WO2023127688A1 - ペレット、成形品およびペレットの製造方法 - Google Patents

ペレット、成形品およびペレットの製造方法 Download PDF

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Publication number
WO2023127688A1
WO2023127688A1 PCT/JP2022/047396 JP2022047396W WO2023127688A1 WO 2023127688 A1 WO2023127688 A1 WO 2023127688A1 JP 2022047396 W JP2022047396 W JP 2022047396W WO 2023127688 A1 WO2023127688 A1 WO 2023127688A1
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Prior art keywords
pellet
pellets
thermoplastic resin
fiber
rayon
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2022/047396
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English (en)
French (fr)
Japanese (ja)
Inventor
尚秀 杉山
哲彦 水阪
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Mitsubishi Gas Chemical Co Inc
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Mitsubishi Gas Chemical Co Inc
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Filing date
Publication date
Application filed by Mitsubishi Gas Chemical Co Inc filed Critical Mitsubishi Gas Chemical Co Inc
Priority to EP22915911.6A priority Critical patent/EP4458886A1/en
Priority to KR1020247023932A priority patent/KR20240130725A/ko
Priority to US18/724,005 priority patent/US20250065537A1/en
Priority to CN202280085806.8A priority patent/CN118434794A/zh
Priority to JP2023570934A priority patent/JPWO2023127688A1/ja
Publication of WO2023127688A1 publication Critical patent/WO2023127688A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B29B9/14—Making granules characterised by structure or composition fibre-reinforced
    • 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
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B29B7/007—Methods for continuous mixing
    • 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
    • B29B11/00—Making preforms
    • B29B11/14—Making preforms characterised by structure or composition
    • B29B11/16—Making preforms characterised by structure or composition comprising fillers or reinforcement
    • 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
    • B29B13/00—Conditioning or physical treatment of the material to be shaped
    • B29B13/06—Conditioning or physical treatment of the material to be shaped by drying
    • B29B13/065—Conditioning or physical treatment of the material to be shaped by drying of powder or pellets
    • 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
    • B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
    • B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
    • B29B15/10—Coating or impregnating independently of the moulding or shaping step
    • B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
    • B29B15/122—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex
    • 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
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
    • 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
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • 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
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • 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
    • B29B9/12—Making granules characterised by structure or composition
    • 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
    • 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
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/046—Reinforcing macromolecular compounds with loose or coherent fibrous material with synthetic macromolecular fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
    • C08L59/04—Copolyoxymethylenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/26—Natural polymers, natural resins or derivatives thereof according to C08L1/00 - C08L5/00, C08L89/00, C08L93/00, C08L97/00 or C08L99/00

Definitions

  • the present invention relates to pellets, molded articles, and pellet manufacturing methods.
  • thermoplastic resin For the purpose of weight reduction, molded products made of thermoplastic resin are used as metal substitutes. In order to increase the mechanical strength of molded articles formed from such thermoplastic resins, production and development of resin compositions containing reinforcing fibers are being promoted.
  • a step of supplying a fiber bundle obtained by bundling fibers and a molten resin to a die, bringing the fiber bundle and the molten resin into contact with each other in the die to impregnate the fiber bundle with the molten resin, and a step of impregnating the fiber bundle with the molten resin. is withdrawn from a die, cooled, and cut, wherein the ratio of the major axis to the minor axis of the fiber cross section (long axis/short axis) is 2.5 to 6.
  • a method for producing fiber-reinforced resin pellets is disclosed, which is characterized by the use of fibers.
  • reinforcing fiber bundles such as glass fibers are impregnated with a thermoplastic resin, taken as long fiber strands, and then cut by a pelletizer to produce pellets.
  • a thermoplastic resin taken as long fiber strands
  • a pelletizer to produce pellets.
  • the pellets obtained in this manner are susceptible to cracking in some cases.
  • An object of the present invention is to solve such problems, and to provide a pellet that is less likely to crack during production, a molded article formed from the pellet, and a method for producing the pellet.
  • the present inventors have conducted studies and found that rayon fibers satisfying predetermined conditions are used as reinforcing fibers, and that having a predetermined MFR is used as a thermoplastic resin to be impregnated, and further, It was found that the cracking of pellets can be effectively suppressed by adjusting the pellet length. Specifically, the above problems have been solved by the following means.
  • thermoplastic resin has a melt flow rate (MFR) of 70 to 200 g/10 minutes when measured at a temperature of 230 ° C. and a load of 2.16 kg
  • MFR melt flow rate
  • the rayon fiber has a number average fiber diameter of 5 to 30 ⁇ m
  • the pellet wherein the number average length of the pellet is 3 to 30 mm.
  • the thermoplastic resin contains at least one selected from polypropylene resin and polyacetal resin.
  • thermoplastic resin comprises an acid-unmodified polypropylene resin and an acid-modified polypropylene resin modified with maleic anhydride and/or maleic acid.
  • thermoplastic resin comprises an acid-unmodified polypropylene resin and an acid-modified polypropylene resin modified with maleic anhydride and/or maleic acid.
  • the pellets are bundled with 2,000 to 30,000 rayon fibers aligned in the length direction, impregnated with the thermoplastic resin in a melted state, and integrated.
  • ⁇ 5> The pellet according to any one of ⁇ 1> to ⁇ 4>, wherein the rayon fibers contained in the pellet have a number average fiber length of 3 to 30 mm.
  • ⁇ 6> The pellet according to any one of ⁇ 1> to ⁇ 5>, wherein the rayon fiber has an apparent Young's modulus of 10 to 50 GPa.
  • ⁇ 7> The pellet according to any one of ⁇ 1> to ⁇ 6>, wherein the rayon fiber has a tensile elongation of 3 to 20%.
  • ⁇ 8> Any one of ⁇ 1> to ⁇ 7>, wherein the thermoplastic resin content is 90 to 60% by mass and the rayon fiber content is 40 to 10% by mass in the pellets.
  • Pellets as described in . ⁇ 9> The pellet according to any one of ⁇ 1> to ⁇ 8>, wherein the degree of X-ray orientation of the rayon fibers is 90% or more.
  • ⁇ 10> A pellet blend containing the pellets according to any one of ⁇ 1> to ⁇ 9> and other thermoplastic resin pellets.
  • ⁇ 11> A molded article formed from the pellet according to any one of ⁇ 1> to ⁇ 9> and/or the pellet blend according to ⁇ 10.
  • ⁇ 12> After 2,000 to 30,000 rayon fibers are bundled in a state of being aligned in the length direction and impregnated with a thermoplastic resin in a molten state and integrated, the number average length is 3 to 3.
  • FIG. 1 is a schematic diagram showing a pellet manufacturing apparatus of an example.
  • the pellet of this embodiment is a pellet containing a thermoplastic resin and a bundle of 2,000 to 30,000 rayon fibers arranged in parallel in the fiber length direction, wherein at least part of the thermoplastic resin is The rayon fiber bundle is impregnated, and the melt flow rate (MFR) when measured at a temperature of 230 ° C. and a load of 2.16 kg according to JIS K 7210 of the thermoplastic resin is 70 to 200 g / 10 minutes.
  • the rayon fiber has a number average fiber diameter of 5 to 30 ⁇ m, and the pellet has a number average length of 3 to 30 mm. With such a configuration, it is possible to provide pellets that are less likely to crack during production, a molded article formed from the pellets, and a method for producing the pellets.
  • a rayon fiber bundle is sometimes referred to as a rayon fiber bundle.
  • a bundle of 2,000 to 30,000 rayon fibers arranged in parallel in the fiber length direction is used.
  • the pelletizer 3 cuts to a desired pellet length.
  • the pelletizer 3 cuts the strand by rotating in the direction of A in FIG.
  • energy is applied to the strand. If this energy is not well absorbed by the strand before the strand breaks, the energy cannot be absorbed at the interface between the thermoplastic resin and the rayon fiber or between the thermoplastic resin, and the pellets obtained are presumed to crack.
  • fibers other than glass fibers are good as reinforcing fibers.
  • the pellets of this embodiment contain a thermoplastic resin.
  • the thermoplastic resin used in this embodiment has a melt flow rate (MFR) of 70 to 200 g/10 minutes when measured at a temperature of 230° C. and a load of 2.16 kg according to JIS K 7210.
  • MFR melt flow rate
  • the rayon fiber bundle can be easily impregnated with the thermoplastic resin, and cracking of the pellets during production can be effectively suppressed.
  • the resin becomes hard, and cracking of pellets during production can be effectively suppressed.
  • the MFR of the thermoplastic resin is preferably 72 g/10 min or more, more preferably 75 g/10 min or more, still more preferably 78 g/10 min or more, and 80 g/10 min or more. More preferably, it may be 90 g/10 minutes or more, or 100 g/10 minutes or more.
  • the MFR of the thermoplastic resin is also preferably 200 g/10 min or less, more preferably 190 g/10 min or less, even more preferably 180 g/10 min or less, and 170 g/10 min or less. is more preferably 160 g/10 minutes or less, and may be 140 g/10 minutes or less, or 120 g/10 minutes or less.
  • thermoplastic resin used in the present embodiment is not particularly defined as long as it satisfies the above MFR, but polyolefin resin, polyamide resin, styrene resin, polycarbonate resin, polyvinyl chloride, polyvinylidene chloride, acrylic resin, polyester resin, Polyacetal resins and polyphenylene sulfide resins can be mentioned, preferably containing at least one selected from polyolefin resins and polyacetal resins, more preferably containing at least one selected from polypropylene resins and polyacetal resins, polypropylene More preferably, it contains a resin.
  • Polyolefin resins include polypropylene resin, polyethylene resin, poly-1-butene resin, polyisobutylene resin, ethylene-propylene copolymer, ethylene-propylene-diene terpolymer (however, the diene component as a raw material is 10 mass % or less), polymethylpentene resin, ethylene and/or propylene (however, these components as raw materials are 50 mol% or more) and other copolymer monomers (vinyl acetate, methacrylate alkyl ester, acrylic acid alkyl ester, aromatic Random, block, and graft copolymers with vinyl, etc.) can be used.
  • a polyolefin resin When a polyolefin resin is used as the thermoplastic resin, part of it is preferably an acid-modified polyolefin resin in order to facilitate the impregnation of the rayon fiber bundle.
  • the acid-modified polyolefin resin maleic anhydride and/or acid-modified polyolefin resin modified with maleic acid (preferably maleic anhydride-modified polypropylene resin) is preferable.
  • the acid content in the thermoplastic resin is 0.005 to 0.5 mass% on average in terms of maleic anhydride. A range is preferred.
  • the thermoplastic resin contains an acid-unmodified polypropylene resin and a maleic anhydride-modified polypropylene resin.
  • the blend ratio is 5 parts by mass or more of the acid-unmodified polyolefin resin per 1 part by mass of the acid-modified polyolefin resin. preferably 7 parts by mass or more, more preferably 10 parts by mass or more, preferably 99 parts by mass or less, more preferably 70 parts by mass or less, It is more preferably 60 parts by mass or less, even more preferably 50 parts by mass or less, and may be 40 parts by mass or less.
  • the thermoplastic resin may contain only one type each of the acid-unmodified polyolefin resin and the acid-modified polyolefin resin, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • thermoplastic resin contains a polyacetal resin
  • its type is not particularly limited.
  • a copolymer containing a divalent oxyalkylene group having 2 to 6 carbon atoms as a structural unit may also be used.
  • Examples of the oxyalkylene group having 2 to 6 carbon atoms include an oxyethylene group, an oxypropylene group, and an oxybutylene group.
  • the ratio of the oxyalkylene group having 2 to 6 carbon atoms to the total number of moles of the oxymethylene group and the oxyalkylene group having 2 to 6 carbon atoms is not particularly limited, and is 0.5 to 10 mol. %.
  • Trioxane is usually used as the main raw material to produce the above polyacetal resin.
  • a cyclic formal or a cyclic ether can be used.
  • Specific examples of cyclic formals include 1,3-dioxolane, 1,3-dioxane, 1,3-dioxepane, 1,3-dioxocane, 1,3,5-trioxepane, 1,3,6-trioxocane and the like.
  • Specific examples of cyclic ethers include ethylene oxide, propylene oxide and butylene oxide.
  • 1,3-dioxolane may be used as the main raw material, and in order to introduce an oxypropylene group, 1,3-dioxane may be used as the main raw material. In order to introduce an oxybutylene group, 1,3-dioxepane may be used as the main raw material.
  • the amount of hemiformal terminal groups, the amount of formyl terminal groups, and the amount of terminal groups unstable to heat, acid and base are small.
  • the hemiformal terminal group is represented by --OCH2OH
  • the formyl terminal group is represented by --CHO.
  • the thermoplastic resin in this embodiment may contain a resin additive within the scope of the present invention. Specifically, stabilizers (thermal stabilizers, antioxidants, etc.), ultraviolet absorbers, antistatic agents, flame retardants, flame retardant aids, anti-dripping agents, anti-fogging agents, anti-blocking agents, fluidity improvers. , plasticizers, dispersants, antibacterial agents, and the like. When these components are blended, the total amount is preferably 10% by mass or less of the thermoplastic resin, and may be 5% by mass or less.
  • the content of the thermoplastic resin in the pellets of the present embodiment is preferably 60% by mass or more, more preferably 62% by mass or more, further preferably 64% by mass or more, and 66% by mass or more. It is more preferable that the content is 67% by mass or more. By making it more than the said lower limit, there exists a tendency for intensity
  • the pellets of the present embodiment may contain only one type of thermoplastic resin, or may contain two or more types thereof. When two or more types are included, the total amount is preferably within the above range.
  • the pellet of this embodiment contains a bundle of 2,000 to 30,000 rayon fibers arranged in parallel in the fiber length direction. In this way, a bundle of 2,000 to 30,000 rayon fibers aligned in the length direction is used and cut as described above to obtain pellets containing long fibers.
  • the length of the pellet is usually the length of the rayon fiber, there is a tendency to easily obtain a molded article having excellent mechanical strength.
  • the rayon fiber used in this embodiment has a number average fiber diameter of 5 to 30 ⁇ m.
  • the number average fiber diameter of the rayon fibers is preferably 7 ⁇ m or more, more preferably 9 ⁇ m or more, still more preferably 10 ⁇ m or more, and even more preferably 11 ⁇ m or more.
  • the number average fiber diameter of the rayon fibers is preferably 28 ⁇ m or less, more preferably 25 ⁇ m or less, even more preferably 20 ⁇ m or less, even more preferably 15 ⁇ m or less, and 13 ⁇ m or less. It is even more preferable to have
  • the rayon fiber used in this embodiment preferably has a degree of X-ray orientation of 90% or more.
  • the degree of X-ray orientation is preferably 91% or more, more preferably 92% or more. Although the upper limit of the degree of X orientation may be 100%, it is practically 99% or less, 98% or less, 97% or less, 96% or less, or 95% or less.
  • the apparent Young's modulus of the rayon fiber used in the present embodiment is preferably 10 GPa or more, more preferably 12 GPa or more, still more preferably 14 GPa or more, even more preferably 15 GPa or more, and 16 GPa.
  • the above is even more preferable.
  • the apparent Young's modulus of the rayon fiber is preferably 50 GPa or less, more preferably 45 GPa or less, even more preferably 40 GPa or less, even more preferably 36 Pa or less, and 35 GPa or less. It is even more preferable to have By making it equal to or less than the upper limit, the effect of reducing pellet cracking tends to be further improved.
  • the tensile elongation of the rayon fiber used in the present embodiment is preferably 3% or more, more preferably 5% or more, even more preferably 7% or more, and even more preferably 9% or more. Preferably, it is 11% or more, and even more preferably 13% or more.
  • the tensile elongation of the rayon fiber is preferably 20% or less, more preferably 19% or less, even more preferably 18% or less, and even more preferably 17% or less.
  • Raw materials for the rayon fibers used in this embodiment include viscose rayon, polynosic, modal, cupra, lyocell (Tencel), Bocell and FORTIZAN (manufactured by CELANESE) obtained by stretching cellulose acetate and then saponifying it with an alkali. fiber) etc. can be used.
  • the content of rayon fiber in the pellets of the present embodiment is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and 30 parts by mass or more with respect to 100 parts by mass of the thermoplastic resin. is more preferred. By setting the content to the above lower limit or more, the strength, rigidity and impact resistance of the resulting molded article tend to be further improved.
  • the content of rayon fiber in the pellets of the present embodiment is preferably 100 parts by mass or less, more preferably 90 parts by mass or less, and 80 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin. more preferably 70 parts by mass or less, and even more preferably 60 parts by mass or less.
  • the content of rayon fibers in the pellets of the present embodiment is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 16% by mass or more, and 17% by mass or more. It is more preferably 18% by mass or more, and even more preferably 19% by mass or more. By setting the content to the above lower limit or more, the strength, rigidity and impact resistance of the resulting molded article tend to be further improved.
  • the content of rayon fiber in the pellets of the present embodiment is preferably 40% by mass or less, more preferably 38% by mass or less, further preferably 36% by mass or less, and 35% by mass. is more preferably 34% by mass or less, and even more preferably 33% by mass or less.
  • the pellets of the present embodiment may contain only one type of rayon fiber, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • ⁇ Pellets> It is a pellet containing a thermoplastic resin and a bundle of 2,000 to 30,000 rayon fibers arranged in parallel in the fiber length direction.
  • the rayon fiber bundle is impregnated with at least a portion of the thermoplastic resin.
  • the thermoplastic resin is impregnated to the center of the rayon fiber bundle, but there may be a region in the center of the rayon fiber bundle that is not impregnated with the thermoplastic resin.
  • the pellets of this embodiment have a number average length of 3 to 30 mm. Moreover, the number average fiber length of the rayon fibers contained in the pellets is usually 3 to 30 mm.
  • Such pellets are also called long fiber pellets and are known as fibers in which the reinforcing fibers in the pellet have a long fiber length.
  • the number average length of the pellets is preferably 4 mm or more, preferably 25 mm or less, more preferably 20 mm or less, further preferably 15 mm or less, and 10 mm or less. is more preferably 8 mm or less, and may be 7 mm or less.
  • the number average fiber length of the rayon fibers contained in the pellets is preferably the same as the number average length of the pellets.
  • the above-mentioned "same" is intended to include things considered to be the same in the technical field of the present invention, in addition to being the same in a geometric sense.
  • the number average fiber length of the rayon fibers in the pellet is the same as the preferred range of the pellet length.
  • the number of rayon fibers is preferably 3,000 or more, more preferably 25,000 or less, even more preferably 20,000 or less, and 15,000 or less. more preferably 10,000 or less, even more preferably 8,000 or less, and may be 7,000 or less, or 6,000 or less.
  • the total content of the thermoplastic resin and the rayon fiber preferably accounts for 85% by mass or more of the pellet, more preferably 90% by mass or more, and 95% by mass or more. is more preferable, it is still more preferable that it accounts for 98% by mass or more, and it is still more preferable that it accounts for 99% by mass or more.
  • the pellet of the present embodiment is obtained by impregnating a bundle of 2,000 to 30,000 rayon fibers aligned in the length direction with the thermoplastic resin in a molten state and integrating them, and then a number average It can be produced by cutting to a length of 3 to 30 mm. More specifically, the pellets of the present embodiment are obtained by attaching 2,000 to 30,000 rayon fibers aligned in the length direction to a bundle of 2,000 to 30,000 rayon fibers in a molten state. It can be taken as and manufactured by cutting the strand with a pelletizer.
  • Strands (rayon fiber bundles of long fibers impregnated with a thermoplastic resin) and pellets can be produced from the strands by other known production methods than those described above.
  • JP-A-7-251437, JP-A-8-118490, etc. can be applied.
  • the pellet of this embodiment can be molded into a molded article.
  • other components can be blended as necessary.
  • Other components are exemplified by thermoplastic resins and resin additives.
  • thermoplastic resins include polyolefin resins, polyamide resins, styrene resins, polycarbonate resins, polyvinyl chloride, polyvinylidene chloride, acrylic resins, polyester resins, polyacetal resins, and polyphenylene sulfide resins. At least one selected is preferred.
  • resin additives include low shrinkage agents, flame retardants, flame retardant aids, plasticizers, antioxidants, ultraviolet absorbers, colorants, pigments, fillers, and the like.
  • the pellets of this embodiment may also be used as a pellet blend together with other thermoplastic resin pellets.
  • the ratio of rayon fibers in the resulting molded article can also be adjusted. Since the pellets of the present embodiment have good dispersibility in the molten resin, the rayon fibers can be uniformly dispersed in the molded article obtained.
  • Molded articles of the present embodiments are formed from the pellets of the present embodiments and/or the pellet blends described above.
  • the molded article of the present embodiment can use rayon fibers in which the cellulose molecules are highly oriented in the longitudinal direction of the fibers (for example, the degree of X-ray orientation is 90% or more), so that the strength of the fibers is high, and damage can occur easily. Shortening of rayon fibers is effectively suppressed.
  • the mechanical strength (flexural elastic modulus, etc.) of the resulting molded product can be increased.
  • the molded article obtained from the pellets of the present embodiment contains rayon fibers having a predetermined apparent Young's modulus, and is lighter than those containing inorganic fibers such as glass fibers ( That is, since the density can be reduced, a molded article having a large specific elastic modulus (bending elastic modulus/density) can be obtained.
  • the molded product of the present embodiment can have a desired shape according to the application, but as described above, since the specific elastic modulus can be increased, when it is made into a thin plate-shaped molded product, it is lightweight and One with high mechanical strength can be obtained. When the molded product of the present embodiment is made into a thin plate-like molded product, high mechanical strength can be obtained even when the thickness is set to 1 to 5 mm, for example. In addition, since the molded article formed from the pellets of the present embodiment contains rayon fibers, it does not leave a combustion residue like glass fibers when burned.
  • the molded product of this embodiment is lightweight and has high mechanical strength (especially specific elastic modulus), so it is a substitute for metal parts used in various fields such as electrical and electronic equipment, communication equipment, automobiles, building materials, and daily necessities. It can be used as a product, and is particularly suitable for housings of various devices and plate-like exterior materials.
  • Raw material PP1 Polypropylene resin (manufacturer: Japan Polypro, product number: BC10HRF, MFR 100 g / 10 minutes)
  • PP2 Dry blend of polypropylene resin (manufacturer: Japan Polypro, product number: BC10HRF, MFR 100g/10 minutes) and soft polypropylene (manufacturer: Idemitsu Kosan, product number: Elmodu S-600, MFR 2600g/10 minutes) at a mass ratio of 100/30. bottom.
  • the MFR after blending was 150 g/10 min.
  • PP3 Dry blend of polypropylene resin (manufacturer: Japan Polypro, product number: BC10HRF, MFR 100 g/10 minutes) and soft polypropylene (manufacturer: Idemitsu Kosan, product number: Elmodu S-600, MFR 2600 g/10 minutes) at a mass ratio of 100/70 bottom.
  • the MFR after blending was 300 g/10 min.
  • PP4 polypropylene resin (manufacturer: Japan Polypro, product number: BC05B, MFR50g/10 minutes)
  • PP5 polypropylene resin (manufacturer: Japan Polypro, product number: BC06C, MFR60g/10 minutes)
  • PP6 polypropylene resin (manufacturer: Japan Polypro, product number: BC08F, MFR75g/10 minutes)
  • MAPP maleic anhydride-modified polypropylene resin, manufacturer: Sanyo Chemical Industries, product number: Yumex 1001, MFR 230 g/10 minutes
  • Rayon fiber bundle manufacturer: Cordenka, product number: RT700, number average fiber diameter 13 ⁇ m, degree of X-ray orientation 92%, number of fibers 1000, apparent Young's modulus 16 GPa, tensile elongation 16%
  • Glass fiber bundle Manufacturer: Nippon Electric Glass, product number: T-431N, number average fiber diameter 17 ⁇ m, number of fibers 4000, apparent Young's modulus 74 GPa, tensile elongation 3%
  • melt flow rate MFR
  • the melt flow rate of the thermoplastic resin and resin component was measured according to JIS K 7210 at a temperature of 230°C and a load of 2.16 kg. The unit is g/10 minutes.
  • ⁇ Tensile elongation> The tensile elongation of the rayon fiber was measured in accordance with JIS L1013 at a sample fiber length of 2.5 cm and a crosshead speed of 2.5 cm/min after conditioning for one week in an atmosphere of 20°C and a relative humidity of 65%. .
  • the unit is %.
  • Examples 1-4, Comparative Examples 1-4 ⁇ Production of pellets> Among the components shown in Table 1, the components excluding rayon fiber are added from the top feed port of a twin-screw extruder (trade name: AS type 30 m / m, manufactured by Nakatani Kikai Co., Ltd.) The ratio shown in Table 1 (unit: mass%) ), and melt-kneaded at a set cylinder temperature of 200° C. and a screw rotation speed of 10 rpm to obtain a melt of the resin component.
  • a twin-screw extruder trade name: AS type 30 m / m, manufactured by Nakatani Kikai Co., Ltd.
  • 31 is a roving
  • 10 is a melt of a resin component
  • 22 is an impregnation die
  • 41, 42, 43 and 44 are impregnation rolls
  • 40B is a guide roll
  • 24 is a nozzle
  • 32 indicate each strand.
  • the pellets of this embodiment were able to effectively suppress pellet cracking during production.

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  • Manufacturing & Machinery (AREA)
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PCT/JP2022/047396 2021-12-28 2022-12-22 ペレット、成形品およびペレットの製造方法 Ceased WO2023127688A1 (ja)

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EP22915911.6A EP4458886A1 (en) 2021-12-28 2022-12-22 Pellets, molded article, and pellet manufacturing method
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US18/724,005 US20250065537A1 (en) 2021-12-28 2022-12-22 Pellets, molded article, and method for producing pellets
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