WO2023243281A1 - 複合樹脂組成物及び複合樹脂成形体 - Google Patents

複合樹脂組成物及び複合樹脂成形体 Download PDF

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WO2023243281A1
WO2023243281A1 PCT/JP2023/018113 JP2023018113W WO2023243281A1 WO 2023243281 A1 WO2023243281 A1 WO 2023243281A1 JP 2023018113 W JP2023018113 W JP 2023018113W WO 2023243281 A1 WO2023243281 A1 WO 2023243281A1
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resin
molecular weight
filler
composite resin
low molecular
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English (en)
French (fr)
Japanese (ja)
Inventor
理史 浜辺
正義 今西
俊文 名木野
彰馬 西野
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to CN202380042262.1A priority Critical patent/CN119173589A/zh
Priority to EP23823582.4A priority patent/EP4541860A4/en
Priority to JP2024528389A priority patent/JPWO2023243281A1/ja
Publication of WO2023243281A1 publication Critical patent/WO2023243281A1/ja
Priority to US18/967,705 priority patent/US20250092229A1/en
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    • 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
    • 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
    • C08J3/203—Solid polymers with solid and/or liquid additives
    • 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
    • C08J5/045—Reinforcing macromolecular compounds with loose or coherent fibrous material with vegetable or animal 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
    • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • 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
    • 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
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethylene
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • 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
    • C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2401/02—Cellulose; Modified cellulose
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/12—Polypropene

Definitions

  • the present disclosure relates to a composite resin composition that has excellent fluidity and moldability and can suppress appearance defects such as bleed-out of a molded article, and a composite resin molded article that is a molded article containing the composite resin composition.
  • general-purpose plastics such as polyethylene (PE), polypropylene (PP), polystyrene (PS), and polyvinyl chloride (PVC) are not only very cheap, but also easy to mold, compared to metals or ceramics. It is lightweight and weighs a fraction of the weight. Therefore, general-purpose plastics are used as materials for a variety of daily necessities such as bags, various packaging, various containers, sheets, etc., as well as industrial parts such as automobile parts and electrical parts, home appliances, construction supplies, daily necessities, and miscellaneous goods. It is often used as a material.
  • PE polyethylene
  • PP polypropylene
  • PS polystyrene
  • PVC polyvinyl chloride
  • general-purpose plastics have drawbacks such as insufficient mechanical strength. Therefore, general-purpose plastics do not have sufficient properties required for materials used in mechanical products such as automobiles, and various industrial products including electrical, electronic, and information products, and their range of application is limited. The current situation is that it is restricted.
  • engineering plastics such as polycarbonate, fluororesins, acrylic resins, and polyamides have excellent mechanical properties and are used in various industrial products such as automobiles and other mechanical products, as well as electrical, electronic, and information products. It is being However, engineering plastics have problems such as being expensive, difficult to recycle monomers, and having a large environmental burden.
  • Dispersing filler in the resin improves mechanical strength, but on the other hand, the fillers get entangled with each other in the composite resin, resulting in poor fluidity and poor moldability. Furthermore, the higher the filler concentration and the longer the fibers are, the more entangled they become and the worse the fluidity becomes.
  • Patent Document 1 cellulose composite polyethylene consisting of 10 to 70% cellulose powder and 25 to 89% polyethylene is used to improve fluidity. , 0.5 to 17.5% of wax is added to provide a molded product with improved surface roughness.
  • Patent Document 1 wax is used to improve fluidity, but since it is uniformly dispersed in the resin, the fluidity is improved, but there is a problem of bleed-out where the wax precipitates on the surface of the molded product. was there. There was also the problem of reduced strength.
  • An object of the present invention is to provide a composite resin composition having good appearance.
  • a composite resin composition according to the present disclosure includes a main resin, a low molecular weight resin, a compatibilizer, and a filler.
  • the low molecular weight resin is the same type of resin as the base resin, the molecular weight of the low molecular weight resin is lower than the molecular weight of the base resin, and the compatibilizer has substantially the same molecular structure as the base resin.
  • the composite resin composition according to the present disclosure it is possible to realize a composite resin molded article that has both fluidity and strength and can suppress the occurrence of bleed-out.
  • FIG. 1 is a schematic cross-sectional view showing a cross-sectional structure of a composite resin molded body according to Embodiment 1.
  • FIG. 1 is an enlarged schematic cross-sectional view of a composite resin molded body according to Embodiment 1.
  • FIG. 2 is a schematic diagram of a fibrous filler that is a component of the composite resin molded body according to Embodiment 1.
  • FIG. 3B is a partially enlarged view including an end portion of the fibrous filler in FIG. 3A.
  • 1 is an electron microscope image of a fibrous filler in a composite resin molded article according to Embodiment 1.
  • 1 is a schematic diagram of a manufacturing process of a composite resin molded body according to Embodiment 1.
  • FIG. Table 1 shows the measurement results in Examples 1 to 5 and Comparative Examples 1 to 7.
  • the composite resin composition according to the first aspect includes a base resin, a low molecular weight resin, a compatibilizer, and a filler, and the low molecular weight resin is a low molecular weight body of the same type of resin as the base resin,
  • the compatibilizer has substantially the same molecular structure as the base resin.
  • the compatibilizer in the composite resin composition may be a graft polymer of a resin having substantially the same molecular structure as the base resin. good.
  • the number average molecular weight Mnk of the base resin in the composite resin composition is 500 or more times the number average molecular weight Mnt of the low molecular weight resin.
  • the molecular weight peak of the composite resin composition may be two peaks.
  • the low molecular weight resin and the compatibilizer are present around the fibrous filler in a larger amount than in the base resin, and the outer periphery thereof It may be a structure in which the base resin is present in the main resin.
  • the filler in the composite resin composition includes a fibrous filler and a particulate filler having a smaller aspect ratio than the fibrous filler.
  • the fibrous filler has an aspect ratio of 10 or more
  • the particulate filler has an aspect ratio of 2 or less
  • the proportion of the fibrous filler is 1 wt% or more and 10 wt% or less
  • the fibrous filler has an aspect ratio of 10 or more.
  • the proportion occupied by the particulate filler is 50 wt% or more and 70 wt% or less.
  • the fibrous filler in the composite resin composition is defibrated only at the ends of the fibrous filler in the fiber length direction.
  • the concentration of low molecular weight resin around the part where the surface area has increased due to defibration may be higher than the concentration of low molecular weight resin around the central part in the fiber length direction which is not defibrated.
  • the filler may be a natural material containing cellulose.
  • the base resin may be an olefin resin.
  • the composite resin molded article according to the ninth aspect is a molded article containing the composite resin composition according to any one of the first to eighth aspects.
  • FIG. 1 is a schematic cross-sectional view showing the cross-sectional structure of a composite resin molded body 10, which is a molded body containing the composite resin composition according to the first embodiment.
  • FIG. 2 is an enlarged schematic cross-sectional view of the composite resin molded body 10 according to the first embodiment.
  • the composite resin composition according to Embodiment 1 consists of a melt-kneaded product containing a base resin, a filler, a low molecular weight resin, and an additive. As shown in the cross-sectional schematic diagrams of FIGS. 1 and 2, the composite resin composition includes a base resin 1, a fibrous filler 2, a particulate filler 3, a low molecular weight resin 4, and at least a compatibilizer as an additive. blended and dispersed.
  • the main resin 1 is preferably a thermoplastic resin in order to ensure good moldability.
  • Thermoplastic resins include olefin resins (including cyclic olefin resins) such as polyethylene and polypropylene, styrene resins, (meth)acrylic resins, organic acid vinyl ester resins or their derivatives, vinyl ether resins, and halogen-containing resins.
  • Resin polycarbonate resin, polyester resin, polyamide resin, thermoplastic polyurethane resin, polysulfone resin (polyether sulfone, polysulfone, etc.), polyphenylene ether resin (2,6-xylenol polymer, etc.), cellulose derivative ( cellulose esters, cellulose carbamates, cellulose ethers, etc.), lignin resin, modified lignin resin, silicone resin (polydimethylsiloxane, polymethylphenylsiloxane, etc.), rubber or elastomer (diene rubber such as polybutadiene, polyisoprene, styrene) -butadiene copolymer, acrylonitrile-butadiene copolymer, acrylic rubber, urethane rubber, silicone rubber, etc.), engineered plastics, etc.
  • the resin may be derived from petroleum, plants, or microorganisms. Further, the resin may be a recycled resin obtained by reprocessing a resin that has been molded once, and examples of the recycling method include material recycling, chemical recycling, and the like.
  • the above resins may be used alone or in combination of two or more. Further, it may be degradable by microorganisms, water, heat, etc. Note that the main resin 1 only needs to have thermoplasticity, and is not limited to the above-mentioned materials.
  • the main resin 1 is preferably an olefin resin or polyamide resin that has a relatively low melting point.
  • Olefin resins include homopolymers of olefin monomers, copolymers of olefin monomers, and copolymers of olefin monomers and other copolymerizable monomers. It will be done.
  • olefinic monomers include chain olefins ( ⁇ -C2-20 olefins such as ethylene, propylene, 1-butene, isobutene, 1-pentene, 4-methyl-1-pentene, and 1-octene). , cyclic olefins, etc.
  • olefinic monomers may be used alone or in combination of two or more.
  • chain olefins such as ethylene and propylene are preferred.
  • other copolymerizable monomers include fatty acid vinyl esters such as vinyl acetate and vinyl propionate; (meth)acrylic monomers such as (meth)acrylic acid, alkyl (meth)acrylate, and glycidyl (meth)acrylate.
  • unsaturated dicarboxylic acids or their anhydrides such as maleic acid, fumaric acid, and maleic anhydride; vinyl esters of carboxylic acids (e.g., vinyl acetate, vinyl propionate, etc.); cyclic olefins such as norbornene and cyclopentadiene; Examples include dienes such as butadiene and isoprene. These copolymerizable monomers may be used alone or in combination of two or more.
  • olefin resins include polyethylene (low density, medium density, high density, linear low density polyethylene, etc.), polypropylene, ethylene-propylene copolymer, ternary copolymer such as ethylene-propylene-butene-1, etc.
  • Examples include copolymers of chain olefins (especially ⁇ -C2-4 olefins) such as polymers.
  • Polyamide resins which are polymers made by bonding many monomers through amide bonds, include nylon (polyamide) 6, nylon 11, nylon 12, nylon 66, nylon 610, nylon 612, nylon 1010, nylon 1012, and nylon 6T. Examples include.
  • the composite resin composition and molded article according to Embodiment 1 have the following objectives, such as improving the adhesiveness between the fibrous filler 2 and the main resin 1 or the dispersibility of the fibrous filler 2 in the main resin 1. It may also contain additives.
  • additives include various titanate coupling agents, silane coupling agents, unsaturated carboxylic acids, maleic acid, maleic anhydride, or modified polyolefins grafted with maleic anhydrides, fatty acids, fatty acid metal salts, fatty acid esters, etc. Can be mentioned.
  • the above-mentioned silane coupling agent is preferably an unsaturated hydrocarbon type or an epoxy type.
  • the additive in this embodiment is preferably a polymer obtained by graft-polymerizing a hydrophilic group such as maleic anhydride to a polymer as described above, and the additive polymer is a resin ( A compatibilizing agent) is more preferable.
  • FIG. 3A is a schematic diagram of a fibrous filler 2 that is a component of the composite resin molded body according to the first embodiment.
  • FIG. 3B is a partially enlarged view including the end portion 5 of the fibrous filler 2 in FIG. 3A.
  • FIG. 4(a) is an electron microscope image of the fibrous filler in the composite resin molded article according to Embodiment 1
  • FIG. 4(b) is an electron micrograph showing a partially enlarged end of the fibrous filler in FIG. 4(a). It is.
  • the fibrous filler 2 will be explained. Among the fibrous fillers, there are also particulate fillers that have approximately the same diameter and fiber length.
  • the particulate filler is basically the same material as the fibrous filler 2, and only differs in filler length and aspect ratio. Therefore, in the following explanation, the fibrous filler 2 will be described in detail.
  • the fibrous filler 2 (hereinafter sometimes simply referred to as "fiber") contained in the composite resin composition and the molded body in this embodiment is a composite resin molded body molded using the composite resin composition. It is used primarily to improve mechanical properties and improve dimensional stability by lowering the coefficient of linear expansion.
  • the fibrous filler 2 preferably has a higher elastic modulus than the base resin 1, and specifically includes carbon fiber, carbon nanotube, pulp, cellulose, cellulose nanofiber, lignocellulose, and lignocellulose.
  • modified fibers whose surfaces and ends are chemically modified. It may be needle-like instead of fibrous, and may be wood powder or bark obtained from cedar, cypress, bamboo, reed, or powder of coffee, barley, tea leaves, etc. Furthermore, among these, carbons and celluloses are particularly preferred from the viewpoints of availability, high elastic modulus, and environmental friendliness. Furthermore, from the perspective of a recycling-oriented society, natural fibers such as cellulose and wood flour, natural materials, and waste materials derived from these materials are preferable.
  • the shapes of the fibrous filler and particulate filler will be explained.
  • the starting materials for the fibrous filler and particulate filler are the same, and the particulate filler is ground into particles more finely.
  • the symbol L in FIG. 3A is the length of the fibrous filler or particulate filler (hereinafter sometimes referred to as "fiber length").
  • the symbol d in FIG. 3B is the width of the fibrous filler or particulate filler (hereinafter sometimes referred to as "fiber diameter").
  • L/d aspect ratio
  • the elastic modulus is improved.
  • the aspect ratio of the fibrous filler is preferably 10 or more. However, if there are many fibers with a large aspect ratio, the fibers will become entangled, resulting in poor fluidity and moldability. On the other hand, when there are many fibers with a small aspect ratio, that is, when there are many particulate fillers, the fluidity is improved and the appearance is good with less fiber aggregates.
  • the aspect ratio of the particulate filler is preferably 2 or less. However, when the aspect ratio of fibers is small, that is, there is a large amount of particulate filler, the elastic modulus decreases.
  • the proportion of the fibrous filler in the filler is, for example, 1 wt% or more and 10 wt% or less, and the proportion of the particulate filler in the filler is, for example, 50 wt% or more and 70 wt% or less.
  • Additives are additives for improving fluidity, and include wax, plasticizers, internal additives, external additives, and the like. If it is not compatible with the base resin, cracks may easily form between the base resin and the base resin, which may become the starting point of cracks. Therefore, the additive is preferably a low molecular weight substance of the base resin.
  • the molecular weight peaks of the composite resin composition and the molded product do not have a single broad waveform, but have two waveforms: a peak of the base resin and a peak of the low molecular weight substance. This makes it possible to achieve both strength as a composite resin and fluidity during molding.
  • the state of the resin and fibrous filler in the composite resin composition and molded article will be described. If the low molecular weight resin is scattered in the composite resin, it will simultaneously cause a decrease in strength and bleed out.
  • a structure is created in which a large amount of low molecular weight resin is present around the fibrous filler and particulate filler, and the base resin is present around the periphery thereof.
  • the particulate filler By covering the particulate filler with a low molecular weight resin, deterioration in fluidity due to fiber entanglement can be suppressed.
  • the soft low molecular weight resin makes it possible to alleviate stress and improve strength.
  • the main resin is present on the outside of the low molecular weight resin, the low molecular weight resin, which tends to bleed out, does not come out to the outside, making it difficult to bleed out as a molded product.
  • the fibrous filler 2 it is most preferable for the fibrous filler 2 to have a structure in which the defibrated portion 6 in the fiber length direction is partially defibrated. By defibrating, a large amount of low molecular weight resin 4 can be entangled and present around it. Defibration section 6 indicates a defibration site.
  • the optimal fiber shape is calculated as follows from experiments and simulation results.
  • the fiber length L of the entire fibrous filler 2 is preferably 5% or more and 30% or less of the fiber length L of the fiber filler 2 as a whole.
  • the fibrillated portion 6 is less than 5% of the total fiber length L, the specific surface area is small, so a large amount of low molecular weight resin cannot exist, and if it is 30% or more, the resin will thicken and the fluidity will deteriorate. do.
  • aspect ratio The relationship between aspect ratio and elastic modulus will be described as the strength of composite resin molded bodies.
  • stress is applied to a composite resin molded article, if there are fibers with a large aspect ratio, even if the resin stretches, the highly rigid fibers do not stretch easily, so the composite resin does not become distorted. Therefore, the elastic modulus is improved.
  • the strain suppressing effect of the fibers is weakened when stress is applied, the composite resin becomes distorted, and the elastic modulus decreases.
  • the fibrous filler has a large specific surface area, since a larger number of bonding interfaces between the fibrous filler and the main resin will lead to an improvement in the elastic modulus.
  • the characteristics of the fibrous filler 2 will be explained.
  • the types of the base resin 1 and the fibrous filler 2 are as described above.
  • the fibrous filler 2 is too soft compared to the base resin 1, that is, has a low elastic modulus, the composite resin molded product as a whole As a result, the elastic modulus decreases, resulting in a decrease in strength.
  • the fibrous filler 2 is too hard compared to the base resin 1, that is, has a high elastic modulus, the shock waves generated during impact will not be propagated and will be absorbed at the interface between the base resin 1 and the fibrous filler 2. Therefore, cracks and crazes are likely to occur near the interface, resulting in a drop in impact resistance.
  • the fibrous filler 2 has a higher elastic modulus and that the difference is as small as possible.
  • the optimal relationship is calculated from simulation results, and the difference in elastic modulus between the main resin 1 and the fibrous filler 2 is preferably within 20 GPa.
  • these fibrous fillers 2 are used with various titanate coupling agents, silane coupling agents, unsaturated carbon dioxide, etc. for the purpose of improving adhesion with the main resin 1 or dispersibility in the composite resin molding.
  • a modified polyolefin grafted with an acid, maleic acid, maleic anhydride, or anhydride thereof, a fatty acid, a fatty acid metal salt, a fatty acid ester, etc. may be used.
  • it may be surface-treated with a thermosetting or thermoplastic polymer component.
  • FIG. 5 is a flow diagram illustrating the manufacturing process of the composite resin molded body in the first embodiment.
  • the fibrous filler including the particulate filler and the powdered or liquid low molecular weight resin (low molecular weight body) are pre-mixed before being introduced into the melt-kneading processing apparatus. Pre-mixing does not involve heating, but rather using a mixer or stirrer. As a result, the low molecular weight resin enters the fluffy portions of the fibers of the fibrous filler.
  • the mixture is put into a melt-kneading device (kneading device) together with the base resin, compatibilizing agent, etc., other additives are added as needed, and the mixture is melt-kneaded in the device.
  • a melt-kneading device kneading device
  • the base resin, low molecular weight resin, additives, and the like are melted, and fibrous fillers and the like are dispersed in the melted base resin and the like.
  • the shearing action of the device promotes defibration of aggregates of the fibrous filler, allowing the fibrous filler to be finely dispersed in the base resin.
  • fibrous fillers and particulate fillers fibers have been defibrated in advance through pretreatment such as wet dispersion.
  • pretreatment such as wet dispersion.
  • the fibrous filler is defibrated in advance in the solvent used in wet dispersion, it is easier to defibrate than in the molten base resin, so it is difficult to defibrate only the ends, and the fibrous filler The entire filler ends up in a defibrated state.
  • adding pre-treatment increases the number of steps, resulting in a problem of poor productivity.
  • the base resin and additives are not pretreated by wet dispersion for the purpose of defibrating and modifying the fibrous filler and particulate filler.
  • Melt-kneading treatment all-dry method
  • wet dispersion treatment of the fibrous filler it is possible to partially defibrate only the ends of the fibrous filler as described above, and the number of steps is small, improving productivity. Can be done.
  • kneading methods include a single-screw kneader, a twin-screw kneader, a roll kneader, and a Banbury kneader. Mixers, combinations thereof, and the like.
  • a continuous twin-screw kneader and a continuous roll kneader are particularly preferred from the viewpoints of ease of applying high shear and high productivity. Any kneading method other than the above may be used as long as it is a method that can apply high shear stress.
  • the composite resin composition extruded from the melt-kneading device is produced into a pellet shape through a cutting process using a pelletizer or the like.
  • Methods for pelletizing immediately after melting the resin include an air hot cut method, an underwater hot cut method, and a strand cut method.
  • a pulverization method in which a molded body or sheet is once formed and then crushed and cut.
  • Example 1 A pulp-dispersed polypropylene composite resin molded body was manufactured by the following manufacturing method.
  • Softwood pulp manufactured by Mitsubishi Paper Mills, trade name: NBKP Celgar
  • This softwood pulp was pulverized using a pulverizer to obtain a mixture of fibrous filler and particulate filler.
  • the aspect ratio and surface area due to fluff were adjusted through the grinding process.
  • the mixture of the fibrous filler and particulate filler and the additive low molecular weight polypropylene manufactured by Sanyo Kasei Co., Ltd., trade name: Viscol 550-P
  • polypropylene manufactured by Prime Polymer Co., Ltd., trade name: J108M
  • maleic anhydride-modified polypropylene manufactured by Sanyo Chemical Industries, Ltd., trade name: Umex
  • the above fibrous filler and additives were added.
  • the mixture was weighed and dry blended in a weight ratio of 38:2:60. Thereafter, the mixture was melt-kneaded and dispersed using a twin-screw kneader (KRC kneader manufactured by Kurimoto Iron Works Co., Ltd.).
  • the shear force can be changed by changing the screw configuration of the twin-screw kneader, and in Example 1, a medium shear type was used.
  • the resin melt was hot-cut to produce pulp-dispersed polypropylene pellets, which are a composite resin composition.
  • test pieces of composite resin molded bodies were produced using an injection molding machine (180AD manufactured by Japan Steel Works).
  • the conditions for producing the test piece were a resin temperature of 210° C., a mold temperature of 60° C., an injection speed of 60 mm/s, and a holding pressure of 80 MPa.
  • the shape of the test piece was changed according to the evaluation items described below, and a size 1 dumbbell was prepared for measuring the elastic modulus.
  • a test piece of the obtained pulp-dispersed polypropylene composite resin molded article was evaluated by the following method.
  • the obtained pulp-dispersed polypropylene pellets were immersed in a xylene solvent to dissolve the polypropylene, and the shape of the remaining pulp fibers was observed using SEM.
  • the average percentage with an aspect ratio of 10 or more was 7.5%
  • the average percentage with an aspect ratio of 2 or less was 55%
  • the rest had an aspect ratio of 2 or more. It was large, less than 10 fibers.
  • Fillers with an aspect ratio of 10 or more are called fibrous fillers
  • fillers with an aspect ratio of 2 or less are called particulate fillers.
  • the ends of the fibers were in a defibrated state, and the average ratio of the defibrated portion to the length of one fiber was 23%.
  • melt viscosity In order to evaluate the fluidity of the obtained pulp-dispersed polypropylene pellets, the melt viscosity was measured using a melt viscometer (trade name: Capillograph F-1, manufactured by Toyo Seiki Seisakusho Co., Ltd.). The melt viscosity was measured at a shear rate in the range of 12 to 2430 [1/sec]. The melt viscosity at a shear rate of 1220 [1/sec] was approximately 250 [Pa ⁇ s].
  • Example 2 In Example 2, a low shear type kneader was used to prevent the fibers from fibrillating. Pulp-dispersed polypropylene pellets and composite resin molded bodies were produced in the same manner as in Example 1 under other material conditions and process conditions. Evaluations were also conducted in the same manner as in Example 1.
  • Example 3 In Example 3, the number of passes through the kneader was increased to 7 times the normal number to facilitate fibrillation of the fibers. Pulp-dispersed polypropylene pellets and composite resin molded bodies were produced in the same manner as in Example 1 under other material conditions and process conditions. Evaluations were also conducted in the same manner as in Example 1.
  • Example 4 In Example 4, the pulp concentration was changed to 70%, and other material conditions and process conditions were the same as in Example 1 to produce pulp-dispersed polypropylene pellets and composite resin molded bodies. Evaluations were also conducted in the same manner as in Example 1.
  • Example 5 In Example 5, the main resin was polyethylene with a number average molecular weight of 200,000, the low molecular weight resin was polyethylene with a number average molecular weight of 2,000, the compatibilizer was acid-modified polyethylene, and the other material conditions and process conditions were as follows. Pulp-dispersed polyethylene pellets and composite resin molded bodies were produced in the same manner as in Example 1. Evaluations were also conducted in the same manner as in Example 1.
  • Comparative example 1 Comparative Example 1, the mixture of fibrous filler and particulate filler and the low molecular weight polypropylene additive were not pre-mixed in a mixer, but the base resin polypropylene and the additive were all mixed at the same time. Pulp-dispersed polyethylene pellets and composite resin molded bodies were produced using the same material and process conditions as in Example 1. Evaluations were also conducted in the same manner as in Example 1.
  • Comparative example 2 In Comparative Example 2, the additive low molecular weight polypropylene was used to have a number average molecular weight of 200, and other material conditions and process conditions were the same as in Example 1 to produce pulp-dispersed polyethylene pellets and composite resin molded bodies. Evaluations were also conducted in the same manner as in Example 1.
  • Comparative example 3 In Comparative Example 3, the additive low molecular weight polypropylene was used to have a number average molecular weight of 20,000, and other material conditions and process conditions were the same as in Example 1 to produce pulp-dispersed polyethylene pellets and composite resin molded bodies. . Evaluations were also conducted in the same manner as in Example 1.
  • Comparative example 4 In Comparative Example 4, the starting material for pulp was changed to powdered cellulose, and other material conditions and process conditions were the same as in Example 1 to produce pulp-dispersed polypropylene pellets and composite resin molded bodies. Evaluations were also conducted in the same manner as in Example 1.
  • Comparative example 5 pulp-dispersed polypropylene pellets and composite resin molded bodies were produced using the same material conditions and process conditions as in Example 1, without pulverizing the pulp. Evaluations were also conducted in the same manner as in Example 1.
  • Comparative example 6 a pulp-dispersed polyethylene pellet and a composite resin molded article were produced using the same material conditions and process conditions as in Example 1, without adding the low molecular weight polypropylene additive. Evaluations were also conducted in the same manner as in Example 1.
  • Comparative Example 7 pulp-dispersed polyethylene pellets and composite resin molded bodies were produced using the same material conditions and process conditions as in Example 1, without adding a compatibilizer. Evaluations were also conducted in the same manner as in Example 1.
  • Example 2 As is clear from Table 1 in Figure 6, in Example 2 where a low shear type kneader was used and the degree of fiber end defibration was 0%, the power to hold the low molecular weight resin around the fibers was Although it was somewhat weak and no obvious bleed-out was observed, some surface precipitation (bleed-out) was observed, resulting in a slightly poor appearance.
  • a fibrous filler and a particulate filler with a smaller aspect ratio than the fibrous filler the fibrous filler has an aspect ratio of 10 or more, the particulate filler has an aspect ratio of 2 or less, and the same resin type as the main resin is used as an additive.
  • a low molecular weight resin is premixed with a fibrous filler, and its number average molecular weight is 10 to 500 times that of the main resin, and the molecular weight peak of the composite resin molded product is two peaks, the flowability and moldability will be affected. It was confirmed that a composite resin molded article having excellent properties and capable of suppressing appearance defects such as bleed-out of the molded article could be obtained.
  • Example 3 in which the number of passes through the kneading machine was increased to 7 times the normal number to facilitate defibration of the fibers, the fibers were considerably defibrated in the composite resin molding, and the degree of end defibration was 60%. . As a result, the low molecular weight resin could be retained around the fibers, and a molded article without bleed-out was obtained, but the elastic modulus was low.
  • Example 4 in which the pulp concentration was changed to 70%, the melt viscosity was slightly higher due to the increased fiber concentration, making it somewhat difficult to mold, but the composite resin molded product was able to suppress appearance defects such as bleed-out of the molded product. was confirmed to be obtained.
  • Example 5 in which polyethylene was used as the main resin and low molecular weight resin, the elastic modulus decreased overall, the melt viscosity increased, and the melt viscosity increased slightly, compared to Example 1 in which polypropylene was used. Although it was difficult to mold, it was confirmed that a composite resin molded product could be obtained that could suppress appearance defects such as bleed-out of the molded product.
  • Comparative Example 1 which was not premixed, there was not much low molecular weight resin around the fibers, and bleed-out where the low molecular weight resin precipitated on the surface was observed, resulting in an unacceptable appearance.
  • Comparative Example 2 in which low molecular weight polypropylene was used with a number average molecular weight of 200, the molecular weight was too small compared to that of the main resin, so they were not compatible, and bleed-out where the low molecular weight resin precipitated on the surface was observed, resulting in poor appearance. It was rejected.
  • the composite resin molded article contains fibrous filler and particulate filler with a smaller aspect ratio than the fibrous filler, and the fibrous filler has an aspect ratio of 10 or more and the particulate filler has an aspect ratio of 2 or less.
  • a low molecular weight resin of the same resin type as the main resin is pre-mixed with the fibrous filler, and its number average molecular weight is 10 to 500 times that of the main resin, so that the molecular weight peak of the composite resin molded product has two peaks. It was confirmed that a composite resin molded article having excellent fluidity and moldability and capable of suppressing appearance defects such as bleed-out of the molded article can be obtained.
  • the composite resin molded article according to the present disclosure can improve fluidity and suppress bleed-out, and can provide a composite resin molded article that has better mechanical strength than conventional general-purpose resins.
  • the properties of the base resin can be improved, so it can be used as a substitute for engineering plastics or a substitute for metal materials. Therefore, the manufacturing cost of various industrial products or daily necessities made of engineering plastics or metals can be significantly reduced. Furthermore, it can be used for daily necessities, home appliance cases, building materials, automobile parts, etc.

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