such as silicon carbide, silicon nitride, boron nitride, and various metal powders; plate-shaped fillers such as mica, glass flakes, talc (plate-shaped), mica, kaolin, clay, alumina (plate-shaped), and various metal foils; and the like. In terms of mechanical strength, heat resistance, and the like, it is preferable to contain an inorganic filler.
  • the content of the organic or inorganic filler in the recycled material (z1) is preferably 10 to 70 mass%, more preferably 15 to 65 mass%, and even more preferably 20 to 60 mass%.
  • the recycled material (z1) may or may not contain an antioxidant. According to the manufacturing method of this embodiment, in either case, a coated recycled material (Z) that causes less mold contamination during molding can be obtained.
  • the recycled material (z1) may be the same type as the antioxidant (A) or a different type.
  • the content thereof may be, for example, 0.05 to 2.0 mass%, 0.1 to 1.0 mass%, or 0.1 to 0.5 mass% relative to the total amount (100 mass%) of the recycled material (z1).
  • the recycled material (z1) is a material obtained by pulverizing the above-mentioned article (recycled product) containing a predetermined amount of the polyarylene sulfide resin (P) and the elastomer (Q) and regenerating it as a raw material for use in producing a molded product, as described above.
  • the recycled material (z1) may be a pulverized product of the recycled product, or may be pellets obtained by melt-kneading the pulverized product.
  • the average particle diameter of the pulverized material is preferably 0.3 to 20 mm, more preferably 0.4 to 15 mm, even more preferably 1 to 10 mm, even more preferably 1 to 5 mm, and particularly preferably 1 to 3 mm, from the viewpoint of reducing the bite of the screw and/or torque of the extruder when producing recycled pellets.
  • the average particle diameter of the pulverized material is the volume-based cumulative 50% diameter (D50) measured by a laser diffraction scattering method.
  • the method of pulverizing the article is not limited, and can be performed by a known method using, for example, a jet mill, a roller mill, a high-speed rotary pulverizer, a container-driven mill, or the like.
  • the preparation step may include a classification process of the pulverized material by sieving, etc., as necessary.
  • the preparation of the pellet-shaped recycled material (z1) may include, for example, melt-kneading and extruding the above-mentioned pulverized material using a melt-kneading device such as a conventionally known single-screw or twin-screw extruder, and cutting the pulverized material into pellets.
  • the melt-kneading temperature is a temperature equal to or higher than the melting point of the polyarylene sulfide resin (P) contained in the recycled material (z1), and is usually 280 to 360°C, and preferably 290 to 350°C.
  • the melt viscosity of the recycled material (z1) is not limited as long as it does not impair the effects of the present disclosure, and the melt viscosity measured at 310°C and a shear rate of 1200 sec -1 may be 10 to 1000 Pa ⁇ s, or 30 to 700 Pa ⁇ s.
  • the melt viscosity can be measured, for example, using a known capillary rheometer, using a 1 mm ⁇ 20 mmL flat die as a capillary, at a barrel temperature of 310°C and a shear rate of 1000 sec -1 .
  • ⁇ Coating process> In the coating step, at least a portion of the surface of the recycled material (z1) is coated with an antioxidant (A).
  • the coating amount of the antioxidant (A) is 0.025 to 0.25 parts by mass per part by mass of the elastomer (Q) contained in the recycled material (z1).
  • the antioxidant (A) may be a phenol-based antioxidant, a phosphorus-based antioxidant, a thioether-based antioxidant, or the like, and preferably contains one or more selected from the group consisting of these, and more preferably contains a phenol-based antioxidant.
  • the antioxidant (A) may be used alone or in combination of two or more.
  • the phenolic antioxidant may be a compound having one or more alkylphenol groups in its molecular structure.
  • a compound having a phenyl group substituted with a hydroxyl group (-OH) and a tert-butyl group is preferred.
  • a compound having two or more tert-butyl groups per phenolic hydroxyl group is more preferred.
  • phenol-based antioxidant examples include 2,6-di-tert-butyl-p-cresol, stearyl-(3,5-dimethyl-4-hydroxybenzyl)thioglycolate, stearyl- ⁇ -(4-hydroxy-3,5-di-tert-butylphenyl)propionate, distearyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, distearyl(4-hydroxy-3-methyl-5-tert-butyl)benzylmalonate, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis[6-(1-methylcyclohexyl) -p-cresol], bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyric acid]glycol ester, 4,4'-butylidenebis(
  • the amount of antioxidant (A) blended (coating amount) is 0.025 to 0.25 parts by mass, preferably 0.026 to 0.20 parts by mass, more preferably 0.027 to 0.15 parts by mass, even more preferably 0.028 to 0.10 parts by mass, and particularly preferably 0.030 to 0.085 parts by mass, per part by mass of elastomer (Q) contained in recycled material (z1).
  • the amount of antioxidant (A) blended (coating amount) may be 0.05 parts by mass per part by mass of elastomer (Q) contained in recycled material (z1). In all aspects, these numerical values may be combined to form the upper or lower limit of the above numerical range.
  • the coating comprises the following coating method (i) or (ii).
  • the melting point of the antioxidant (A) is a value measured according to the DSC method (method described in JIS K7121).
  • the melting point of the recycled material (z1) is the melting point Tm1 measured by a differential scanning calorimeter, which is the peak top temperature of the endothermic peak in the first run observed when heated from room temperature at a heating rate of 10°C/min (1st run) according to a method based on JIS K7121.
  • the melting point of the antioxidant (A) is preferably 50 to 135°C, more preferably 55 to 135°C, even more preferably 60 to 130°C, and most preferably 70 to 125°C.
  • the melting point of the antioxidant (A) include triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] (76 to 79°C) and tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, which have a melting point of 110 to 125°C.
  • the temperature at which the recycled material (z1) is brought into contact with the antioxidant (A) may be, for example, 80 to 160°C, or 100 to 140°C.
  • the contact time is not limited and may be, for example, 5 minutes or more, or 3 to 8 hours.
  • the contacting is usually carried out by mixing the recycled material (z1) with the antioxidant (A) using a known agitator or the like.
  • the recycled material (z1) and the antioxidant (A) can be contacted with each other using a known dryer such as an air circulation dryer while heating or by using residual heat after heating, preferably while stirring.
  • the coating step can be performed by coating method (i) during the step of drying the pellet-shaped recycled material (z1) or immediately after the drying step in a state in which the temperature of the recycled material (z1) is equal to or higher than the melting point (°C) of the antioxidant (A).
  • the heat from the drying step can be effectively utilized for coating.
  • the antioxidant (A) used in the coating method (i) may be a solid or liquid at room temperature (25°C), and is preferably a solid. Even if the antioxidant (A) is a solid, it is brought into contact with the recycled material (z1) at a temperature equal to or higher than the melting point of the antioxidant (A), and therefore the antioxidant (A) melts and can wet and spread over at least a portion of the surface of the recycled material (z1). As a result, at least a portion of the surface of the recycled material (z1) can be coated.
  • the antioxidant (A) is preferably in a powder, flake, or granular form. That is, in one embodiment, the coating preferably includes contacting the regenerator (z1) with the antioxidant (A) in a powder, flake, or granular form at a temperature equal to or higher than the melting point of the antioxidant (A).
  • the powder-like antioxidant (A) may be formed of granular fine particles.
  • the flake-like antioxidant (A) may be formed of plate-like fine particles.
  • the granular antioxidant (A) may be formed of a plurality of fine particles gathering together to form one particle.
  • the coating preferably includes (ii) contacting the recycled material (z1) with a liquid antioxidant (A).
  • the liquid antioxidant (A) may be an antioxidant (A) that is liquid at room temperature (25°C), or may be a liquid antioxidant (A) obtained by heating a solid antioxidant (A) at room temperature (25°C) to a melting point or higher. It may also be a liquid antioxidant (A) obtained by dissolving a solid antioxidant (A) in a solvent at room temperature (25°C). By using a liquid antioxidant (A), it is not necessary to heat the recycled material (z1) in the coating step.
  • the method of contacting is not limited, and examples include a method of applying the liquid antioxidant (A) to the surface of the recycled material (z1) by coating, spraying, etc., and a method of stirring and mixing the recycled material (z1) and the liquid antioxidant (A).
  • the resulting coated recycled material (Z) After the coating process, it is preferable to cool the resulting coated recycled material (Z) to preferably room temperature to 80°C, more preferably room temperature to 40°C, to fix the surface coating layer (or the coated area).
  • the compound By fixing the coating layer, the compound can be maintained in a uniformly dispersed state, and stable release properties can be improved.
  • the cooling method is not limited, and may be left to cool, blowing air, etc.
  • the amount of antioxidant (A) coated on the recycled material (z1) is 0.025 to 0.25 parts by mass per part by mass of elastomer (Q), making it possible to produce a coated recycled material (Z) that causes less mold contamination during molding.
  • the types and amounts of polyarylene sulfide resin (P), elastomer (Q), recycled material (z1), and antioxidant (A), as well as the manufacturing method for the coated recycled material (Z), are as described above.
  • the coating amount of the antioxidant (A) on the recycled material (z1) is preferably 0.026 to 0.20 parts by mass, more preferably 0.027 to 0.15 parts by mass, even more preferably 0.028 to 0.10 parts by mass, and particularly preferably 0.030 to 0.085 parts by mass, per 100 parts by mass of the elastomer (Q) contained in the recycled material (z1).
  • the coating amount of the antioxidant (A) may be 0.05 parts by mass per 100 parts by mass of the elastomer (Q) contained in the recycled material (z1). In all aspects, these numerical values may be combined to form the upper or lower limit of the above numerical range.
  • the coating amount of the antioxidant (A) can be measured, for example, by NMR or the like.
  • the content of the elastomer (Q) is 1 to 20 parts by mass, preferably 2 to 15 parts by mass, more preferably 3 to 10 parts by mass, and even more preferably 3 to 8.5 parts by mass, per 100 parts by mass of the polyarylene sulfide resin (P).
  • the content of the elastomer (Q) may be 6.2 parts by mass per 100 parts by mass of the polyarylene sulfide resin (P). In all aspects, these values may be combined to form the upper or lower limit of the above numerical range.
  • the content of the elastomer (Q) in the coated recycled material (Z) can be measured, for example, by thermogravimetry.
  • the elastomer (Q) may have a reactive functional group.
  • the elastomer (Q) may include an elastomer (Q) that includes a structural unit derived from an ⁇ -olefin and a structural unit derived from a glycidyl ester of an ⁇ , ⁇ -unsaturated acid.
  • the reactive functional group and the like are also as described above. The other descriptions regarding the elastomer (Q) in the first embodiment also apply here.
  • the melt viscosity of the coated recycled material (Z) is not limited as long as it does not impair the effects of the present disclosure, and the melt viscosity measured at 310°C and a shear rate of 1200 sec -1 may be 10 to 1000 Pa ⁇ s, or 30 to 700 Pa ⁇ s.
  • the method for measuring the melt viscosity is as described in the section on recycled material (z1).
  • the coated recycled material (Z) may contain other components that may generally be blended into thermoplastic resins.
  • other components include organic or inorganic fillers, and other additives that are generally added to thermoplastic resins (e.g., flame retardants, colorants such as dyes and pigments, stabilizers such as UV absorbers, lubricants, crystallization accelerators, crystal nucleating agents, etc.).
  • organic or inorganic fillers include those exemplified as organic or inorganic fillers that may be contained in the recycled material (z1).
  • the method for producing the coated recycled material (Z) is as described above.
  • the form of the coated recycled material (Z) is not limited, and may be any desired form such as powder, flakes, pellets, etc.
  • the coated regenerated material (Z) has a mold adhesion amount, measured by the following method, of preferably 0 to 45 ⁇ g, more preferably 0 to 40 ⁇ g, even more preferably 0 to 35 ⁇ g, and particularly preferably 0 to 30 ⁇ g.
  • ⁇ Measurement method> Using a nested mold in which the vent and cavity are detachable, the molded article shown in Fig. 1 is continuously molded for 4 hours (1000 times) using an injection molding machine under the following conditions: Before and after the continuous molding, the total weight of the vent and cavity removed from the mold is measured, and the total weight change of the vent and cavity before and after the continuous molding is regarded as the weight of the material adhering to the mold.
  • ⁇ Injection molding conditions> Cylinder temperature: 340°C Injection time: 2 seconds Cooling time: 10 seconds Mold temperature: 140°C
  • the recycled coated material (Z) can suppress mold contamination during molding, and can therefore be suitably used as a resin composition for injection molding or a resin composition for extrusion molding.
  • the above-mentioned coated recycled material (Z) can be mixed with other thermoplastic resins as necessary and used as a molding material.
  • the other thermoplastic resins include virgin polyarylene sulfide resins, and preferably virgin polyarylene sulfide resins or virgin polyarylene sulfide resin compositions.
  • the manufacturing method according to this embodiment is a method for manufacturing a coated recycled material-virgin material mixed resin composition (W), and includes mixing the coated recycled material (Z) manufactured by the above-mentioned manufacturing method of the coated recycled material (Z) with a virgin polyarylene sulfide resin or a composition thereof (V).
  • a virgin polyarylene sulfide resin or a composition thereof (V) By mixing with the virgin polyarylene sulfide resin or a composition thereof (V), the excellent physical properties of the polyarylene sulfide resin can be reinforced.
  • the manufacturing method of the coated recycled material (Z) and the coated recycled material (Z) are as described above, so the description will be omitted here.
  • the virgin polyarylene sulfide resin is a virgin material of the polyarylene sulfide resin.
  • the virgin polyarylene sulfide resin composition may be a composition containing a virgin polyarylene sulfide resin and, if necessary, other components.
  • Examples of the polyarylene sulfide resin containing the virgin polyarylene sulfide resin or its composition (V) include the same ones as those described for the coated recycled material (Z) above, and from the viewpoint of quality control, etc., it is preferable that the composition is the same as that of the polyarylene sulfide resin in the coated recycled material (Z).
  • the other components include compounds similar to the other components that may be contained in the coated recycled material (Z), elastomers, and antioxidants.
  • the virgin polyarylene sulfide resin or its composition (V) is a composition, it is preferable that the composition is the same as that of the coated recycled material (Z) from the viewpoint of quality control, etc. (for example, the type and content of additives are the same).
  • the amount of coated recycled material (Z) is preferably 50% by mass or more, more preferably 50 to 99.99% by mass, and even more preferably 60 to 100% by mass, relative to the total amount (100% by mass) of coated recycled material (Z) and virgin polyarylene sulfide resin or composition thereof (V), in order to increase the amount of recycled material used. Even if the amount of coated recycled material (Z) is increased, a coated recycled material-virgin material mixed resin composition (W) with less mold contamination during molding can be obtained.
  • the mixing method is not limited, and the coated recycled material (Z) and the virgin polyarylene sulfide resin or composition thereof (V) may be dry blended, melt-kneaded using a conventional melt-kneading device such as a single-screw or twin-screw extruder, or mixed in the hopper (material supply member) of an injection molding machine.
  • the resulting recycled material-virgin material mixed resin composition (W) can be processed into the desired form such as powder, flakes, pellets, etc.
  • the total content of the coated recycled material (Z) and virgin polyarylene sulfide resin or a composition thereof is preferably 80 to 100 mass %, more preferably 90 to 100 mass %, even more preferably 95 to 100 mass %, and may be 100 mass %, relative to the total amount (100 mass %) of resin components contained in the coated recycled material-virgin material mixed resin composition (W).
  • the melt viscosity of the coated recycled material-virgin material mixed resin composition (W) is not limited as long as it does not impair the effects of the present disclosure, and the melt viscosity measured at 310°C and a shear rate of 1200 sec -1 may be 10 to 1000 Pa ⁇ s, or 30 to 700 Pa ⁇ s.
  • the method for measuring the melt viscosity is as described in the section on recycled material (z1).
  • the coated recycled material-virgin material mixed resin composition (W) may contain other components that can be generally blended into thermoplastic resins.
  • other components include organic or inorganic fillers, and other additives that are generally added to thermoplastic resins (e.g., flame retardants, colorants such as dyes and pigments, stabilizers such as ultraviolet absorbers, lubricants, crystallization accelerators, crystal nucleating agents, etc.).
  • organic or inorganic fillers include those exemplified as organic or inorganic fillers that may be contained in the recycled material (z1).
  • the form of the coated recycled material-virgin material mixed resin composition (W) is not limited, and may be in any desired form such as powder, flakes, pellets, etc.
  • the mixed resin composition (W) of recycled coated material and virgin material can suppress mold contamination during molding, and therefore can be suitably used as a resin composition for injection molding or extrusion molding.
  • the recycled molded product according to this embodiment is a molded product containing the above-mentioned coated recycled material (Z).
  • the manufacturing method of the recycled molded product is not limited, and the coated recycled material (Z) can be manufactured by performing known injection molding, profile/solidification extrusion processing, press molding, spinning processing, etc., using the coated recycled material (Z) together with other thermoplastic resins and additives as necessary.
  • the coated recycled material (Z) causes less mold contamination during molding, so the number of mold replacements can be reduced, and the productivity of the recycled molded product can be improved.
  • the coating preferably includes contacting the recycled material (z1) with the antioxidant (A) in a powder, flake or granular form at a temperature equal to or higher than the melting point of the antioxidant (A).
  • the method of contacting the recycled material (z1) with the antioxidant (A) at a temperature equal to or higher than the melting point of the antioxidant (A) is as described above.
  • the coating preferably includes contacting the recycled material (z1) with a liquid antioxidant (A).
  • the method for contacting the recycled material (z1) with the liquid antioxidant (A) is as described above.
  • this method may be a method for suppressing mold contamination during molding of a recycled material (z1) of an article that contains 100 parts by mass of a polyarylene sulfide resin (P) and 1 to 20 parts by mass of an elastomer (Q) having a reactive functional group.
  • this method may be a method for suppressing mold contamination during molding of a recycled material (z1) of an article that contains 100 parts by mass of a polyarylene sulfide resin (P) and 1 to 20 parts by mass of an elastomer (Q) that contains structural units derived from an ⁇ -olefin and structural units derived from a glycidyl ester of an ⁇ , ⁇ -unsaturated acid.
  • the method according to the present embodiment is to use an antioxidant (A) for suppressing mold contamination during molding of a recycled material (z1) of an article comprising 100 parts by mass of a polyarylene sulfide resin (P) and 1 to 20 parts by mass of an elastomer (Q),
  • the method includes coating at least a portion of the surface of the recycled material (z1) with an antioxidant (A),
  • the coating step includes coating at least a portion of the surface of the recycled material (z1) with the antioxidant (A) in an amount of 0.025 to 0.25 parts by mass per part by mass of the elastomer (Q) contained in the recycled material (z1).
  • preparing the recycled material (z1) includes preparing a recycled material (z1) of an article containing an elastomer (Q) having a reactive functional group.
  • preparing the recycled material (z1) includes preparing a pellet-shaped recycled material (z1) obtained by melt-kneading a pulverized material of the article.
  • the coating step includes contacting the recycled material (z1) with an antioxidant (A) including one or more selected from the group consisting of a phenol-based antioxidant, a phosphorus-based antioxidant, and a thioether-based antioxidant.
  • [5] The method according to any one of [1] to [4], wherein the coating step includes contacting the recycled material (z1) with the antioxidant (A) in a powder, flake, or granular form at a temperature equal to or higher than the melting point of the antioxidant (A).
  • [6] The method according to any one of [1] to [5], wherein the coating step includes contacting the recycled material (z1) with a liquid antioxidant (A).
  • At least a part of the surface of a recycled material (z1) of an article containing 100 parts by mass of a polyarylene sulfide resin (P) and 1 to 20 parts by mass of an elastomer (Q) is coated with an antioxidant (A);
  • the coated recycled material (Z) has a coating amount of the antioxidant (A) of 0.025 to 0.25 parts by mass per part by mass of the elastomer (Q) contained in the recycled material (z1).
  • a coated recycled material-virgin material mixed resin composition (W) comprising the coated recycled material (Z) according to any one of [8] to [10] and a virgin polyarylene sulfide resin or a composition thereof (V).
  • the coating step includes contacting the recycled material (z1) with the antioxidant (A) in a powder, flake, or granular form at a temperature equal to or higher than the melting point of the antioxidant (A).
  • the coating step includes contacting the regenerant (z1) with a liquid antioxidant (A).
  • an antioxidant (A) for suppressing mold contamination during molding of a recycled material (z1) of an article comprising 100 parts by mass of a polyarylene sulfide resin (P) and 1 to 20 parts by mass of an elastomer (Q)
  • the method includes coating at least a portion of the surface of the recycled material (z1) with an antioxidant (A),
  • the coating step includes coating at least a part of the surface of the recycled material (z1) with the antioxidant (A) in an amount of 0.025 to 0.25 parts by mass per part by mass of the elastomer (Q) contained in the recycled material (z1).
  • Recycled pellets (1) Recycled injection-molded products that do not contain antioxidants
  • PPS polyphenylene sulfide resin
  • GF glass fiber
  • elastomer Composition: E-GMA-MA (glycidyl methacrylate content: 3% by mass)
  • the pulverized product obtained was put into a twin-screw extruder with a cylinder temperature of 320 ° C. and melt-kneaded to obtain a pellet-shaped recycled material (recycled pellets (1)).
  • the content ratio of each component relative to 100 parts by mass of polyarylene sulfide resin in the recycled pellets (1) is shown in Table 1 as "composition of resin composition A”.
  • Recycled pellets (2) Recycled injection moldings containing antioxidants
  • resin composition B containing 64.8% by mass of polyphenylene sulfide resin (PPS) (manufactured by Kureha Corporation, Fortron (registered trademark) KPS), 30% by mass of glass fiber (GF), 4% by mass of elastomer (composition: E-GMA-MA (glycidyl methacrylate content: 3% by mass)), and 0.2% by mass of antioxidant, with the balance being other additives, was pulverized by a mechanical pulverizer to obtain a pulverized product having an average particle diameter D50 of 3 mm.
  • PPS polyphenylene sulfide resin
  • GF glass fiber
  • elastomer composition: E-GMA-MA (glycidyl methacrylate content: 3% by mass)
  • antioxidant 0.2% by mass of antioxidant
  • the pulverized product obtained was put into a twin-screw extruder with a cylinder temperature of 320 ° C. and melt-kneaded to obtain a pellet-shaped recycled material (recycled pellets (2)).
  • the content ratio of each component relative to 100 parts by mass of polyarylene sulfide resin in the recycled pellets (2) is shown in Table 1 as "composition of resin composition B".
  • Antioxidant (A) Tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, IRGANOX 1010 (product name), manufactured by BASF Japan Ltd., melting point: 110 to 125° C. The melting point of the antioxidant (A) was determined from the value in the manufacturer's catalogue.
  • Example 1 10 kg of the recycled pellets (1) and 20 g of the powdered antioxidant (A) (0.05 parts by mass per part by mass of the elastomer in the recycled pellets (1)) were placed in a metal container (30 cm x 60 cm x 15 cm), heated at 140°C for 3 hours in a blower dryer, and then cooled to room temperature. The mixture was then stirred (dispersed) in a mixer to obtain coated recycled pellets (Z1).
  • Reference Example 1 As Reference Example 1, virgin pellets of the above polyarylene sulfide resin composition A (containing no antioxidant) were used.
  • Reference Example 2 As Reference Example 2, virgin pellets of the above polyarylene sulfide resin composition B (containing an antioxidant) were used.
  • the amount of material adhering to the die was 27 ⁇ g when the coated regenerated pellets (Z1) of Example 1 were used.
  • the amount of material adhering to the die was 69 ⁇ g when the regenerated pellets (1) of Comparative Example 1, which were not coated with the antioxidant (A), were used, and the amount of material adhering to the die was 57 ⁇ g when the regenerated pellets (2) of Comparative Example 2, which were not coated with the antioxidant (A), were used.
  • Comparative Examples 3 and 4 in which the powdered antioxidant (A) was mixed with the regenerated pellets (1) or (2) at room temperature, the amount of material adhering to the die was 66 ⁇ g or 54 ⁇ g.
  • the amount of material adhering to the mold when the virgin pellets of Reference Example 1 were used was 51 ⁇ g
  • the amount of material adhering to the mold when the virgin pellets of Reference Example 2 were used was 31 ⁇ g.
  • the coated recycled pellets (Z1) of Example 1 resulted in less mold fouling than the virgin pellets of Reference Examples 1 and 2, and the mold fouling was reduced to about 40% of that of the recycled pellets (1) of Comparative Example 1 that were not coated with the antioxidant (A) (i.e., the mold fouling was reduced to about 60%). Furthermore, the mold fouling was reduced to about 47% of that of the recycled pellets (2) of Comparative Example 2 that were not coated with the antioxidant (A) (i.e., the mold fouling was reduced to about 53%). In contrast, the recycled pellets (1) of Comparative Example 1, which were not coated with the antioxidant (A), resulted in more mold fouling than the virgin pellets of Reference Example 1.
  • the recycled pellets (2) of Comparative Example 2 which were not coated with the antioxidant (A), resulted in more mold fouling than the virgin pellets of Reference Example 2, and also resulted in more mold fouling than the virgin pellets of Reference Example 1. From these results, it can be seen that the recycled pellets suffer from worse mold fouling than the virgin pellets, and that even when the raw material for recycling contains an antioxidant, the effect of suppressing mold fouling when molding the resulting recycled material is low. Furthermore, as shown in Comparative Examples 3 and 4, even when the antioxidant (A) is blended during molding, if the antioxidant (A) is not attached to the surface of the recycled pellets (1) or (2), the antioxidant (A) segregates during molding, and the effect of suppressing mold fouling is not sufficiently obtained.
  • the method for producing the recycled polyarylene sulfide resin composition of this embodiment can suppress mold contamination during molding, and therefore has industrial applicability as a method for producing a resin composition for injection molding or a resin composition for extrusion molding.

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004169027A (ja) * 2002-11-08 2004-06-17 Asahi Kasei Chemicals Corp 添加剤を含有する熱可塑性樹脂ペレットの製造方法
WO2009096075A1 (ja) * 2008-01-31 2009-08-06 Polyplastics Co., Ltd. 多層筒状成形体
JP2017031248A (ja) * 2015-07-29 2017-02-09 宇部興産株式会社 ポリプロピレン樹脂成形体廃棄物の再利用方法
JP2017148997A (ja) * 2016-02-23 2017-08-31 学校法人福岡大学 樹脂組成物成形機および樹脂組成物の成形方法
WO2023167151A1 (ja) * 2022-03-04 2023-09-07 旭化成株式会社 ブロック共重合体、樹脂組成物、硬化物、樹脂フィルム、プリプレグ、積層体、及び電子回路基板用の材料

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004169027A (ja) * 2002-11-08 2004-06-17 Asahi Kasei Chemicals Corp 添加剤を含有する熱可塑性樹脂ペレットの製造方法
WO2009096075A1 (ja) * 2008-01-31 2009-08-06 Polyplastics Co., Ltd. 多層筒状成形体
JP2017031248A (ja) * 2015-07-29 2017-02-09 宇部興産株式会社 ポリプロピレン樹脂成形体廃棄物の再利用方法
JP2017148997A (ja) * 2016-02-23 2017-08-31 学校法人福岡大学 樹脂組成物成形機および樹脂組成物の成形方法
WO2023167151A1 (ja) * 2022-03-04 2023-09-07 旭化成株式会社 ブロック共重合体、樹脂組成物、硬化物、樹脂フィルム、プリプレグ、積層体、及び電子回路基板用の材料

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