WO2019155929A1 - Composition de résine renforcée par des fibres et son procédé de production - Google Patents

Composition de résine renforcée par des fibres et son procédé de production Download PDF

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Publication number
WO2019155929A1
WO2019155929A1 PCT/JP2019/002785 JP2019002785W WO2019155929A1 WO 2019155929 A1 WO2019155929 A1 WO 2019155929A1 JP 2019002785 W JP2019002785 W JP 2019002785W WO 2019155929 A1 WO2019155929 A1 WO 2019155929A1
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Prior art keywords
fiber
water
cellulose
resin composition
reinforced resin
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PCT/JP2019/002785
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English (en)
Japanese (ja)
Inventor
茂樹 森井
伸一 足立
信博 山田
裕也 田原
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長瀬産業株式会社
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Priority to JP2019570687A priority Critical patent/JP6994520B2/ja
Publication of WO2019155929A1 publication Critical patent/WO2019155929A1/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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00

Definitions

  • the present invention relates to a fiber reinforced resin composition and a manufacturing method thereof, and a coated fiber and a manufacturing method thereof.
  • thermoplastic resins Since thermoplastic resins have excellent moldability, they are molded by various molding methods such as injection molding, extrusion molding, and blow molding, and are used for various applications.
  • a composite material in which strength and rigidity are improved by dispersing a filler in such a thermoplastic resin is known.
  • inorganic materials such as talc and glass fiber are filled. Strength and rigidity are improved as an agent.
  • inorganic materials such as talc and glass fiber have a large specific gravity of 2.5 to 2.7, so they deprive the resin of being lightweight, leave residue as sludge when incinerated, For reasons such as the possibility that the composite inorganic material may be scattered in the living space due to deterioration, it has been studied to convert the filler to another material.
  • fibers such as polyacrylonitrile fiber, aliphatic nylon fiber, aromatic nylon fiber, cellulose fiber, and polyvinyl alcohol fiber are used as a filler.
  • cellulose fibers have a specific gravity of about 1.5, which is lighter than inorganic materials, can be sintered by combustion, and are being studied for use as plant-derived renewable materials.
  • an object of the present invention is to provide a fiber reinforced resin composition capable of obtaining a molded body having sufficient strength and rigidity.
  • the present inventors unexpectedly added a water-soluble polysaccharide to a fiber-reinforced resin composition containing cellulose fibers and a thermoplastic resin composition, thereby unexpectedly reinforcing the fiber-reinforced resin composition.
  • the present invention has been completed by finding that the strength and rigidity of a molded product obtained from the product are improved.
  • a fiber reinforced resin composition containing a thermoplastic resin, cellulose fibers, and at least one water-soluble polysaccharide is provided.
  • the strength and rigidity of the molded body are improved as compared with a fiber reinforced resin composition containing cellulose fibers and not containing water-soluble polysaccharides.
  • a fiber reinforced resin composition containing cellulose fibers and not containing water-soluble polysaccharides.
  • Water-soluble polysaccharide forms a film on the surface of cellulose fiber. Therefore, when the molten thermoplastic resin and the cellulose fiber are kneaded, the polysaccharide coating suppresses recombination of the cellulose fibers and reduces the aggregation of the cellulose fibers, so that the cellulose fibers are contained in the thermoplastic resin. It is conceivable that it is easy to disperse uniformly and that the cellulose fibers are easily defibrated during kneading.
  • the water-soluble polysaccharide coating increases the adhesion between the thermoplastic resin and the cellulose fibers, thereby improving the strength and rigidity of the molded product.
  • the polysaccharide may be at least one selected from the group consisting of pullulan and dextrins.
  • the polysaccharide is preferably pullulan.
  • Pullulan has excellent film properties and adhesiveness among polysaccharides, and therefore can efficiently form a film firmly adhered to cellulose fibers. Furthermore, since pullulan has excellent lubricity, the cellulose fibers are easily dispersed uniformly in the thermoplastic resin. Pullulan is a Newtonian fluid having a relatively low viscosity among polysaccharides, and therefore has an advantage that it is easy to knead thermoplastic resin and cellulose fibers.
  • the thermoplastic resin is preferably a polyolefin resin or a polyamide resin.
  • Polyolefin resins and polyamide resins have the advantage of low specific gravity and light weight, but there is room for improvement in the strength and rigidity of the molded body. Therefore, by strengthening with cellulose fibers in the present invention, the strength and rigidity of the molded body are improved. The effect of improvement is exhibited more remarkably.
  • the polyolefin resin has advantages such as easy control of the molecular weight, various modifications by the copolymer, and establishment of a synthesis method.
  • the water-soluble polysaccharide may cover the surface of the cellulose fiber.
  • the fiber reinforced resin composition may contain 0.1 to 30 parts by weight of a water-soluble polysaccharide with respect to 100 parts by weight of cellulose fiber.
  • the present invention also provides a method for producing a fiber-reinforced resin composition, which includes a step of kneading a molten thermoplastic resin, cellulose fibers, and at least one water-soluble polysaccharide. According to the method of the present invention, it is not necessary to control a complex reaction, and the fiber-reinforced resin composition of the present invention can be produced simply and efficiently.
  • the surface of the cellulose fiber used in the step of kneading the molten thermoplastic resin, the cellulose fiber, and the water-soluble polysaccharide may be coated with the water-soluble polysaccharide in advance. It can. Since it is difficult for water to exist at the temperature at which the thermoplastic resin melts, and it is not easy to coat the cellulose fiber with a water-soluble polysaccharide, it is preferable to coat the thermoplastic resin before melting.
  • a step of heating the mixture containing the thermoplastic resin, the cellulose fiber, the water-soluble polysaccharide, and water to remove water from the mixture can be included.
  • the step of heating the mixture and the step of kneading can be performed in a kneader.
  • the heating step of the mixture may be performed outside the kneader.
  • the mixture before heating may contain 5 to 100 parts by weight of water with respect to 1 part by weight of the water-soluble polysaccharide.
  • the present invention also provides a coated fiber comprising cellulose fiber and a film of at least one water-soluble polysaccharide that coats the surface of the cellulose fiber.
  • the fiber reinforced resin composition of the present invention can be efficiently produced.
  • strength and rigidity can be shape
  • the present invention also provides a method for producing a coated fiber, comprising the step of coating cellulose fiber with at least one water-soluble polysaccharide. According to this method, the coated fiber of the present invention can be produced efficiently.
  • the coating step includes contacting the cellulose fiber with an aqueous solution containing the polysaccharide and drying the aqueous solution in contact with the cellulose fiber.
  • a fiber reinforced resin composition capable of giving sufficient strength and rigidity is provided.
  • the fiber reinforced resin composition of the present invention contains a thermoplastic resin, cellulose fibers, and a water-soluble polysaccharide.
  • a thermoplastic resin e.g., polyethylene glycol
  • cellulose fibers e.g., polypropylene glycol
  • a water-soluble polysaccharide e.g., polyethylene glycol
  • thermoplastic resin constitutes a base material on which cellulose fibers are dispersed.
  • the type of the thermoplastic resin is not particularly limited.
  • polyolefin resin, polyamide resin, polycarbonate resin, vinyl acetate resin, aromatic polyester resin, aliphatic polyester resin, polyether resin, vinyl chloride resin, fluorine resin, acrylic resin, A polystyrene resin, a polyacetal resin, etc. can be mentioned.
  • a thermoplastic resin can be used alone or in combination of two or more resins.
  • the thermoplastic resin used in the present invention preferably has a processing temperature of 280 ° C. or lower.
  • the processing temperature is 280 ° C. or lower, when the thermoplastic resin, the cellulose fiber, and the water-soluble polysaccharide are mixed at the processing temperature of the thermoplastic resin, and a molded product from the obtained fiber reinforced resin composition
  • the resin having such a processing temperature include a polyolefin resin and a polyamide resin among the resins listed above.
  • thermoplastic resins crystalline resins such as polyolefin resins and polyamide resins are preferable.
  • the thermoplastic resin includes a crystalline resin and an amorphous resin.
  • a crystalline resin is processed at a melting point +20 to 50 ° C.
  • an amorphous resin is processed at a glass transition temperature +100 to 120 ° C. . Therefore, in this specification, the processing temperature refers to a melting point +20 to 50 ° C. in the case of a crystalline resin, and refers to a glass transition temperature +100 to 120 ° C. in the case of an amorphous resin. Therefore, for example, when the thermoplastic resin is a crystalline resin, it preferably has a melting point of 260 ° C. or lower, more preferably 230 ° C. or lower.
  • the thermoplastic resin when the thermoplastic resin is an amorphous resin, the thermoplastic resin preferably has a glass transition temperature of 180 ° C. or lower, and more preferably has a glass transition temperature of 160 ° C. or lower. It is preferable to adjust the processing temperature to 280 ° C. or lower according to the melting point or glass transition temperature of the thermoplastic resin used.
  • the melting point and glass transition temperature of the thermoplastic resin can be adjusted by modifying the functional group of the monomer constituting the thermoplastic resin.
  • the thermoplastic resin is preferably a polyolefin resin or a polyamide resin. While polyolefin resins and polyamide resins have the advantage of being light in weight with a small specific gravity, there is room for improvement in the strength and rigidity of the molded body. Therefore, by strengthening with cellulose fibers in the present invention, the strength and rigidity of the molded body The effect of improvement is exhibited more remarkably. In addition, polyolefin resins and polyamide resins also have advantages such as easy control of molecular weight, various modifications by the copolymer, and establishment of a synthesis method.
  • polystyrene resin examples include olefin polymers such as low density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, and cyclic polyolefin, copolymers thereof, and modified products thereof.
  • the polyolefin resin may be a copolymer of ethylene and / or propylene and an ⁇ -olefin having 4 or more carbon atoms, such as an ethylene ⁇ -olefin copolymer or a propylene ⁇ -olefin copolymer.
  • polypropylene is particularly preferable because it is lightweight and has excellent heat resistance, chemical resistance, and moldability.
  • polypropylene include an ethylene / propylene block copolymer, an ethylene / propylene random copolymer, and a propylene / butene copolymer in addition to a homopolymer.
  • the thermoplastic resin is a polyolefin having an acid group, such as an acid-modified polyolefin to which maleic anhydride is added or a copolymer of maleic anhydride and an olefin such as an ⁇ -olefin in order to improve adhesion to cellulose fibers. Can be included.
  • the amount of the polyolefin having an acid group is preferably 0.5 to 50% by weight based on the whole thermoplastic resin.
  • polyamide resin polyamide polymers such as nylon 6, nylon 66, nylon 12, nylon 6,66 copolymer, nylon 6,12 copolymer, metaxylene adipamide / nylon 6 copolymer, and the like Denatured products can be mentioned.
  • nylon 6 and nylon 66 are preferably used.
  • the content of the thermoplastic resin in the fiber reinforced resin composition of the present invention is preferably 60 to 99 parts by weight with respect to 100 parts by weight of the fiber reinforced resin composition.
  • the content of the thermoplastic resin is preferably 65 to 99 parts by weight, more preferably 75 to 90 parts by weight.
  • the cellulose fibers are dispersed in the thermoplastic resin to increase the strength and rigidity of the molded body.
  • the cellulose fiber used in the present invention is a fiber containing cellulose as a main component.
  • the cellulose fiber source is not particularly limited, and various known materials can be used. Specifically, wood, plants other than wood (cotton, hemp, bamboo, kenaf, hemp, seaweed, etc.); animal fibers produced by sea squirts; bacterial cellulose produced by bacteria such as acetic acid bacteria; waste paper; rayon, polynosic, And regenerated cellulose such as cupra, lyocell, and acetate. Cellulose fibers can be used alone or in combination of two or more.
  • the form of the cellulose fiber used in the present invention is not particularly limited, and examples thereof include cellulose nanofiber, microfibrillated cellulose, and pulp.
  • KP kraft pulp
  • L material hardwood
  • N material coniferous tree
  • SP sulfide pulp
  • hemp and cotton which are representative examples of non-wood pulp, have a long fiber length, they are often entangled with the fiber itself when combined with a resin.
  • Cotton linter pulp a kind of cotton pulp, is easy to handle because it has a fiber length similar to wood pulp. The pulp is preferably defibrated.
  • Regenerated cellulose is characterized by easy fiber length control.
  • the cellulose nanofiber means cellulose having a fiber diameter of 3 nm to 35 nm or less, and the diameter of the cellulose nanofiber of the carboxylic acid-modified product produced with a TEMPO-based catalyst is also said to be 3 to 6 nm.
  • Microfibrillated cellulose is a cellulose fiber such as pulp that has been mechanically defibrated, which means cellulose fibers from micro to nano level, and such materials can also be used in the present invention as cellulose fibers. .
  • the average fiber length of the cellulose fibers in the resin is not particularly limited, but for example, the average fiber length of the cellulose fibers can be 0.2 to 20 mm. If the average fiber length of a cellulose fiber is the said range, the intensity
  • the average fiber diameter of the cellulose fibers in the resin is not particularly limited, but for example, the average fiber diameter of the cellulose fibers can be 15 nm to 30 ⁇ m.
  • the fiber diameter of the cellulose fiber can be appropriately adjusted by selecting the raw material of the cellulose fiber, the method of defibrating treatment, and the like.
  • the fiber length and fiber diameter of the cellulose fiber can be measured by, for example, a scanning electron microscope (SEM), an optical microscope or the like.
  • the content of the cellulose fiber in the fiber reinforced resin composition of the present invention is not particularly limited, but can be 0.5 to 75 parts by weight with respect to 100 parts by weight of the thermoplastic resin.
  • the cellulose fiber content is more preferably 1 to 50 parts by weight, and even more preferably 10 to 50 parts by weight.
  • the water-soluble polysaccharide forms a film on the surface (for example, side surface) of the cellulose fiber.
  • Polysaccharide refers to a sugar obtained by polymerizing a large number (eg, 10 or more) of monosaccharide molecules by glycosidic bonds. It is considered that a coating / coating effect that cannot be obtained with a monosaccharide and a disaccharide due to a small molecular weight (molecular length) can be obtained with a polysaccharide with a large molecular weight (molecular length).
  • Water-soluble means that 1 g of solid is powdered and then placed in water, and when it is shaken vigorously every 5 minutes at 100 ° C. or lower for 30 seconds, it dissolves in less than 30 mL of water within 30 minutes. Say. Even if the polysaccharide does not dissolve when the water temperature is low, if the water dissolves when the water is heated, a film can be formed on the cellulose fiber by heating. In the present invention, it is “water-soluble”.
  • the weight average molecular weight based on GPC of the water-soluble polysaccharide used in the present invention is preferably 100,000 or more, more preferably 200,000 or more from the viewpoint of easy formation of a film on cellulose fibers, and the upper limit is particularly high. Although it is not, it is preferable that it is 400,000 or less.
  • the type of water-soluble polysaccharide is not particularly limited, and any of synthetic polysaccharides, natural polysaccharides, and natural product modified polysaccharides can be used.
  • ⁇ -1,4-glucan (amylose, amylopectin, glycogen), ⁇ - 1,6-glucan (dextran), ⁇ -1,6-glucan (pustulan), ⁇ -1,3-glucan (eg curdlan, schizophyllan, etc.), ⁇ -1,3-glucan, ⁇ -1,2- Glucan, ⁇ -1,4-galactan, ⁇ -1,4-mannan, ⁇ -1,6-mannan, ⁇ -1,2-fructan (inulin), ⁇ -2,6-fructan (levan), ⁇ - Mention may be made of 1,4-xylan, ⁇ -1,3-xylan, pullulan, agarose, alginic acid and the like and their salts and derivatives.
  • starch containing amylose may be used.
  • Dextrins may also be used.
  • One or a combination of two or more water-soluble polysaccharides can be used.
  • cellulose since cellulose is not water-soluble, it is not included in the “water-soluble polysaccharide” in the present invention.
  • pullulan is a water-soluble compound having a structure in which maltotriose in which three molecules of glucose are linked by ⁇ -1,4 bonds is a structural unit and maltotriose is linked through ⁇ -1,6 bonds. Since pullulan has excellent coating properties and adhesiveness among polysaccharides, it can efficiently form a coating firmly adhered to cellulose fibers, and the effect of preventing aggregation of cellulose fibers becomes higher. Furthermore, since pullulan has excellent lubricity, the cellulose fibers are easily dispersed uniformly in the thermoplastic resin. Further, since it is a Newtonian fluid having a relatively low viscosity among the polysaccharides, it has an advantage of being easily kneaded when the thermoplastic resin and the cellulose fiber are kneaded.
  • the pullulan used in the present invention is not particularly limited in the obtaining method and type, but preferably has a weight average molecular weight based on GPC of 5,000 to 500,000, more preferably 50,000 to 400,000. .
  • a weight average molecular weight based on GPC of 5,000 to 500,000, more preferably 50,000 to 400,000.
  • dextrins are also preferable.
  • Dextrins can be obtained by hydrolysis of starch or glycogen, and are compounds having a molecular structure in which ⁇ -glucose is polymerized by ⁇ -1,4 or ⁇ -1,6 glycosidic bonds.
  • Dextrins include dextrin, maltodextrin, and powdered candy. Since dextrins also have excellent film properties and adhesiveness, a film firmly adhered to cellulose fibers can be efficiently formed, and the effect of preventing aggregation of cellulose fibers is enhanced.
  • the dextrins used in the present invention are not particularly limited in the obtaining method and type, but those having a dextrose equivalent (DE) of 10 or less are preferred, and those having a dextrose equivalent of 3.0 or less are more preferred. Further, those having a weight average molecular weight based on GPC of 5,000 to 500,000 are preferred, and those having a weight average molecular weight of 50,000 to 400,000 are more preferred. By using dextrins having a weight average molecular weight within the above range, it is considered that the coating effect on the cellulose fibers by the coating of dextrins becomes better.
  • DE dextrose equivalent
  • the content of the water-soluble polysaccharide in the fiber-reinforced resin composition of the present invention is not particularly limited, but is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of cellulose fibers.
  • the polysaccharide can efficiently form a film on the cellulose fiber.
  • the water-soluble polysaccharide is more preferably 0.2 to 10 parts by weight with respect to 100 parts by weight of the cellulose fiber.
  • the fiber reinforced resin composition of the present invention may contain components other than the above-described thermoplastic resin, cellulose fiber, and water-soluble polysaccharide, if necessary.
  • components include various additives usually used in thermoplastic resin compositions, such as antioxidants, light stabilizers, ultraviolet absorbers, neutralizers, lubricants, antiblocking agents, dispersants, and fluidity.
  • additives such as an improving agent, a release agent, a flame retardant, a foaming agent, a colorant, a filler, a thickener, a low viscosity agent, and a crystal nucleating agent.
  • the content ratio of the fiber reinforced resin composition of these additives is preferably 30 parts by weight or less when the entire fiber reinforced resin composition is 100 parts by weight.
  • strength and rigidity of a molded object become high compared with the fiber reinforced resin composition which does not contain water-soluble polysaccharide although it contains a cellulose fiber. The reason is not clear, but the following can be considered.
  • Water-soluble polysaccharide forms a film on the surface of cellulose fiber. Therefore, when the melted thermoplastic resin and the cellulose fiber are mixed, the polysaccharide coating suppresses recombination of the cellulose fibers and reduces the aggregation of the cellulose fibers, and the cellulose fibers are contained in the thermoplastic resin. It is conceivable that it is easy to disperse uniformly and the cellulose fibers are easily defibrated during mixing.
  • the water-soluble polysaccharide coating increases the adhesion between the thermoplastic resin and the cellulose fiber, thereby improving the strength and rigidity.
  • the method for producing a fiber-reinforced resin composition of the present invention includes a step of kneading a molten thermoplastic resin, cellulose fibers, and a water-soluble polysaccharide. According to the method of the present invention, complicated reaction control is unnecessary, and the above-described fiber-reinforced resin composition can be produced simply and efficiently.
  • the above kneading can be performed by various kneaders such as a single or twin screw extruder, a roll, a Banbury mixer, a kneader, and a Brabender.
  • the cellulose fiber to be charged into the kneader may be an aqueous dispersion or a dry body.
  • the temperature at which the molten thermoplastic resin and the cellulose fiber are kneaded may be any temperature at which the thermoplastic resin dissolves.
  • the melting point of the crystalline thermoplastic resin can be +20 to 50 ° C.
  • the glass transition temperature of the amorphous thermoplastic resin can be set to +100 to 120 ° C.
  • the cellulose fiber is preferably defibrated in advance.
  • the method of defibrating treatment is not particularly limited, and examples thereof include physical treatment such as a grinder method, a high-pressure homogenizer method, an underwater counter impact method, a refiner method, an ultrasonic homogenizer method, a biaxial kneading method, a TEMPO oxidation method, and ozone. Chemical treatments such as an oxidation method and an enzyme treatment method, and combinations thereof can be performed.
  • the dry method there are generally two methods for defibrating sheet-like pulp, one of which is the dry method.
  • the dry method when the pulverized material is recovered by air blow while the pulp sheet is pulverized with a hammer mill or the like, the defibrated fiber can be obtained. Obstacles such as shortening the length may appear.
  • a special apparatus since the obtained defibrated material becomes a low-density cotton, a special apparatus may be required when it is put into the kneader together with the resin.
  • Another method of defibrating sheet-like pulp is a wet method.
  • pulp is well-familiar with water and can be fibrillated with a weak force in water, for example, with a normal stirring device or a pulper (stirring device).
  • a suction filtration method, a centrifugal separation method, a belt press method, or the like a fibrillated cellulose fiber (water dispersion) is obtained.
  • a kneader having a function of removing residual water such as a vent is required, but the crystallization degree is not lowered during defibration and the fiber length can be preserved.
  • the cellulose fiber concentration obtained by wet defibration is about 15 to 30% by weight for KP, about 20 to 35% by weight for cotton linter, and 5 to 20% by weight for microfibrillated cellulose. In the case of cellulose nanofibers, it can be 0.3 to 3% by weight.
  • a water-soluble polysaccharide film is formed on the surface of the cellulose fiber in advance.
  • the cellulose fiber and the cellulose fiber are brought into contact with the cellulose fiber by bringing the aqueous solution A containing a water-soluble polysaccharide into contact with the cellulose fiber, and drying the aqueous solution A in contact with the cellulose fiber by heating, decompression, or the like. It is possible to obtain a coated fiber having a water-soluble polysaccharide film covering the surface.
  • the aqueous solution A can be dried by a known method such as heating, reduced pressure, or natural drying.
  • the coating of the cellulose fiber with the water-soluble polysaccharide can also be performed in a kneader.
  • a mixture B of solid thermoplastic resin, cellulose fiber, water-soluble polysaccharide, and water may be kneaded in a kneader.
  • the mixture B is heated by the kneading of the mixture B, and the water in the mixture B can be removed out of the system as water vapor.
  • a water-soluble polysaccharide film is formed on the surface of the cellulose fiber.
  • the thermoplastic resin is melted, and the melted thermoplastic resin and cellulose fibers having a polysaccharide coating are kneaded.
  • the cellulose fiber contains 5 to 9% by weight of adsorbed water even in a dry body. Therefore, even when liquid water is not added to the kneader, the mixture containing the thermoplastic resin, cellulose fiber, and water-soluble polysaccharide is heated by shearing in the kneader, and the adsorbed water is separated from the cellulose fiber. Since it is desorbed to form free water, a mixture of thermoplastic resin, cellulose fiber, water-soluble polysaccharide, and water can be formed in the kneader. Therefore, the above-mentioned fiber reinforced resin composition can be produced without adding liquid water.
  • the aqueous solution A and the mixture B are 5 to 100 parts by weight with respect to 1 part by weight of the water-soluble polysaccharide. It is preferred to contain water.
  • a molded body can be produced from the above-described fiber-reinforced resin composition of the present invention.
  • the molding method various known methods can be used without particular limitation, and examples thereof include compression molding, injection molding, extrusion molding, extrusion lamination molding, rotational molding, calendar molding, vacuum molding, blow molding and the like.
  • the shape of the molded body is not particularly limited.
  • the molded product obtained from the fiber-reinforced resin composition of the present invention has sufficient strength and rigidity.
  • aqueous dispersion of cellulose fiber 1 A water slurry containing 2% by weight of NBKP (bleached kraft pulp made from softwood) was prepared. This was mechanically defibrated with a pulper (stirrer) to obtain an aqueous dispersion of cellulose fibers 1. Thereafter, excess water was removed by a centrifuge and concentrated to finally produce an aqueous dispersion of cellulose fibers 1 in which the concentration of cellulose fibers 1 was 25% by weight. The average fiber length of the cellulose fiber 1 was 2.8 mm, and the average fiber diameter was 25 ⁇ m.
  • Examples 1 to 6 In Examples 1 to 4, an aqueous dispersion of cellulose fiber 1, polypropylene (BC06C, manufactured by Nippon Polypro), acid-modified polypropylene (H1000P, manufactured by Toyobo), and powdered pullulan (food grade grade “Pullan”, manufactured by Hayashibara) Blended in the amounts shown in Table 1, supplied to a biaxial kneader with a vent, kneaded while discharging water vapor from the vent, and further kneaded while melting polypropylene at 230 ° C. to produce a fiber reinforced resin composition did. From the obtained fiber reinforced resin composition, an injection-molded article was prepared, and the flexural modulus was measured.
  • Example 5 was the same as Example 2 except that 20 parts by weight of a 10% by weight pullulan aqueous solution was blended to increase the amount of water. In Example 6, 2 parts by weight of a 10% by weight aqueous pullulan solution was blended.
  • Example 7 a fiber reinforced resin was prepared by the formulation shown in Table 1 in the same manner as in Example 2, except that a fluffy dried cellulose fiber 2 was used instead of the aqueous dispersion of cellulose fiber 1. did.
  • the cellulose fiber 2 does not contain liquid water but contains 7% by weight of adsorbed water.
  • Examples 8 to 10 were the same as Example 7 except that liquid water was further added according to the formulation shown in Table 1.
  • Example 11 was the same as Example 7 except that 20 parts by weight of a 10% by weight aqueous pullulan solution was blended.
  • Example 12 A cellulose fiber reinforced resin was prepared according to the formulation shown in Table 1 in the same manner as in Example 7 except that cellulose fiber 3 previously coated with pullulan was used instead of the combination of powdered pullulan and cellulose fiber 2. In addition, 2 parts of pullulan covers 20 parts of cellulose fibers.
  • Example 6 A fiber reinforced resin was produced in the same manner as in Example 1 except that 10 parts by weight of powdered trehalose was blended instead of the powdered pullulan.
  • Example 1 to 6 and Comparative Examples 1 to 4 an aqueous dispersion of cellulose fiber 1 obtained by wet defibrating treatment was used. According to the comparison between Examples 1 to 4 and Comparative Examples 1 to 4, the bending elastic modulus tended to improve as the amount of cellulose fiber increased regardless of whether or not pullulan was added. Is constant, the flexural modulus is significantly improved in each example with pullulan added as compared with each comparative example without pullulan added. It can also be seen that in the system to which pullulan is added, the degree of crystallinity of the resin increases as the amount of cellulose fibers increases.
  • Example 5 the crystallinity and the flexural modulus were obtained when the powdered pullulan was added to the cellulose fiber aqueous dispersion and when the aqueous pullulan solution was added to the cellulose fiber aqueous dispersion. It can be seen that it does not affect Further, when Example 5 and Example 6 were compared, the amount of pullulan added was one-tenth that of Example 5 in Example 6, but the same was true for the crystallinity of the resin and the flexural modulus. Showed the effect.
  • Comparative Example 6 in which 10 parts by weight of powdered trehalose was mixed in place of powdered pullulan, unlike Examples 1 to 4, the effects of increasing the crystallinity of the resin and improving the flexural modulus were observed. There wasn't.
  • Example 7 In Examples 7 to 11 and Comparative Example 5, dried cellulose fiber 2 obtained by dry defibrating treatment was used. Comparing Example 7 in which dried cellulose fiber 2 and pullulan in powder form were added and liquid water was not added, and Comparative Example 5 in which neither pullulan nor water was added, the crystallinity of polypropylene The bending elastic modulus of the molded body of Example 7 was slightly higher. Further, when Examples 7 to 10 are compared, when the same amount of cellulose fiber and the same amount of pullulan are used, as the amount of liquid water added increases, the degree of crystallinity of polypropylene increases, and the bending of the molded body increases. Elastic modulus increased.
  • Example 7 Even when liquid water is not added as in Example 7, the cellulose fibers contain moisture as adsorbed water, so that the pullulan is separated from the cellulose fibers by the process of heating. A film can be formed on the film, but it is considered that the effect of forming the film is enhanced by adding liquid water as in Examples 8 to 10.
  • Example 11 pullulan was added in the form of an aqueous solution. Compared with Example 9 in which the same amount of powder pullulan and almost the same amount of water were added, in Example 11, the crystallinity of polypropylene and the flexural modulus of the molded product were significantly increased. While there was no difference between Example 2 and Example 5 of wet defibrated cellulose fibers as described above, the reason why such difference appears in dry defibrated cellulose fibers is not clear, but wet defibrated cellulose Unlike fibers, dry defibrated cellulose fibers are considered more effective when added as an aqueous solution from the beginning.
  • Example 12 is an example in which cellulose fiber 3 in which cellulose fiber 2 was previously coated with pullulan was used for kneading.
  • Example 12 the same degree of polypropylene crystallinity and bending elastic modulus as in Examples 10 and 11 were obtained. That is, by using cellulose fibers pre-coated with pullulan, it was possible to effectively increase the flexural modulus of the molded body without adding water during kneading.
  • the present invention provides a fiber reinforced resin composition from which a molded article having excellent strength and rigidity can be obtained, and can be used in various fields.

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

Un but de la présente invention est de fournir une composition de résine renforcée par des fibres capable de donner des objets moulés ayant une résistance et une rigidité suffisantes. La composition de résine renforcée par des fibres de la présente invention comprend une résine thermoplastique, des fibres de cellulose et au moins un polysaccharide soluble dans l'eau.
PCT/JP2019/002785 2018-02-08 2019-01-28 Composition de résine renforcée par des fibres et son procédé de production WO2019155929A1 (fr)

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CN113795545A (zh) * 2020-02-17 2021-12-14 古河电气工业株式会社 树脂复合材料和树脂成型体
CN114181435A (zh) * 2020-09-14 2022-03-15 精工爱普生株式会社 复合体、成形体以及成形体的制造方法

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