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WO2025121259A1 - Composition de résine, procédé de production d'une composition de résine, composition de résine à base de polyoléfine, procédé de production d'une composition de résine à base de polyoléfine et corps moulé - Google Patents

Composition de résine, procédé de production d'une composition de résine, composition de résine à base de polyoléfine, procédé de production d'une composition de résine à base de polyoléfine et corps moulé Download PDF

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Publication number
WO2025121259A1
WO2025121259A1 PCT/JP2024/042325 JP2024042325W WO2025121259A1 WO 2025121259 A1 WO2025121259 A1 WO 2025121259A1 JP 2024042325 W JP2024042325 W JP 2024042325W WO 2025121259 A1 WO2025121259 A1 WO 2025121259A1
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WO
WIPO (PCT)
Prior art keywords
mass
resin composition
propylene
polyolefin
ethylene
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Pending
Application number
PCT/JP2024/042325
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English (en)
Japanese (ja)
Inventor
龍二 大橋
賢一 瀬野
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Publication of WO2025121259A1 publication Critical patent/WO2025121259A1/fr
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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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • 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
    • 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
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids

Definitions

  • the present invention relates to a resin composition, a method for producing the resin composition, a polyolefin-based resin composition, a method for producing the polyolefin-based resin composition, and a molded article containing the resin composition or the polyolefin-based resin composition.
  • Molded articles containing resin compositions are used in household goods, automobile parts, industrial parts such as electrical parts, daily necessities, miscellaneous goods, etc. Fillers are blended into such resin compositions to increase mechanical strength, etc. Examples of such fillers include inorganic powders such as talc and silica; cellulose-based powders such as wood flour and bamboo flour; and fibrous fillers such as natural fibers, glass fibers, and carbon fibers.
  • inorganic powders such as talc and silica
  • cellulose-based powders such as wood flour and bamboo flour
  • fibrous fillers such as natural fibers, glass fibers, and carbon fibers.
  • Patent Document 1 discloses wood flour pellets containing atactic polypropylene and wood flour as such resin compositions.
  • VOCs volatile organic compounds
  • the present invention was made in consideration of such problems, and aims to provide a resin composition that contains a plant-derived filler but is capable of producing a molded article with a relatively low amount of VOC emissions, a method for producing the resin composition, a polyolefin-based resin composition, a method for producing the polyolefin-based resin composition, and a molded article containing the resin composition or the polyolefin-based resin composition.
  • the resin composition according to the present invention contains a plant-derived filler (C) and a hydrophilic resin (D) having a hydroxyl group,
  • the total content of (C) and (D) is 100 mass%,
  • the content of the plant-derived filler (C) is 20% by mass or more and 91% by mass or less,
  • the method for producing a resin composition according to the present invention is a method for producing the resin composition, The method includes a step of kneading the plant-derived filler (C) and the hydrophilic resin having a hydroxyl group (D) using a kneader.
  • the polyolefin resin composition according to the present invention comprises a polyolefin resin (A), a modified polyolefin resin (B), a plant-derived filler (C), and a hydrophilic resin having a hydroxyl group (D),
  • the total content of (A), (B), (C) and (D) is taken as 100 mass%
  • the content of the polyolefin resin (A) is 1% by mass or more and 96.4% by mass or less
  • the content of the modified polyolefin resin (B) is 1% by mass or more and 20% by mass or less
  • the content of the plant-derived filler (C) is 1% by mass or more and 80% by mass or less
  • the content of the hydrophilic resin (D) having a hydroxyl group is from 1% by mass to 30% by mass.
  • the method for producing a polyolefin resin composition according to the present invention is a method for producing the polyolefin resin composition, and includes the following steps 1 and 2.
  • Step 1 A step of kneading the plant-derived filler (C) and the hydrophilic resin (D) having a hydroxyl group using a kneader.
  • Step 2 After step 1, a step of further adding and kneading the polyolefin resin (A) and the modified polyolefin resin (B).
  • the molded article according to the present invention contains the resin composition or the polyolefin-based resin composition.
  • the present invention provides a resin composition that contains a plant-derived filler but is capable of producing a molded article with a relatively low amount of VOC emissions, a method for producing the resin composition, a polyolefin-based resin composition, a method for producing the polyolefin-based resin composition, and a molded article that contains the resin composition or the polyolefin-based resin composition.
  • Resin Composition contains a plant-derived filler (C) and a hydrophilic resin having a hydroxyl group (D).
  • the plant-derived filler (C) may be any component that contains at least a plant-derived component and can be dispersed in the polyolefin resin (A).
  • the plant-derived filler (C) various known plant-derived fillers can be used.
  • the plant-derived filler (C) include cellulose, wood flour, bamboo flour, rice, rice bran, starch, and the like.
  • the plant-derived filler (C) is preferably cellulose, wood flour, or bamboo flour, and more preferably cellulose or wood flour.
  • the plant-derived filler (C) may be a bundle solidified using an adhesive such as a fiber bundle agent.
  • the resin composition may contain only one type of plant-derived filler (C), or may contain two or more types.
  • Examples of cellulose include powdered cellulose, cellulose fibers, and lignocellulose fibers.
  • Examples of raw materials for cellulose include natural materials such as wood (coniferous and broadleaf trees), cotton linters, kenaf, Manila hemp (abaca), sisal, jute, sabai grass, esparto grass, bagasse, rice straw, wheat straw, reed, and bamboo.
  • Cellulose may also be modified with functional monomers including, for example, acids, amines, and epoxies. Of these, the cellulose is preferably cellulose fiber.
  • Cellulose fibers include, for example, wood-based pulp obtained from conifers, broad-leaved trees, etc.; waste paper pulp, which is a recycled product of such wood-based pulp; non-wood-based pulp such as cotton or linters obtained from cotton, straw obtained from rice, bamboo obtained from bamboo, abaca obtained from Manila hemp, jute obtained from Indian hemp, and hemp obtained from hemp; and further, pulp using cereal fibers discarded during food processing, rayon fiber, regenerated cellulose fibers such as lyocell, etc.
  • the cellulose fibers are preferably wood-based pulp or waste paper pulp, and more preferably wood-based pulp.
  • Pulp is the cellulose, lignin, hemicellulose, oil, etc. contained in the molded body of a plant from which lignin and oil have been removed, or from which the hemicellulose content has been minimized. Depending on the application, pulp may be bleached to make it white.
  • the above-mentioned cellulose fibers may be those obtained by chemically or mechanically pulverizing the pulp to produce fine particles of 1 mm or less, or may be fine microfibrillated cellulose fibers that have been partially converted into nanocellulose.
  • biomass nanofibers refer to either long fiber biomass nanofibers or short fiber biomass nanofibers.
  • biomass nanofibers examples include cellulose nanofibers (CNF), chitin nanofibers, chitosan nanofibers, and silk nanofibers.
  • CNF cellulose nanofiber
  • the biomass nanofiber is preferably cellulose nanofiber (CNF) from the standpoints of chemical stability, thermal stability, and cost.
  • the average fiber diameter of the biomass nanofibers is preferably 3 nm or more and 100 nm or less, and more preferably 10 nm or more and 50 nm or less, from the viewpoint of the aspect ratio.
  • biomass nanofibers examples include mechanically defibrated biomass nanofibers produced by mechanical defibration, and chemically modified biomass nanofibers produced through chemical modification. Of these, the biomass nanofibers are preferably mechanically defibrated biomass nanofibers.
  • biomass nanofibers commercially available products may be used.
  • biomass nanofibers include BiNFi-s (registered trademark) manufactured by Sugino Machine Co., Ltd., Cellenpia (registered trademark) manufactured by Nippon Paper Industries Co., Ltd., ELLEX (registered trademark) manufactured by Daio Paper Co., Ltd., and nanoforest (registered trademark) manufactured by Chuetsu Pulp Industry Co., Ltd.
  • wood fiber refers to lignocellulosic fibers in general.
  • Lignocellulosic fibers are made by mechanically, thermomechanically, biologically, chemically, chemomechanically, or chemothermo-mechanically treating lignocellulosic materials derived from wood or non-wood plants, thereby softening, destroying, loosening, and pulverizing the middle layer that binds the fibers together like an adhesive.
  • lignocellulosic fibers is a general term, and plant fibrous materials that have been physically, chemically, or biologically treated (for example, delignification treatment in wood pulping, or retting treatment of herbs) to remove lignin, hemicellulose, etc. are also included in lignocellulosic fibers.
  • lignocellulosic fibers the above-mentioned can be used without any particular restrictions.
  • the wood may be either coniferous or broadleaf.
  • lignocellulosic fibers derived from non-wood plants include straw pulp, bagasse pulp, reed pulp, kenaf pulp, linen pulp, ramie pulp, hemp pulp, flax pulp, bamboo pulp, etc.
  • lignocellulose fibers for example, lignocellulose powder, kraft pulp, semi-chemical pulp, chemi-ground pulp, refiner ground pulp, thermomechanical pulp, ground wood pulp, dissolving pulp, mechanical pulp, fiberboard fibers, etc. can be preferably used.
  • Fiber for fiberboard is, in a broad sense, thermomechanical pulp, and in a narrow sense, the relatively coarse fibers within that.
  • thermomechanical pulp can be given as a form with a diameter of about 30 ⁇ m and a length of about 2 to 3 mm.
  • Such lignocellulosic fibers may be used alone or in combination of two or more types.
  • Any known method can be used to convert lignocellulosic materials into lignocellulosic fibers without any particular restrictions.
  • conventional methods for producing pulp, conventional methods for producing fibers for fiberboard, etc. can be used as appropriate.
  • One example of a method for converting lignocellulosic material into lignocellulosic fibers is to crush the lignocellulosic material into chips, then steam it in a preheater or presteamer at a pressure of about 1 to 10 Bar to soften the lignin and hemicellulose that are the components of the lignocellulosic material, and then defibrate it into fibers or fiber bundles using a disk-type blade while applying pressure in a pressurized refiner to produce the desired fibers.
  • Wood flour is mainly wood powder made by finely crushing wood.
  • wood include cypress, cedar, pine, Japanese larch, fir, birch, maple, ash, ash, oak, beech, persimmon, cherry, hornbeam, camellia, Chinese linden, chestnut, horse chestnut, poplar, magnolia, beech, Japanese bean, western hemlock, Douglas fir, maple, alder, rubber tree, ramin, lauan,ntang, mango, rengas, Japanese laurel, Japanese laurel, sumac, Japanese hazenoki, Japanese hazel, alder, birch, asada, catalpa, tabebuya, ibe, gayakan, corzia, canarywood, canarium, katsura, terminalia, idigbo, theme, erima, mersawa, parosapis, chengal, lesak, apitong, kruin, yang, and chu
  • the size of the plant-derived filler (C) is preferably 5000 ⁇ m or less, more preferably 3000 ⁇ m or less, even more preferably 1000 ⁇ m or less, and particularly preferably 200 ⁇ m or less.
  • the width of the wood fiber is preferably 1 ⁇ m or more and 100 ⁇ m or less, more preferably 10 ⁇ m or more and 50 ⁇ m or less.
  • the length of the wood fiber is preferably 0.1 mm or more and 50 mm or less, more preferably 1 mm or more and 5 mm or less. The length and width of such fibers can be adjusted to the desired length and width by adjusting the operating conditions such as the spacing between the refiner discs.
  • the width of the convergent is preferably 0.01 mm or more and 50 mm or less, and more preferably 0.1 mm or more and 40 mm or less.
  • the length of the convergent is preferably 0.5 mm or more and 20 mm or less, and more preferably 1 mm or more and 10 mm or less.
  • the plant-derived filler (C) can be obtained, for example, by processing at least one raw material selected from the group consisting of wood, pulp, paper, plant stems or leaves, and plant shells using a grinder.
  • Cellulose fibers from the plant-derived filler (C) can be obtained, for example, by the following method. Wood from the above-mentioned cellulose raw materials is coarsely crushed using a cutting machine such as a shredder, if necessary. The coarsely crushed wood is then processed or dried using an impact crusher or extruder. The processed cellulose raw material is then stirred using a media crusher to obtain cellulose fibers.
  • the plant-derived filler (C) may contain acetaldehyde as a VOC in an amount of 0.01 ppm or more and 5.00 ppm or less, or in an amount of 0.01 ppm or more and 1.00 ppm or less.
  • the content of the plant-derived filler (C) is from 20% to 91% by mass, preferably from 40% to 80% by mass, and more preferably from 40% to 70% by mass, with the total content of (C) and (D) being 100% by mass. Note that when the resin composition contains two or more types of plant-derived filler (C), the content of the plant-derived filler (C) is the total content.
  • hydrophilic resin having hydroxyl group (D) examples include polyvinyl alcohol, polyethylene oxide, polyethylene glycol, polyglycerin, etc.
  • the hydrophilic resin (D) having a hydroxyl group is preferably polyvinyl alcohol, polyethylene oxide, or polyethylene glycol, more preferably polyvinyl alcohol, from the viewpoint of obtaining a molded product having a relatively excellent tensile strength.
  • the resin composition may contain only one type of hydrophilic resin (D) having a hydroxyl group, or may contain two or more types.
  • Polyvinyl alcohol is a water-soluble polymer obtained as a hydrolysis (saponification) product of vinyl acetate.
  • examples of polyvinyl alcohol include various types of polyvinyl alcohol, such as low saponification, partial saponification, and complete saponification.
  • examples of polyvinyl alcohol include various types of polyvinyl alcohol, such as polyvinyl alcohol having functional groups such as carboxylic acid, sulfonic acid, quaternary ammonium salt, polyethylene oxide group, and acetoacetyl group; and copolymer polyvinyl alcohol of ethylene, butene, butenediol, etc.
  • the degree of polymerization of polyvinyl alcohol is preferably 100 or more and 1,000 or less, more preferably 100 or more and 600 or less, from the viewpoint of obtaining a molded article that contains a plant-derived filler but emits relatively little VOC.
  • the degree of saponification of polyvinyl alcohol is preferably 10 or more and 90 or less, more preferably 30 or more and 90 or less, and even more preferably 50 or more and 80 or less, from the viewpoint of obtaining a molded article that contains a plant-derived filler but emits relatively little VOC.
  • the hydrophilic resin (D) having a hydroxyl group is polyvinyl alcohol having a degree of polymerization of 100 or more and 1,000 or less, and a degree of saponification of 10 or more and 90 or less.
  • the degree of saponification and polymerization of polyvinyl alcohol can be measured in accordance with JIS K6726-1994.
  • the manufacturer's values measured using this method may be used for the degree of saponification and polymerization of polyvinyl alcohol.
  • polyvinyl alcohol commercially available products may be used.
  • examples of commercially available polyvinyl alcohol include Denka Poval manufactured by Denka Co., Ltd., Kuraray Poval manufactured by Kuraray Co., Ltd., JMR manufactured by Nippon Vinyl Acetate & Poval Co., Ltd., and Poval manufactured by Nippon Vinyl Acetate & Poval Co., Ltd.
  • the content of the hydrophilic resin (D) having hydroxyl groups is from 9 to 80% by mass, preferably from 20 to 60% by mass, and more preferably from 30 to 60% by mass, with the total content of (C) and (D) being 100% by mass. Note that when the resin composition contains hydrophilic resin (D) having two or more types of hydroxyl groups, the content of the hydrophilic resin (D) having hydroxyl groups is the total content.
  • the resin composition according to the present embodiment may contain other additives as necessary.
  • the other additives include pigments, dyes, inorganic fillers, neutralizers, antioxidants, lubricants, copper inhibitors, antifogging agents, antistatic agents, processing stabilizers, UV absorbers, light stabilizers, nucleating agents, transparent nucleating agents, processing aids, metal soaps, foaming agents, antibacterial agents, plasticizers, flame retardants, flame retardant aids, crosslinking agents, crosslinking aids, brightness enhancers, flowability modifiers, and crystallization retarders.
  • the method for producing a resin composition according to this embodiment is a method for producing the above-described resin composition, and includes a step of kneading the plant-derived filler (C) and the hydrophilic resin having a hydroxyl group (D) using a kneader.
  • the kneading method may be, for example, melt kneading, solid-phase shear continuous kneading, etc. Among these, the kneading method is preferably melt kneading.
  • the kneading machine used for the kneading may be, for example, a single screw extruder, a twin screw extruder, a Banbury mixer, a heat roll, a Labo Plastomill, etc.
  • the kneading machine is preferably a single screw extruder, a twin screw extruder, a Banbury mixer, or a Labo Plastomill, and more preferably a twin screw extruder, a Banbury mixer, or a Labo Plastomill.
  • the kneading temperature is preferably 160°C or higher and 230°C or lower, and more preferably 170°C or higher and 200°C or lower.
  • the rotation speed of the screw of the kneading machine is preferably 50 rpm or more and 500 rpm or less, more preferably 100 rpm or more and 500 rpm or less, and even more preferably 100 rpm or more and 300 rpm or less.
  • the kneading time is preferably from 1 minute to 15 minutes.
  • the components may be mixed simultaneously or sequentially.
  • the method for producing the resin composition according to this embodiment is, for example, as follows.
  • the hydrophilic resin (D) having hydroxyl groups is fed into a kneader (such as Labo Plastomill manufactured by Toyo Seiki Seisakusho), and then the plant-derived filler (C) is fed into the kneader.
  • the mixture is melt-kneaded for 5 minutes at a temperature of 180°C and a rotation speed of 100 rpm to obtain a resin composition.
  • the polyolefin resin composition according to this embodiment contains a polyolefin resin (A), a modified polyolefin resin (B), a plant-derived filler (C), and a hydrophilic resin having a hydroxyl group (D).
  • the polyolefin resin (A) is a resin containing an olefin polymer.
  • the polyolefin resin (A) means an unmodified polyolefin resin.
  • polystyrene resin (A) examples include polyethylene resin, polypropylene resin, etc.
  • the polyolefin resin (A) is preferably a polypropylene resin from the viewpoint of obtaining a molded article that contains a plant-derived filler but emits relatively little VOC.
  • the polypropylene resin is a resin containing a propylene polymer.
  • Propylene-based polymers are polymers that contain more than 50% by mass of monomer units derived from propylene.
  • Examples of propylene-based polymers include propylene homopolymers, random copolymers of propylene and monomers other than propylene, and heterophasic propylene polymer materials.
  • Polypropylene-based resins may contain only one type of propylene-based polymer, or may contain two or more types.
  • the polypropylene-based resin preferably contains, as a propylene-based polymer, at least one selected from the group consisting of propylene homopolymers and heterophasic propylene polymer materials, and more preferably contains a heterophasic propylene polymer material.
  • Propylene homopolymer can be produced, for example, by carrying out a polymerization process in which propylene is polymerized using a polymerization catalyst.
  • polymerization catalysts examples include Ziegler catalysts; Ziegler-Natta catalysts; catalysts containing a compound of a transition metal of Group 4 of the periodic table having a cyclopentadienyl ring and an alkylaluminoxane; catalysts containing a compound of a transition metal of Group 4 of the periodic table having a cyclopentadienyl ring, a compound that reacts with the transition metal compound to form an ionic complex, and an organoaluminum compound; and modified catalysts in which catalytic components (a compound of a transition metal of Group 4 of the periodic table having a cyclopentadienyl ring, a compound that forms an ionic complex, an organoaluminum compound, etc.) are supported on inorganic particles (silica, clay minerals, etc.).
  • polymerization catalyst examples include the catalysts described in JP-A-61-218606, JP-A-5-194685, JP-A-7-216017, JP-A-9-316147, JP-A-10-212319, JP-A-2004-182981, JP-A-2010-168545, and JP-A-2011-246699.
  • a polymer obtained by prepolymerizing propylene in the presence of the polymerization catalyst can also be used as the polymerization catalyst.
  • Polymerization methods include, for example, bulk polymerization, solution polymerization, and gas phase polymerization.
  • bulk polymerization refers to a method in which polymerization is carried out using a liquid olefin as a medium at the polymerization temperature.
  • Solution polymerization refers to a method in which polymerization is carried out in an inert hydrocarbon solvent such as propane, butane, isobutane, pentane, hexane, heptane, or octane.
  • Gas phase polymerization refers to a method in which a gaseous monomer is used as a medium and the gaseous monomer is polymerized in that medium.
  • Polymerization methods include, for example, batch, continuous, and combinations of these.
  • the polymerization method may be a multi-stage method in which multiple polymerization reaction tanks are connected in series.
  • the polymerization method is preferably a continuous gas phase polymerization method or a bulk-gas phase polymerization method in which bulk polymerization and gas phase polymerization are carried out continuously.
  • polymerization temperature polymerization pressure
  • monomer concentration polymer concentration
  • catalyst input amount polymerization time, and other polymerization conditions
  • the polymer may be dried at a temperature below the melting point of the polymer, if necessary, to remove residual solvent contained in the polymer and ultra-low molecular weight oligomers produced as by-products during production.
  • drying methods include those described in JP-A-55-75410 and Japanese Patent No. 2,565,753, etc.
  • the random copolymer of propylene and a monomer other than propylene contains monomer units derived from propylene and monomer units derived from a monomer other than propylene.
  • the content of monomer units derived from a monomer other than propylene is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.1% by mass or more and 20% by mass or less, based on the total mass of the copolymer (100% by mass).
  • Examples of monomers other than propylene include ethylene and ⁇ -olefins having 4 to 12 carbon atoms.
  • ⁇ -olefins are aliphatic unsaturated hydrocarbons having a carbon-carbon unsaturated double bond at the ⁇ -position.
  • Examples of ⁇ -olefins having 4 to 12 carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene, and 4-methyl-1-hexene.
  • the monomer other than propylene is preferably at least one selected from the group consisting of ethylene and ⁇ -olefins having 4 to 10 carbon atoms, more preferably at least one selected from the group consisting of ethylene, 1-butene, 1-hexene, and 1-octene, and even more preferably at least one selected from the group consisting of ethylene and 1-butene.
  • random copolymers of propylene and monomers other than propylene include propylene-ethylene random copolymers, propylene-1-butene random copolymers, propylene-1-hexene random copolymers, propylene-1-octene random copolymers, propylene-ethylene-1-butene random copolymers, propylene-ethylene-1-hexene random copolymers, and propylene-ethylene-1-octene random copolymers.
  • a random copolymer of propylene and a monomer other than propylene can be produced, for example, by polymerizing propylene and a monomer other than propylene according to the polymerization catalyst, polymerization method, polymerization method, and polymerization conditions that can be used in the production of the propylene homopolymer described above.
  • the heterophasic propylene polymerization material is a mixture containing polymer I containing monomer units derived from propylene, and polymer II containing monomer units derived from at least one ⁇ -olefin selected from the group consisting of ethylene and ⁇ -olefins having 4 to 12 carbon atoms, and monomer units derived from propylene.
  • the heterophasic propylene polymerization material can be produced, for example, by carrying out a first polymerization step of polymerizing polymer I and a second polymerization step of polymerizing polymer II. These polymerization steps can be carried out according to the polymerization catalyst, polymerization method, polymerization system, and polymerization conditions that can be used in the production of the above-mentioned propylene homopolymer.
  • the heterophasic propylene polymerization material may be such that the sum of polymer I and polymer II contained in the heterophasic propylene polymerization material is 100% by mass, relative to the total mass of the heterophasic propylene polymerization material being 100% by mass.
  • Polymer I may contain 70% by mass or more of monomer units derived from propylene (where the total mass of polymer I is taken as 100% by mass). Polymer I may be, for example, a propylene homopolymer, or may contain monomer units derived from monomers other than propylene. When polymer I contains monomer units derived from monomers other than propylene, the content is usually 0.01% by mass or more and 30% by mass or less with respect to the total mass of polymer I, 100% by mass.
  • Monomers other than propylene include, for example, ethylene and ⁇ -olefins having 4 or more carbon atoms.
  • ⁇ -olefins having 4 or more carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene, 4-methyl-1-hexene, etc.
  • the monomer other than propylene is preferably at least one selected from the group consisting of ethylene and ⁇ -olefins having 4 to 10 carbon atoms, more preferably at least one selected from the group consisting of ethylene, 1-butene, 1-hexene, and 1-octene, and even more preferably at least one selected from the group consisting of ethylene and 1-butene.
  • polymer I containing monomer units derived from a monomer other than propylene examples include propylene-ethylene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer, propylene-ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer, propylene-ethylene-1-octene copolymer, etc.
  • Polymer I is preferably a propylene homopolymer, a propylene-ethylene copolymer, a propylene-1-butene copolymer, or a propylene-1-hexene copolymer, and more preferably a propylene homopolymer.
  • the content of polymer I is usually 30% by mass or more and 99% by mass or less, preferably 50% by mass or more and 95% by mass or less, and more preferably 60% by mass or more and 90% by mass or less, based on the total mass of the heterophasic propylene polymerization material (100% by mass).
  • polymer II contains monomer units derived from at least one ⁇ -olefin selected from the group consisting of ethylene and ⁇ -olefins having 4 to 12 carbon atoms, and monomer units derived from propylene.
  • ⁇ -olefins having 4 to 12 carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene, and 4-methyl-1-hexene.
  • Polymer II preferably contains 30% by mass or more of monomer units derived from at least one ⁇ -olefin selected from the group consisting of ethylene and ⁇ -olefins having 4 to 12 carbon atoms, and also contains monomer units derived from propylene (where the total mass of Polymer II is taken as 100% by mass).
  • the content of monomer units derived from at least one ⁇ -olefin selected from the group consisting of ethylene and ⁇ -olefins having 4 to 12 carbon atoms is usually 1% by mass to 80% by mass, preferably 20% by mass to 70% by mass, and more preferably 30% by mass to 60% by mass (where the total mass of polymer II is taken as 100% by mass).
  • the at least one ⁇ -olefin selected from the group consisting of ethylene and ⁇ -olefins having 4 to 12 carbon atoms is preferably at least one selected from the group consisting of ethylene and ⁇ -olefins having 4 to 10 carbon atoms, more preferably at least one selected from the group consisting of ethylene, 1-butene, 1-hexene, 1-octene, and 1-decene, and even more preferably at least one selected from the group consisting of ethylene and 1-butene.
  • polymer II examples include propylene-ethylene copolymer, propylene-ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer, propylene-ethylene-1-octene copolymer, propylene-ethylene-1-decene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer, propylene-1-decene copolymer, etc.
  • polymer II is preferably a propylene-ethylene copolymer, a propylene-1-butene copolymer, or a propylene-ethylene-1-butene copolymer, and more preferably a propylene-ethylene copolymer.
  • the content of polymer II is usually 1% by mass or more and 70% by mass or less, preferably 5% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 40% by mass or less, based on the total mass of the heterophasic propylene polymerization material (100% by mass).
  • Heterophasic propylene polymerization materials include, for example, (propylene)-(propylene-ethylene) polymerization materials, (propylene)-(propylene-ethylene-1-butene) polymerization materials, (propylene)-(propylene-ethylene-1-hexene) polymerization materials, (propylene)-(propylene-ethylene-1-octene) polymerization materials, (propylene)-(propylene-1-butene) polymerization materials, (propylene)-(propylene-1-hexene) polymerization materials, (propylene)-(propylene-1-octene) polymerization materials, (propylene)-(propylene-1-decene) polymerization materials, (propylene- (ethylene)-(propylene-ethylene) polymerization material, (propylene-ethylene)-(propylene-ethylene-1-butene) polymerization material, (propylene-ethylene)-(propylene-ethylene
  • (propylene)-(propylene-ethylene) polymer material means "a heterophasic propylene polymer material in which polymer I is a propylene homopolymer and polymer II is a propylene-ethylene copolymer.” The same applies to other similar expressions.
  • the heterophasic propylene polymeric material is preferably a (propylene)-(propylene-ethylene) polymeric material, a (propylene)-(propylene-ethylene-1-butene) polymeric material, a (propylene-ethylene)-(propylene-ethylene) polymeric material, a (propylene-ethylene)-(propylene-ethylene-1-butene) polymeric material, or a (propylene-1-butene)-(propylene-1-butene) polymeric material, and more preferably a (propylene)-(propylene-ethylene) polymeric material.
  • the melt flow rate (MFR) of the propylene polymer is preferably 1 g/10 min or more and 300 g/10 min or less, more preferably 10 g/10 min or more and 200 g/10 min or less, from the viewpoint of improving the moldability of the polypropylene resin composition.
  • melt flow rate (MFR) of propylene-based polymers is measured by Method A under conditions of a temperature of 230°C and a load of 2.16 kg, in accordance with the method specified in JIS K7210-1:2014 and K7210-2:2014.
  • the polyethylene resin is a resin containing an ethylene polymer.
  • An ethylene-based polymer is a polymer containing more than 50% by mass of monomer units derived from ethylene.
  • ethylene-based polymers include ethylene homopolymers, copolymers of ethylene and ⁇ -olefins, and copolymers of ethylene and ⁇ -olefins substituted with alicyclic compounds.
  • the ethylene-based polymer may also be a mixture of an ethylene homopolymer and a copolymer of ethylene and ⁇ -olefins.
  • the amount of monomer units derived from ⁇ -olefins in the ethylene-based polymer is not particularly limited, and may be, for example, 4.0% by mass or more and 20% by mass or less.
  • ethylene homopolymers examples include high-pressure low-density polyethylene (LDPE) produced by high-pressure radical polymerization using a radical initiator.
  • LDPE high-pressure low-density polyethylene
  • LDPE is a material in which repeating units of ethylene are randomly bonded to form a branched structure.
  • the high-pressure low-density polyethylene (LDPE) may have a density of, for example, 910 to 935 kg/ m3 .
  • copolymers of ethylene and ⁇ -olefins include linear low-density polyethylene that has crystallinity, and elastomers of copolymers of ethylene and ⁇ -olefins that have low crystallinity and rubber-like elastic properties.
  • the density of the linear low density polyethylene may be, for example, 900 to 940 kg/m 3.
  • the density of the elastomer of a copolymer of ethylene and an ⁇ -olefin may be, for example, 860 to 900 kg/m 3 .
  • Examples of ⁇ -olefins include ⁇ -olefins having 3 to 10 carbon atoms.
  • ⁇ -olefins having 3 to 10 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, and 3-methyl-1-butene.
  • they are ⁇ -olefins having 4 to 10 carbon atoms, and more preferably, they are 1-butene, 1-hexene, or 1-octene.
  • copolymers of ethylene and ⁇ -olefins examples include ethylene-1-butene copolymers, ethylene-1-hexene copolymers, ethylene-1-octene copolymers, ethylene-1-decene copolymers, and ethylene-(3-methyl-1-butene) copolymers.
  • the copolymers of ethylene and ⁇ -olefins may be one of these alone or a mixture of two or more of them.
  • Examples of ⁇ -olefins substituted with alicyclic compounds include vinylcyclohexane.
  • the melt flow rate (MFR) of the ethylene polymer is preferably 0.5 g/10 min or more and 50 g/10 min or less, more preferably 1 g/10 min or more and 30 g/10 min or less, and even more preferably 1 g/10 min or more and 20 g/10 min or less.
  • melt flow rate (MFR) of ethylene polymers is measured by Method A under conditions of a temperature of 190°C and a load of 2.16 kg, in accordance with the method specified in JIS K7210-1:2014 and K7210-2:2014.
  • Ethylene-based polymers can be produced by known polymerization methods using known polymerization catalysts.
  • Polymerization catalysts include homogeneous catalyst systems such as metallocene catalysts, Ziegler catalyst systems, and Ziegler-Natta catalyst systems.
  • homogeneous catalyst systems include catalyst systems consisting of a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl ring and an alkylaluminoxane, or catalyst systems consisting of a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl ring and a compound that reacts with it to form an ionic complex and an organoaluminum compound, catalyst systems in which inorganic particles such as silica and clay minerals are supported and modified with catalyst components such as a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl ring, a compound that forms an ionic complex, and an organoaluminum compound, and prepolymerization catalyst systems prepared by prepolymerizing ethylene or ⁇ -olefins in the presence of the above catalyst systems.
  • a radical initiator can be used as a polymerization catalyst for high-pressure low-density polyethylene (LDPE).
  • LDPE high-pressure low-density polyethylene
  • the content of the polyolefin resin (A) is from 1 to 96.4% by mass, preferably from 20 to 90% by mass, more preferably from 25 to 80% by mass, and even more preferably from 50 to 80% by mass, where the total content of the (A), (B), (C) and (D) is taken as 100% by mass. Note that when the polyolefin resin (A) is a combination of two or more types, the content of the polyolefin resin (A) is the total content.
  • the modified polyolefin resin (B) is a resin containing a modified polyolefin polymer.
  • modified polyolefin resins (B) include modified polyethylene resins and modified polypropylene resins.
  • modified polyolefin resins (B) are preferably modified polypropylene resins from the viewpoint of obtaining a molded article that contains a plant-derived filler but emits relatively little VOC.
  • modified polyolefin polymers include acid-modified polyolefin polymers, hydroxyl-modified polyolefin polymers, epoxy-modified polyolefin polymers, carbodiimide-modified polyolefin polymers, amine-modified polyolefin polymers, acrylic-modified polyolefin polymers, and polyoxyethylene-modified polyolefin polymers.
  • the modified polyolefin polymer is preferably at least one selected from the group consisting of acid-modified polyolefin polymers, hydroxyl-modified polyolefin polymers, epoxy-modified polyolefin polymers, carbodiimide-modified polyolefin polymers, amine-modified polyolefin polymers, and acrylic-modified polyolefin polymers, from the viewpoint of obtaining a molded body having relatively excellent tensile strength while containing a plant-derived filler, and more preferably at least one selected from the group consisting of acid-modified polyolefin polymers, hydroxyl-modified polyolefin polymers, epoxy-modified polyolefin polymers, and carbodiimide-modified polyolefin polymers.
  • the modified polyolefin resin (B) may contain only one type of modified polyolefin polymer, or may contain two or more types.
  • the modified polyolefin resin (B) includes at least one selected from the group consisting of acid-modified polyolefin polymers, hydroxyl-modified polyolefin polymers, epoxy-modified polyolefin polymers, and carbodiimide-modified polyolefin polymers.
  • the acid-modified polyolefin polymer is shown in the following (1) or (2), that is, has a monomer unit (modifying group) derived from at least one of an unsaturated carboxylic acid and a derivative thereof.
  • (1) An olefin homopolymer identical or different from the above-mentioned olefin polymer, a copolymer of at least two kinds of olefins, or a block copolymer obtained by homopolymerizing an olefin and then copolymerizing at least two kinds of olefins, which is subjected to a graft reaction or a terminal reaction with at least one of an unsaturated carboxylic acid or a derivative thereof.
  • (2) A copolymer of at least one olefin with at least one of an unsaturated carboxylic acid and its derivatives.
  • unsaturated carboxylic acids include maleic acid, fumaric acid, itaconic acid, acrylic acid, and methacrylic acid.
  • Derivatives of unsaturated carboxylic acids include unsaturated carboxylic anhydrides such as maleic anhydride and itaconic anhydride; unsaturated carboxylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, monoethyl maleate, diethyl maleate, monomethyl fumarate, and dimethyl fumarate; unsaturated carboxylic amides such as acrylamide, methacrylamide, monoamide maleate, diamide maleate, and monoamide fumarate; unsaturated carboxylic imides such as maleimide and N-butylmaleimide; and unsaturated carboxylic acid metal salts such as sodium me
  • the unsaturated carboxylic acid may be produced by dehydrating citric acid, malic acid, or the like in the process of grafting to the polyolefin. At least one of the unsaturated carboxylic acid and its derivative is preferably maleic anhydride, glycidyl acrylate, or glycidyl methacrylate.
  • One embodiment of the acid-modified polyolefin polymer is shown in the following (1') or (2').
  • acid-modified polyolefin polymers include maleic anhydride-modified polypropylene, maleic anhydride-modified polyethylene, maleic acid-modified polypropylene, itaconic acid-modified polypropylene, methacrylic acid-modified polypropylene, glycidyl acrylate-modified polypropylene, and glycidyl methacrylate-modified polypropylene.
  • the acid-modified polyolefin polymer is preferably maleic anhydride-modified polypropylene, maleic anhydride-modified polyethylene, maleic acid-modified polypropylene, itaconic acid-modified polypropylene, glycidyl acrylate-modified polypropylene, or glycidyl methacrylate-modified polypropylene, and more preferably maleic anhydride-modified polypropylene, maleic anhydride-modified polyethylene, maleic acid-modified polypropylene, glycidyl acrylate-modified polypropylene, or glycidyl methacrylate-modified polypropylene.
  • Hydroxyl-modified polyolefin polymers are similar to acid-modified polyolefin polymers except that the "unsaturated carboxylic acid and/or its derivative" shown in (1) or (2) above is replaced with "unsaturated alcohol or unsaturated carboxylic acid ester having a hydroxyl group”; that is, they have monomer units (modifying groups) derived from unsaturated alcohol or unsaturated carboxylic acid ester having a hydroxyl group.
  • unsaturated alcohols include allyl alcohol, crotyl alcohol, methyl vinyl carbinol, allyl carbinol, methyl propipenyl carbinol, 4-penten-1-ol, 10-undecen-1-ol, propargyl alcohol, 1,4-pentadiene-3-ol, 1,4-hexadiene-3-ol, 3,5-hexadiene-2-ol, 2,4-hexadiene-1-ol, 3-butene-1,2-diol, 2,5-dimethyl-3-hexene-2,5-diol, 1,5-hexadiene-3,4-diol, and 2,6-octadiene-4,5-diol.
  • the unsaturated alcohol is preferably allyl alcohol or allyl carbinol.
  • unsaturated carboxylate esters having a hydroxyl group examples include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 4-hydroxybutyl acrylate.
  • hydroxyl group-modified polyolefin polymers include ethylene-allyl alcohol copolymer, ethylene-crotyl alcohol copolymer, ethylene-methylvinylcarbinol copolymer, ethylene-allylcarbinol copolymer, ethylene-4-penten-1-ol copolymer, ethylene-10-undecen-1-ol copolymer, propylene-allyl alcohol copolymer, propylene-crotyl alcohol copolymer, propylene-methylvinylcarbinol copolymer, propylene-allylcarbinol copolymer, propylene-4-penten-1-ol copolymer, propylene-10-undecen-1-ol copolymer, 2-hydroxyethyl methacrylate-modified polypropylene, 2-hydroxypropyl methacrylate-modified polypropylene, 4-hydroxybutyl acrylate-modified polypropylene, 2-hydroxyethyl methacrylate
  • the hydroxyl group-modified polyolefin polymer is preferably a propylene-4-penten-1-ol copolymer, a propylene-10-undecen-1-ol copolymer, a 2-hydroxyethyl methacrylate-modified polypropylene, or a 4-hydroxybutyl acrylate-modified polypropylene, and more preferably a 2-hydroxyethyl methacrylate-modified polypropylene or a 4-hydroxybutyl acrylate-modified polypropylene.
  • Hydroxyl-modified polyolefin polymers can be produced by converting the functional groups introduced during polymerization using a chain transfer agent, or by converting the functional groups introduced to the terminal double bonds of the polyolefin polymer, and the hydroxyl groups may be introduced using any method.
  • the position of the hydroxyl group in the hydroxyl group-modified polyolefin polymer is not particularly limited, and the polymer may be one in which the polyolefin chain is modified with hydroxyl groups, one in which both ends are modified with hydroxyl groups, or one end is modified with a hydroxyl group.
  • the position of the hydroxyl group may be any combination of the above.
  • the epoxy-modified polyolefin polymer is similar to the acid-modified polyolefin polymer, except that the "unsaturated carboxylic acid and/or its derivative" shown in (1) or (2) above is replaced with an "unsaturated epoxy compound", i.e., it has a monomer unit (modifying group) derived from an unsaturated epoxy compound.
  • unsaturated epoxy compounds include glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl ester, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether, etc.
  • the unsaturated epoxy compound is preferably glycidyl acrylate or glycidyl methacrylate.
  • epoxy-modified polyolefin polymers include ethylene-glycidyl (meth)acrylate copolymer, ethylene-glycidyl (meth)acrylate-methyl (meth)acrylate copolymer, ethylene-glycidyl (meth)acrylate-ethyl (meth)acrylate copolymer, ethylene-glycidyl (meth)acrylate-normal propyl (meth)acrylate copolymer, ethylene-glycidyl (meth)acrylate-isopropyl (meth)acrylate copolymer, ethylene-glycidyl (meth)acrylate-normal butyl (meth)acrylate copolymer, ethylene-glycidyl (meth)acrylate-isobutyl (meth)acrylate copolymer, ethylene-glycidyl (meth)acrylate-2-ethylhexyl (meth)acrylate copolymer, and ethylene-glycidyl
  • the epoxy-modified polyolefin polymer is preferably an ethylene-glycidyl (meth)acrylate copolymer, a glycidyl (meth)acrylate-modified polyethylene, or a glycidyl (meth)acrylate-modified polypropylene, and more preferably an ethylene-glycidyl (meth)acrylate copolymer or a glycidyl (meth)acrylate-modified polypropylene.
  • the epoxy-modified polyolefin polymer may be one obtained by reacting a polyolefin having a group reactive with an epoxy group with an epoxy-group-containing compound. Specifically, the two may be melt-kneaded.
  • Polyolefins having groups that react with epoxy groups can be obtained by introducing a compound that reacts with epoxy groups into polyolefins.
  • Examples of compounds that react with epoxy groups include compounds having a group with active hydrogen that is reactive with epoxy groups, and specifically include compounds having a group derived from carboxylic acid, amine, phenol, thiol, etc.
  • the compound that reacts with epoxy groups is preferably a compound having a group derived from carboxylic acid, and more preferably an unsaturated carboxylic acid or a derivative thereof.
  • the compounds that react with epoxy groups may be used alone or in combination of two or more types.
  • Unsaturated carboxylic acids include unsaturated compounds having one or more carboxylic acid groups, and unsaturated compounds having one or more carboxylic anhydride groups.
  • unsaturated groups in unsaturated carboxylic acids include vinyl groups, vinylene groups, and unsaturated cyclic hydrocarbon groups.
  • unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, and bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic acid.
  • Examples of derivatives of unsaturated carboxylic acids include unsaturated carboxylic anhydrides, unsaturated carboxylic acid halides, unsaturated carboxylic acid amides, unsaturated carboxylic acid imides, and unsaturated carboxylic acid esters.
  • Examples of derivatives of unsaturated carboxylic acids include malenyl chloride, malenylimide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic anhydride, dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citraconic acid, dimethyl tetrahydrophthalate, dimethyl bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, aminoethyl methacrylate, and aminopropyl methacrylate.
  • the unsaturated carboxylic acid or its derivative is preferably maleic anhydride, (meth)acrylic acid, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic anhydride, hydroxyethyl (meth)acrylate, or aminopropyl methacrylate, and more preferably maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, or bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic anhydride.
  • the compound that reacts with the epoxy group is particularly preferably maleic anhydride.
  • Various methods can be used to introduce a compound that reacts with epoxy groups into a polyolefin, including, for example, a method of grafting or terminally reacting a compound that reacts with epoxy groups onto the polyolefin main chain, and a method of radically copolymerizing an olefin such as ethylene or propylene with a compound that reacts with epoxy groups.
  • the epoxy group-containing compound is preferably a polyepoxide having a repeating unit represented by the following general formula (i):
  • R E1 represents a divalent organic group
  • R E2 and R E3 each independently represent a monovalent organic group
  • the asymmetric carbon may have any configuration provided that it does not contradict the epoxide structure.
  • Monopoxides may be added to the epoxy group-containing compound, and it is also possible to use a single epoxy group-containing compound or a mixture of multiple epoxy group-containing compounds.
  • Examples of epoxy-modified polyolefins obtained by reacting a polyolefin having a group reactive with an epoxy group with an epoxy-containing compound include a reaction product of maleic anhydride-modified polyethylene with TEPIC-S, and a reaction product of maleic anhydride-modified polypropylene with TEPIC-S, and preferably a reaction product of maleic anhydride-modified polypropylene with TEPIC-S.
  • Carbodiimide-modified polyolefin polymers are obtained by reacting a polyolefin having a group reactive with a carbodiimide group with a compound containing a carbodiimide group. Specifically, they are obtained by a method such as melt-kneading the two.
  • Polyolefins having groups that react with carbodiimide groups can be obtained by introducing a compound that reacts with carbodiimide groups into a polyolefin.
  • Examples of compounds that react with carbodiimide groups include compounds having a group with active hydrogen that is reactive with carbodiimide groups, and specifically, compounds having a group derived from carboxylic acid, amine, alcohol, thiol, etc.
  • compounds that react with carbodiimide groups are preferably compounds having a group derived from carboxylic acid, and more preferably unsaturated carboxylic acid or a derivative thereof.
  • compounds having a group with active hydrogen compounds having a group that is easily converted into a group with active hydrogen by water or the like can also be preferably used as compounds that react with carbodiimide groups, and specifically, compounds having an epoxy group or a glycidyl group can be mentioned. It should be noted that the compounds that react with carbodiimide groups may be used alone or in combination of two or more types.
  • Examples of unsaturated carboxylic acids include unsaturated compounds having one or more carboxylic acid groups, and unsaturated compounds having one or more carboxylic acid anhydride groups.
  • Examples of unsaturated groups in unsaturated carboxylic acids include vinyl groups, vinylene groups, and unsaturated cyclic hydrocarbon groups.
  • Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, and bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic acid.
  • Examples of derivatives of unsaturated carboxylic acids include unsaturated carboxylic anhydrides, unsaturated carboxylic acid halides, unsaturated carboxylic acid amides, unsaturated carboxylic acid imides, and unsaturated carboxylic acid esters.
  • Examples of derivatives of unsaturated carboxylic acids include malenyl chloride, malenylimide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic anhydride, dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citraconic acid, dimethyl tetrahydrophthalate, dimethyl bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, aminoethyl methacrylate, and aminopropyl methacrylate.
  • the unsaturated carboxylic acid or its derivative is preferably maleic anhydride, (meth)acrylic acid, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic anhydride, hydroxyethyl (meth)acrylate, glycidyl methacrylate, or aminopropyl methacrylate, and more preferably maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, or bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic anhydride.
  • the compound that reacts with the carbodiimide group is particularly preferably maleic anhydride.
  • Various methods can be used to introduce a compound that reacts with carbodiimide groups into a polyolefin, including, for example, a method of grafting or terminally reacting a compound that reacts with carbodiimide groups onto the polyolefin main chain, and a method of radical copolymerizing an olefin such as propylene with a compound that reacts with carbodiimide groups.
  • polycarbodiimide can be synthesized by reacting an organic polyisocyanate in the presence of a catalyst that promotes the carbodiimidization reaction of the isocyanate group.
  • Monocarbodiimide may be added to polycarbodiimide, and it is also possible to use a single compound or a mixture of multiple compounds containing carbodiimide groups.
  • carbodiimide group-containing compounds are as the carbodiimide group-containing compound.
  • Examples of commercially available carbodiimide group-containing compounds include Carbodilite (registered trademark) HMV-15CA, Carbodilite (registered trademark) HMV-8CA, and Carbodilite (registered trademark) LA1 manufactured by Nisshinbo Industries, Inc., and Stavaxol (registered trademark) P and Stavaxol (registered trademark) P400 manufactured by Rhein Chemie.
  • carbodiimide-modified polyolefin polymers include reaction products of maleic anhydride-modified polyethylene and Carbodilite HMV-15CA, reaction products of maleic anhydride-modified polyethylene and Carbodilite HMV-8CA, reaction products of maleic anhydride-modified polyethylene and Carbodilite LA1, reaction products of maleic anhydride-modified polyethylene and Stabaxol P400, reaction products of maleic anhydride-modified polypropylene and Carbodilite HMV-15CA, reaction products of maleic anhydride-modified polypropylene and Carbodilite HMV-8CA, reaction products of maleic anhydride-modified polypropylene and Carbodilite LA1, reaction products of maleic anhydride-modified polypropylene and Stabaxol P400, etc.
  • the carbodiimide-modified polyolefin polymer is preferably a reaction product of maleic anhydride-modified polypropylene and Carbodilite HMV-15CA, a reaction product of maleic anhydride-modified polypropylene and Carbodilite HMV-8CA, or a reaction product of maleic anhydride-modified polypropylene and Carbodilite LA1, and more preferably a reaction product of maleic anhydride-modified polypropylene and Carbodilite HMV-15CA.
  • the modified group content of the modified polyolefin resin (B) is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 6% by mass or less, even more preferably 0.1% by mass or more and 5% by mass or less, and particularly preferably 0.1% by mass or more and 1% by mass or less.
  • the modified polyolefin resin (B) contains a modified polypropylene polymer obtained by a graft reaction or a terminal reaction
  • the modified group content of the modified polyolefin resin (B) is preferably 0.1% by mass or more and 5% by mass or less.
  • the modified group content of the modified polyolefin resin (B) is preferably 0.1% by mass or more and 5% by mass or less.
  • the intrinsic viscosity number ([ ⁇ ]) of the modified polyolefin polymer is preferably 0.1 dl/g or more and 3.0 dl/g or less, and more preferably 0.1 dl/g or more and 1.0 dl/g or less.
  • the intrinsic viscosity (unit: dl/g) is a value measured at a temperature of 135°C using tetralin as a solvent by the following method.
  • Ubbelohde viscometer is used to measure the reduced viscosity at three concentrations: 0.1 g/dl, 0.2 g/dl, and 0.5 g/dl.
  • the reduced viscosity is plotted against the concentration, and the intrinsic viscosity is calculated by the extrapolation method, which extrapolates the concentration to zero.
  • the method for calculating the limiting viscosity using the extrapolation method is described, for example, on page 491 of "Polymer Solutions, Polymer Experiments 11" (published by Kyoritsu Publishing Co., Ltd. in 1982).
  • the modified polyolefin polymer may be produced, for example, by the methods exemplified in "Practical Polymer Alloy Design” (by Ide Fumio, Kogyo Chosakai (1996)), Prog. Polym. Sci., 24, 81-142 (1999), and JP-A 2002-308947.
  • the modified polyolefin polymer may be produced, for example, by any of the solution method, bulk method, and melt kneading method.
  • the modified polyolefin polymer may be produced by a combination of these methods.
  • modified polyolefin polymer commercially available products may be used.
  • modified polyolefin polymers include UMEX (registered trademark) manufactured by Sanyo Chemical Industries, Ltd., TOYOTAC (registered trademark) manufactured by Toyobo Co., Ltd., TUFMER M (registered trademark) manufactured by Mitsui Chemicals, Inc., ADMER (registered trademark) manufactured by Mitsui Chemicals, Inc., MODIC (registered trademark) manufactured by Mitsubishi Chemical Corporation, ARROWBASE (registered trademark) manufactured by Unitika Ltd., SUMIFITT (registered trademark) manufactured by Sumitomo Chemical Co., Ltd., and BONDFAST (registered trademark) manufactured by Sumitomo Chemical Co., Ltd.
  • the content of the modified polyolefin resin (B) is from 1 to 20% by mass, preferably from 1 to 15% by mass, and more preferably from 1 to 10% by mass, based on 100% by mass of the total content of (A), (B), (C), and (D). Note that when the modified polyolefin resin (B) contains two or more types of modified polyolefin polymers, the content of the modified polyolefin resin (B) is the total content.
  • Plant-derived filler (C) As the plant-derived filler (C), the same plant-derived filler (C) as in the resin composition according to this embodiment can be used.
  • the content of the plant-derived filler (C) is from 1% to 80% by mass, preferably from 10% to 70% by mass, and more preferably from 20% to 65% by mass, where the total content of the plant-derived fillers (A), (B), (C) and (D) is taken as 100% by mass. Note that when the plant-derived filler (C) is a combination of two or more types, the content of the plant-derived filler (C) is the total content.
  • the content of the hydrophilic resin (D) having hydroxyl groups is from 1 to 30% by mass, preferably from 1 to 25% by mass, and more preferably from 5 to 25% by mass, with the total content of (A), (B), (C) and (D) being 100% by mass. Note that when the hydrophilic resin (D) having hydroxyl groups is a combination of two or more types, the content of the hydrophilic resin (D) having hydroxyl groups is the total content.
  • the polyolefin resin composition according to the present embodiment may contain other additives as necessary.
  • the same additives as those in the resin composition according to the present embodiment can be used.
  • the method for producing a polyolefin resin composition is a method for producing the above-mentioned polyolefin resin composition, and includes the following steps 1 and 2.
  • Step 1 A step of kneading the plant-derived filler (C) and the hydrophilic resin (D) having a hydroxyl group using a kneader.
  • Step 2 After step 1, a step of further adding and kneading the polyolefin resin (A) and the modified polyolefin resin (B).
  • the kneading method may be, for example, melt kneading, solid-phase shear continuous kneading, etc. Among these, the kneading method is preferably melt kneading.
  • the kneading machine used for the kneading may be, for example, a single screw extruder, a twin screw extruder, a Banbury mixer, a heat roll, a Labo Plastomill, etc.
  • the kneading machine is preferably a single screw extruder, a twin screw extruder, a Banbury mixer, or a Labo Plastomill, and more preferably a twin screw extruder, a Banbury mixer, or a Labo Plastomill.
  • the kneading temperature is preferably 160°C or higher and 230°C or lower, and more preferably 170°C or higher and 200°C or lower.
  • the rotation speed of the screw of the kneading machine is preferably 50 rpm or more and 500 rpm or less, more preferably 100 rpm or more and 500 rpm or less, and even more preferably 100 rpm or more and 300 rpm or less.
  • the kneading time is preferably from 1 minute to 15 minutes.
  • steps 1 and 2 the components may be mixed simultaneously or sequentially.
  • the method for producing the polyolefin resin composition according to this embodiment is, for example, as follows.
  • Step 1 Hydrophilic resin (D) having hydroxyl groups is fed into a kneader (such as Labo Plastomill manufactured by Toyo Seiki Seisakusho), and then plant-derived filler (C) is fed into the kneader. The mixture is melt-kneaded for 5 minutes at a temperature of 180°C and a rotation speed of 100 rpm to obtain a resin composition.
  • a kneader such as Labo Plastomill manufactured by Toyo Seiki Seisakusho
  • Step 2 The resin composition obtained in step 1 is crushed using a crusher to obtain a crushed resin composition.
  • the crushed resin composition obtained is homogeneously mixed with the modified polyolefin resin composition (B) and the polyolefin resin composition (A) to obtain a mixture.
  • the resulting mixture is fed to a kneader (e.g., Labo Plastomill manufactured by Toyo Seiki Seisakusho) and melt-kneaded for 5 minutes at a temperature of 180°C and a rotation speed of 100 rpm to obtain a polyolefin resin composition.
  • a kneader e.g., Labo Plastomill manufactured by Toyo Seiki Seisakusho
  • the molded product according to this embodiment includes the polyolefin resin composition described above.
  • the molded product is a molded product molded by a conventionally known method. Examples of such molded products include injection molded products, press molded products, vacuum molded products, vacuum press molded products, pressure molded products, foam molded products, extrusion molded products, etc. Examples of the molding method for such molded products include injection molding, press molding, vacuum molding, vacuum press molding, pressure molding, foam molding, extrusion molding, etc.
  • the molded article according to this embodiment is preferably an injection molded article.
  • injection molding methods for forming the injection molded article include general injection molding, injection foam molding, supercritical injection foam molding, ultra-high speed injection molding, injection compression molding, injection press molding, gas-assisted injection molding, sandwich molding, sandwich foam molding, and insert-outsert molding.
  • Applications of the molded article according to this embodiment include, for example, automobile interior and exterior parts, home appliance parts, building materials, miscellaneous goods, furniture, food containers, beverage containers, medical containers, containers, etc.
  • the application of the molded article is preferably automobile interior and exterior parts or home appliance parts.
  • the molded article according to the present embodiment may be obtained by the method described in steps 3 and 4 below.
  • Step 3 A step of pulverizing the molded product containing the polyolefin-based resin composition to obtain a pulverized product.
  • Step 4 A step of molding the pulverized product to obtain a molded product containing the polyolefin-based resin composition.
  • a composition comprising a plant-derived filler (C) and a hydrophilic resin (D) having a hydroxyl group, The total content of (C) and (D) is 100 mass%, The content of the plant-derived filler (C) is 20% by mass or more and 91% by mass or less, A resin composition, comprising a hydrophilic resin (D) having a hydroxyl group in an amount of 9% by mass or more and 80% by mass or less.
  • the hydrophilic resin (D) having a hydroxyl group is polyvinyl alcohol having a degree of polymerization of 100 or more and 1,000 or less and a degree of saponification of 10 or more and 90 or less.
  • a method for producing the resin composition according to [1] or [2], A method for producing a resin composition, comprising a step of kneading a plant-derived filler (C) and a hydrophilic resin (D) having a hydroxyl group using a kneader.
  • a composition comprising a polyolefin resin (A), a modified polyolefin resin (B), a plant-derived filler (C), and a hydrophilic resin having a hydroxyl group (D),
  • the total content of (A), (B), (C) and (D) is taken as 100 mass%
  • the content of the polyolefin resin (A) is 1% by mass or more and 96.4% by mass or less
  • the content of the modified polyolefin resin (B) is 1% by mass or more and 20% by mass or less
  • the content of the plant-derived filler (C) is 1% by mass or more and 80% by mass or less
  • a polyolefin resin composition comprising a hydrophilic resin (D) having a hydroxyl group in an amount of 1% by mass or more and 30% by mass or less.
  • polyolefin-based resin composition according to [4], wherein the polyolefin-based resin (A) is a polypropylene-based resin.
  • modified polyolefin resin (B) comprises at least one selected from the group consisting of an acid-modified polyolefin polymer, a hydroxyl-modified polyolefin polymer, an epoxy-modified polyolefin polymer, and a carbodiimide-modified polyolefin polymer.
  • Step 2 After Step 1, a polyolefin-based resin (A) and a modified polyolefin-based resin (B) are further added and kneaded. [9] A molded article comprising the resin composition according to [1] or [2], or the polyolefin-based resin composition according to any one of [4] to [7].
  • hPP-1 The physical properties of hPP-1 were as follows: Melt flow rate (temperature 230°C, load 2.16 kg): 23-25 g/10 min. Melting point: 164°C
  • MAH-1 The physical properties of MAH-1 were as follows: Content of maleic anhydride monomer units contained in MAH-1: 0.3% by mass ⁇ Intrinsic viscosity number: 0.8 dl/g
  • Wood fiber 1 (NF-1, acetaldehyde content: 0.22 ppm) Lignocellulosic fibers for fiberboards produced using a pressurized refiner at a fiberboard factory were used as the wood fibers. The fiber length was approximately 3 mm and the fiber width was approximately 30 ⁇ m.
  • Wood fiber 2 (NF-2, acetaldehyde content: 0.38 ppm) Lignocellulosic fibers for fiberboards, which were produced in a fiberboard factory using a pressure refiner, were consolidated with a fiber consolidating agent and then cut into small pieces to obtain a sheet-like bundle. The length of the convergence was approximately 4 mm and the width of the convergence was approximately 4 mm.
  • the polymerization degree and saponification degree of PVA-1 to PVA-6 were determined based on information provided by the manufacturers.
  • the polymerization degree and saponification degree provided by the manufacturers were measured in accordance with JIS K6726-1994.
  • Antioxidant 1 (Sumilizer GA80; manufactured by Sumitomo Chemical Co., Ltd.)
  • Antioxidant 2 (Sumilizer GP; manufactured by Sumitomo Chemical Co., Ltd.)
  • Neutralizer (calcium stearate)
  • Example 1 A mixture was obtained by mixing 50% by mass of PVA-1, 0.1% by mass of antioxidant 1, 0.1% by mass of antioxidant 2, and 0.05% by mass of a neutralizing agent. The mixture was fed to a kneader (Labo Plastomill manufactured by Toyo Seiki Seisakusho), and then 50% by mass of NF-1 was fed to the kneader and melt-kneaded for 5 minutes under conditions of a temperature of 180° C. and a rotation speed of 100 rpm, to obtain a resin composition.
  • a kneader Labo Plastomill manufactured by Toyo Seiki Seisakusho
  • the resulting resin composition was preheated at 190°C for 5 minutes and subjected to a pressure of 5 MPa for 3 minutes to obtain a sheet-like press molded product with a thickness of 300 ⁇ m.
  • Example 2 A resin composition and a press-molded product were obtained in the same manner as in Example 1, except that 50% by mass of PVA-2 was used instead of PVA-1.
  • Example 3 A resin composition and a press-molded body were obtained in the same manner as in Example 1, except that 50% by mass of PVA-3 was used instead of PVA-1.
  • Example 4 A resin composition and a press-molded body were obtained in the same manner as in Example 1, except that 50% by mass of PVA-4 was used instead of PVA-1.
  • Example 5 A resin composition was obtained in the same manner as in Example 1, except that 50% by mass of PVA-5 and 50% by mass of NF-2 were used instead of PVA-1 and NF-1.
  • the resulting resin composition was preheated at 210°C for 5 minutes and subjected to a pressure of 5 MPa for 3 minutes to obtain a sheet-like press molded product with a thickness of 300 ⁇ m.
  • Comparative Example 2 A resin composition and a press-molded product were obtained in the same manner as in Example 1, except that 50% by mass of hPP-1 was used instead of PVA-1.
  • Example 6 The resin composition obtained in Example 3 was crushed using a crusher to obtain a crushed resin composition F-3. 40% by mass of the crushed F-3, 2% by mass of MAH-1, 58% by mass of hPP-1, 0.1% by mass of antioxidant 1, 0.1% by mass of antioxidant 2, and 0.05% by mass of neutralizing agent 1 were uniformly mixed to obtain a mixture. The obtained mixture was supplied to a kneader (Labo Plastomill manufactured by Toyo Seiki Seisakusho) and melt-kneaded for 5 minutes under conditions of a temperature of 180 ° C. and a rotation speed of 100 rpm to obtain a polyolefin resin composition.
  • a kneader Labo Plastomill manufactured by Toyo Seiki Seisakusho
  • the resin composition obtained above was preheated at 190°C for 5 minutes and subjected to a pressure of 5 MPa for 3 minutes to obtain a sheet-like press molded product with a thickness of 300 ⁇ m.
  • Comparative Example 4 The resin composition obtained in Comparative Example 2 was crushed using a crusher to obtain a crushed resin composition F-5.
  • a polyolefin resin composition and a press molded product were obtained in the same manner as in Example 6, except that 50% by mass of the crushed resin F-5 and 78% by mass of hPP-1 were used.
  • Incubation temperature 60°C Incubation time: 15 min ⁇ Injection volume: 5000 ⁇ L ⁇ GC main body injector temperature: 220°C Trap temperature: 5°C Desorption temperature: 240° C.
  • the acetaldehyde content was calculated from the values obtained by the above measurements using a calibration curve created from values obtained by measuring the acetaldehyde standard solution in advance.
  • Tables 1 and 2 show that molded articles that satisfy all of the constituent requirements of the present invention emit relatively small amounts of VOCs, even though they contain plant-derived fillers.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne : une composition de résine qui permet la production d'un corps moulé émettant des quantités relativement faibles de COV bien qu'une matière de charge dérivée de plante soit contenue; un procédé de production de la composition de résine; une composition de résine à base de polyoléfine; un procédé de production de la composition de résine à base de polyoléfine; et un corps moulé comprenant la composition de résine ou la composition de résine à base de polyoléfine.
PCT/JP2024/042325 2023-12-05 2024-11-29 Composition de résine, procédé de production d'une composition de résine, composition de résine à base de polyoléfine, procédé de production d'une composition de résine à base de polyoléfine et corps moulé Pending WO2025121259A1 (fr)

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JP2023-205435 2023-12-05
JP2024-205687 2024-11-26
JP2024205687 2024-11-26

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011125801A1 (fr) * 2010-04-01 2011-10-13 三菱化学株式会社 Procédé de fabrication d'une dispersion de fibres de cellulose fines
JP2018203940A (ja) * 2017-06-08 2018-12-27 三菱製紙株式会社 セルロース樹脂複合体の製造方法
JP2019526694A (ja) * 2016-08-23 2019-09-19 ナショナル リサーチ カウンシル オブ カナダ リグニンペレット及びその製造方法
JP2019218450A (ja) * 2018-06-19 2019-12-26 三菱製紙株式会社 セルロース樹脂複合体の製造方法
JP2020084391A (ja) * 2018-11-30 2020-06-04 株式会社富山環境整備 繊維材料の製造方法及び複合材料の製造方法並びに繊維材料及び複合材料並びに植物栽培用シート
JP2021172705A (ja) * 2020-04-21 2021-11-01 オイレス工業株式会社 摺動部材用樹脂組成物及び摺動部材

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011125801A1 (fr) * 2010-04-01 2011-10-13 三菱化学株式会社 Procédé de fabrication d'une dispersion de fibres de cellulose fines
JP2019526694A (ja) * 2016-08-23 2019-09-19 ナショナル リサーチ カウンシル オブ カナダ リグニンペレット及びその製造方法
JP2018203940A (ja) * 2017-06-08 2018-12-27 三菱製紙株式会社 セルロース樹脂複合体の製造方法
JP2019218450A (ja) * 2018-06-19 2019-12-26 三菱製紙株式会社 セルロース樹脂複合体の製造方法
JP2020084391A (ja) * 2018-11-30 2020-06-04 株式会社富山環境整備 繊維材料の製造方法及び複合材料の製造方法並びに繊維材料及び複合材料並びに植物栽培用シート
JP2021172705A (ja) * 2020-04-21 2021-11-01 オイレス工業株式会社 摺動部材用樹脂組成物及び摺動部材

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