WO2014087767A1 - Composite material and molded body using same - Google Patents

Composite material and molded body using same Download PDF

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Publication number
WO2014087767A1
WO2014087767A1 PCT/JP2013/079404 JP2013079404W WO2014087767A1 WO 2014087767 A1 WO2014087767 A1 WO 2014087767A1 JP 2013079404 W JP2013079404 W JP 2013079404W WO 2014087767 A1 WO2014087767 A1 WO 2014087767A1
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Prior art keywords
composite material
acid
cellulose fiber
modified
repeating unit
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PCT/JP2013/079404
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French (fr)
Japanese (ja)
Inventor
丈史 中谷
木村　浩司
伸治 佐藤
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日本製紙株式会社
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Priority to JP2014550992A priority Critical patent/JP6275651B2/en
Publication of WO2014087767A1 publication Critical patent/WO2014087767A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/045—Reinforcing macromolecular compounds with loose or coherent fibrous material with vegetable or animal fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/26—Cellulose ethers
    • C08L1/28—Alkyl ethers
    • C08L1/286—Alkyl ethers substituted with acid radicals, e.g. carboxymethyl cellulose [CMC]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2439/00—Characterised by the use 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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
    • C08J2439/02—Homopolymers or copolymers of vinylamine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils

Definitions

  • the present invention relates to a composite resin containing a carboxymethylated cellulose fiber and a polyolefin resin, and a molded product obtained by heat-treating the composite resin.
  • Composite materials composed of cellulosic fibers and polypropylene are well known, but polyolefin resins such as PP are highly hydrophobic, while cellulosic fibers are hydrophilic. Since it is high, it was difficult to mix uniformly. For this reason, it is known to use maleic acid-modified polypropylene (hereinafter sometimes abbreviated as “MAPP”) as a compatibilizing agent or an interfacial reinforcing agent (for example, Patent Document 1).
  • MAPP maleic acid-modified polypropylene
  • Patent Document 1 maleic acid-modified polypropylene
  • the Example of patent document 2 is disclosing the composite material which consists of cellulose fiber containing lignin, PP, and MAPP.
  • the Example of patent document 3 is disclosing the composite material which consists of a cellulosic fiber, PP, MAPP, and the compound which has a specific primary amino group.
  • An object of the present invention is to provide a composite material of a high strength and high elasticity cellulose fiber and a polyolefin resin by enhancing the uniform dispersibility and interfacial interaction between the cellulose fiber and the polyolefin resin.
  • the present inventors have carboxymethylated the cellulose fiber so that the amino group of the polymer compound having a primary amino group and the cellulose fiber It has been found that a molding material containing a cellulosic fiber and a polyolefin resin having an improved electrostatic interaction and greatly improved strength and elastic modulus can be obtained.
  • the present invention includes, but is not limited to: 1. (1) Carboxymethylated cellulose fiber, (2) a polymer compound having a primary amino group, (3) acid-modified polyolefin, and (4) a composite material containing a polyolefin resin. 2.
  • the compound in which the polymer compound having the primary amino group has a repeating unit represented by the following general formula (A):
  • the composite material according to any one of 1 to 4 above which is at least one selected from the group consisting of a compound having a repeating unit represented by the formula: and a salt thereof. 6).
  • Carboxymethylated cellulose fiber (2) a polymer compound having a primary amino group, (3) an acid-modified polyolefin, and (4) a step of kneading a polyolefin resin.
  • the carboxymethylation of the cellulosic fiber improves the electrostatic interaction between the cellulosic fiber and the primary amino group and the interfacial adhesion between the cellulosic fiber and the acid-modified polyolefin.
  • a molded product having high strength and high elastic modulus can be obtained.
  • the composite material of the present invention comprises (1) carboxymethylated cellulose fiber (hereinafter sometimes abbreviated as “CM cellulose fiber”), (2) a polymer compound having a primary amino group, (3 A) an acid-modified polyolefin; and (4) a polyolefin resin.
  • CM cellulose fiber carboxymethylated cellulose fiber
  • 3 A a polymer compound having a primary amino group
  • 3 A an acid-modified polyolefin
  • (4) a polyolefin resin a polyolefin resin
  • CMized cellulose fiber The cellulose fiber contained in the composite material of the present invention contains a carboxymethyl group. By introducing a carboxymethyl substituent into cellulose, electrostatic interaction between the cellulose fiber and (2) the amino group of the polymer compound having a primary amino group is increased. This reinforces (1) the network structure of the CMized cellulose fibers. Further, (3) the hydrophilic group portion of the acid-modified polyolefin reacts with (1) CM-modified cellulose fiber and the hydrophobic group portion reacts with (4) polyolefin resin, respectively, and (1) CM-modified cellulose fiber and (4) Interfacial interaction with polyolefin resin is reinforced.
  • the degree of carboxymethyl substitution per anhydroglucose unit of cellulose is preferably 0.01 to 0.40, and more preferably 0.05 to 0.20.
  • the degree of crystallinity of cellulose type I in the CMized cellulose fiber is preferably 60% or more, more preferably 70% or more, and further preferably 80% or more.
  • the carboxymethyl group substituent per anhydroglucose unit is smaller than 0.01, the effect may not be sufficiently exhibited.
  • the carboxymethyl substituent per anhydroglucose unit is larger than 0.40, the CM-ized cellulose fiber swells or dissolves, so that the fiber form cannot be maintained and may not be obtained as a fiber.
  • the crystallinity of cellulose I type is less than 60%, the strength of the cellulose fiber is lowered, and a sufficient reinforcing effect as a reinforcing material for the polyolefin resin may not be obtained.
  • CM cellulose fiber is not particularly limited, it can be obtained by carboxymethylating the cellulose raw material.
  • cellulose raw material examples include plants (for example, wood, bamboo, hemp, jute, kenaf, agricultural land residue, cloth, pulp (coniferous unbleached kraft pulp (NUKP), conifer bleached kraft pulp (NBKP), hardwood unbleached kraft pulp ( LUKP), hardwood bleached kraft pulp (LBKP), softwood unbleached sulfite pulp (NUSP), softwood bleached sulfite pulp (NBSP) thermomechanical pulp (TMP), recycled pulp, waste paper, etc.), animals (for example, ascidians), Those originating from algae, microorganisms (for example, acetic acid bacteria (Acetobacter)), microbial products, etc. are known, and any of them can be used in the present invention, preferably cellulose derived from plants or microorganisms, more preferably. Is plant-derived cellulose.
  • Carboxymethylation of a cellulose raw material can be performed using a well-known method, and is not specifically limited. Commercially available CMized cellulose fibers may also be used. In the present invention, the substitution degree of carboxymethyl group per anhydroglucose unit of cellulose is 0.01 to 0.40, and the crystallinity of cellulose type I is 60% or more, preferably 70% or more, more preferably 80%. It is preferable to adjust so that it may become above. As an example, the following manufacturing method can be mentioned. Cellulose is used as the bottoming material.
  • a solvent 3 to 20 times by weight of water and / or lower alcohol, specifically, methanol, ethanol, N-propyl alcohol, isopropyl alcohol, N-butanol, isobutanol, tertiary butanol and the like alone or two kinds
  • the above mixed medium is used.
  • the mixing ratio of the lower alcohol in the solvent is 60 to 95% by weight.
  • the mercerizing agent 0.5 to 20 times moles of alkali metal hydroxide, specifically sodium hydroxide or potassium hydroxide is used per anhydroglucose residue of the bottoming material.
  • a bottoming raw material, a solvent, and a mercerizing agent are mixed and subjected to mercerization treatment at a reaction temperature of 0 to 70 ° C., preferably 10 to 60 ° C., and a reaction time of 15 minutes to 8 hours, preferably 30 minutes to 7 hours. .
  • a carboxymethylating agent for example, monochloroacetic acid, sodium monochloroacetate, etc.
  • the reaction temperature is 30 to 90 ° C., preferably 40 to 80 ° C.
  • the etherification reaction is carried out for 30 minutes to 10 hours, preferably 1 to 4 hours.
  • the average fiber diameter of the CM-converted cellulose fiber contained in the composite material of the present invention is preferably 4 nm to 50 ⁇ m, more preferably 200 nm to 50 ⁇ m, and even more preferably 500 nm to 20 ⁇ m. Further, the average fiber length of the CMized cellulose fiber is preferably 0.5 mm to 5.0 mm. When the average fiber diameter and average fiber length of the CM-converted cellulose fiber are adjusted within the above ranges, the reinforcing effect of the polyolefin resin by the CM-converted cellulose fiber is enhanced.
  • the fiber diameter and fiber length of the CMized cellulose fiber were measured with 100 representative fibers using a transmission electron microscope (TEM), scanning electron microscope (SEM), or digital CCD microscope, and the average value was calculated. did.
  • defibration is performed as necessary so that the fiber diameter and fiber length of the CMized cellulose fiber are in the above ranges.
  • the defibrating may be performed after carboxymethylation of the cellulose raw material, or carboxymethylation may be performed after the cellulose raw material is defibrated to be in the above range.
  • defibrating it is not limited to this, but it is preferable to use an aqueous dispersion of CM-modified cellulose fiber from the viewpoint of ease of handling.
  • the device for defibration is not particularly limited, and a high-speed rotation type, a colloid mill type, a high-pressure type, a roll mill type, an ultrasonic type, or a mass collider can be used as necessary.
  • defibration and mixing with other components may be performed simultaneously in a twin screw extruder (a twin screw kneader).
  • a twin screw extruder a twin screw kneader
  • a wet high pressure or ultra high pressure homogenizer that can apply a pressure of 50 MPa or more to the aqueous dispersion may be used.
  • the pressure is more preferably 100 MPa or more, and further preferably 140 MPa or more.
  • the CM-modified cellulose fiber is pretreated using a known mixing, stirring, emulsifying, and dispersing device such as a high-speed shear mixer. May be.
  • the blending amount of the CMized cellulose fiber is usually about 1 to 94% by mass, preferably about 2 to 92% by mass, based on the total amount of the composite material.
  • the composite material of the present invention includes a polymer compound having a primary amino group in the molecule.
  • the weight average molecular weight of the polymer compound having a primary amino group is usually about 1,000 to 1,000,000, preferably about 1200 to 700,000.
  • the weight average molecular weight is determined by gel permeation chromatography (GPC) method (PEG conversion), GPC method (pullulan conversion) or GPC-MALLS with a multi-angle light scattering detector connected to a GPC column. It is a value measured by any method.
  • GPC gel permeation chromatography
  • the amino group of the polymer compound having a primary amino group may form a salt with an organic acid or inorganic acid.
  • examples of the inorganic acid from which the amino group can form a salt include hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, hydrobromic acid, hydroiodic acid, and the like
  • examples of the organic acid include formic acid, acetic acid, and the like.
  • the polymer compound having a primary amino group may be used alone or in combination of two or more.
  • the polymer compound having a primary amino group may be synthesized by a known method, or a commercially available product may be used.
  • polymer compound having a primary amino group examples include the following general formula (A):
  • the compound having a repeating unit represented by the general formula (A) may be a copolymer or graft polymer containing other repeating units in addition to the repeating unit represented by the general formula (A). .
  • Examples of other repeating units that form a copolymer or graft polymer by combining with the repeating unit represented by the general formula (A) include polyacrylate units, polymethacrylate units, polyacrylamide units, and polydiallylamine units. Examples thereof include a unit containing a secondary amine, a unit containing a tertiary amine such as a polymethyldiallylamine unit, and a unit containing a quaternary ammonium salt such as a polydiallyldimethylammonium salt unit.
  • the order of combining the repeating units is not limited, and may be random or block.
  • the compound containing the repeating unit represented by the general formula (A) is more preferably a homopolymer containing only the repeating unit represented by the general formula (A) or a salt thereof.
  • the weight average molecular weight of the compound having the repeating unit represented by the general formula (A) is usually about 1,000 to 1,000,000, preferably about 1200 to 700,000 as described above for the polymer compound having a primary amino group. It is.
  • Examples of the salt of the compound having a repeating unit represented by formula (A) include inorganic acid salts such as hydrochloride, sulfate, phosphoric acid and hydrobromide, formate, acetate, propionate, p Organic salts such as toluenesulfonate, methanesulfonate, citrate, tartrate, etc.
  • the compound having a repeating unit represented by formula (A) can be synthesized by a known polymerization method using allylamine or the like as a raw material. Commercial products are also available.
  • the compound having a repeating unit represented by the general formula (B) may be a copolymer or graft polymer containing other repeating units in addition to the repeating unit represented by the general formula (B). .
  • repeating units that form a copolymer or graft polymer by combining with the repeating unit represented by the general formula (B) include a polyacrylate unit, a polymethyl methacrylate unit, a polyacrylamide unit, a polyvinyl formamide unit, Examples include units containing secondary amines such as polyvinylacetamide units, polydiallylamine units, units containing tertiary amines such as polymethyldiallylamine units, units containing quaternary ammonium salts such as polydiallyldimethylammonium salt units, and the like. It is done.
  • the order of combining the repeating units is not limited, and may be random or block.
  • the compound containing the repeating unit represented by the general formula (B) is more preferably a homopolymer containing only the repeating unit represented by the general formula (B) or a salt thereof.
  • the weight average molecular weight of the compound having a repeating unit represented by formula (B) is usually about 1,000 to 1,000,000, preferably about 1200 to 700,000 as described above for the polymer compound having a primary amino group. It is.
  • Examples of the salt of the compound having the repeating unit represented by the general formula (B) include hydrochloride, sulfate, phosphate, hydrobromide, hydroiodide and other inorganic acid salts, formate salts, acetic acid And organic acid salts such as salts, propionates, p-toluenesulfonates, methanesulfonates, citrates and tartrates.
  • the compound having a repeating unit represented by the general formula (B) can be obtained by, for example, hydrolyzing a polymer of N-substituted amides such as N-vinylformamide and N-vinylacetamide, or modifying polyacrylamide with Hoffman. It can be synthesized by a known polymerization method. Commercial products are also available.
  • the repeating unit represented by the general formula (C) may extend on a straight chain or may have a branched structure.
  • a graft polymer containing another repeating unit may be used.
  • the compound containing the repeating unit represented by the general formula (C) is more preferably a homopolymer containing only the repeating unit represented by the general formula (C) or a salt thereof.
  • a preferred homopolymer or a salt thereof include polyethyleneimine or a salt thereof.
  • the weight average molecular weight of the compound having a repeating unit represented by the general formula (C) is usually about 1,000 to 1,000,000, preferably about 1200 to 700,000 as described above for the polymer compound having a primary amino group. It is.
  • Examples of the salt of the compound having a repeating unit represented by the general formula (C) include inorganic acid salts such as hydrochloride, sulfate, phosphate, hydrobromide, hydroiodide, formate, and acetic acid. And organic acid salts such as salts, propionates, p-toluenesulfonates, methanesulfonates, citrates and tartrates.
  • the compound having a repeating unit represented by the general formula (C) is known as a force thione polymer, and can be synthesized by a known polymerization method using aziridine as a raw material. Commercial products are also available.
  • the composite material of the present invention preferably contains at least one selected from the group consisting of compounds having repeating units represented by the general formulas (A), (B) and (C), and salts thereof.
  • the amount of the polymer compound having a primary amino group is usually about 1 to 30 parts by mass, preferably 5 to 30 parts by mass with respect to 100 parts by mass of (1) CMized cellulose fiber. Part by weight, particularly preferably about 10 to 20 parts by weight.
  • the composite material of the present invention includes an acid-modified polyolefin.
  • acid-modified polyolefins include ⁇ , ⁇ -unsaturated carboxylic acids or acid anhydrides thereof, such as maleic acid, fumaric acid, itaconic acid, citraconic acid, allyl succinic acid, mesaconic acid, annicotic acid, and acid anhydrides thereof.
  • acid-modified polyolefins include polyolefins modified with products.
  • maleic anhydride-modified polyolefin that can be produced at low cost is preferable from the viewpoint of reaction efficiency.
  • the acid-modified polyolefin has a weight average molecular weight of usually about 10,000 to 100,000, preferably about 20,000 to 80,000. Moreover, the polyolefin modified with an acid may be used individually by 1 type, and 2 or more types may be mixed and used for it. The acid-modified polyolefin may be synthesized by a known method, or a commercially available product may be used.
  • maleic anhydride-modified polyolefin examples include maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, maleic anhydride-modified polybutadiene, maleic anhydride-modified polystyrene, and maleic anhydride-modified polymethacrylate.
  • linear olefins such as ethylene, propylene, 1-butene, 1-pentene and 1-hexene, and branches such as 3-methyl-1-butene, 3-methyl-1-pentene and 4-methyl-1-pentene
  • maleic anhydride-modified copolymers having a copolymer olefin, butadiene, styrene and the like.
  • the polyolefin modified with maleic anhydride preferably has the same skeleton as (4) polyolefin resin described later. That is, for example, when (4) a polypropylene resin is used as the polyolefin resin, it is particularly preferable to use an acid-modified polypropylene resin such as maleic anhydride-modified polypropylene as the (3) acid-modified polyolefin.
  • the acid modification rate of the acid-modified polyolefin is usually about 0.2 to 10% by mass, preferably about 3 to 7% by mass.
  • the compounding amount of the acid-modified polymer compound is (1) about 4 to 50 parts by mass, preferably about 10 to 30 parts by mass with respect to 100 parts by mass of the CMized cellulose fiber. is there.
  • the composite material of the present invention contains a polyolefin resin as a main component.
  • a known polyolefin resin may be used.
  • the polyolefin include linear ⁇ -olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl- Examples thereof include branched olefins such as 1-pentene, homopolymers or copolymers such as styrene, butadiene, isoprene, chloroprene, isobutylene and isoprene, and cyclic polyolefins having a norbornene skeleton.
  • the weight average molecular weight of the polyolefin resin is usually about 100,000 to 400,000, preferably about 200,000 to 300,000.
  • the polyolefin resin may be used alone or in combination of two or more.
  • the polyolefin resin may be synthesized by a known method, or a commercially available product may be used.
  • the blending amount of polyolefin is usually about 1 to 98% by mass, preferably about 2 to 96% by mass in the total amount of the composite material.
  • CM-modified cellulose fiber (2) polymer compound having primary amino group, (3) acid-modified polyolefin, and (4) polyolefin resin
  • other components include water; alkalis such as sodium hydroxide, potassium hydride, magnesium hydroxide, and calcium hydroxide; inorganic fillers such as clay, talc, calcium carbonate, my strength, titanium dioxide, and zinc oxide; Organic fillers such as carbon black, graphite, glass flakes; dyes or pigments such as bengara, azo pigments, phthalocyanines; dispersants, lubricants, plasticizers, mold release agents, flame retardants, antioxidants (phenolic antioxidants, phosphorus Antioxidants, sulfur-based antioxidants), antistatic agents, light stabilizers, UV absorbers, metal deactivators, crystallization accelerators (nucleating agents), foaming agents, crosslinking agents, antibacterial agents, etc. Additives and the like.
  • CM cellulose fiber By using together (1) CM cellulose fiber, (2) amine polymer compound having primary amino group, and (3) acid-modified polyolefin, (1) CM cellulose fiber and (4)
  • the polyolefin resin can be uniformly dispersed in the composite material, and a composite material having high strength and high elastic modulus can be obtained. Moreover, by heat-treating the composite material thus obtained, a CM-containing cellulose fiber-containing molded body having high strength and high elastic modulus can be obtained as described later.
  • the production method of the composite material is not particularly limited.
  • (1) CM-modified cellulose fiber, (2) polymer compound having primary amino group, (3) acid-modified polyolefin, and (4 ) Polyolefin resin and other components may be mixed if necessary.
  • the order of kneading each component (1) to (4) and other components is not particularly limited.
  • the mixing method of the components (1) to (4) and other components is not particularly limited, and a known method may be used.
  • the components (1) to (4) and other components can be uniformly dispersed by kneading them with a twin screw extruder (a twin screw kneader) or the like.
  • a twin screw extruder a twin screw kneader
  • an acid-modified polyolefin are both mixed into the composite material.
  • Each component to be dispersed can be uniformly dispersed.
  • the temperature at the time of mixing each component is not particularly limited, and is usually about 0 to 300 ° C.
  • CM cellulose fiber is defibrated with a twin screw extruder or the like, and each of the components (2), (3), (4) and other components such as water used as necessary are added thereto.
  • the composite material of the present invention may be obtained by stirring.
  • each component of (2), (3), (4) and other components used as necessary may be mixed together, and the production of CM-modified cellulose fibers by defibration of the carboxymethylated cellulose raw material and the stirring of each component may be performed simultaneously.
  • the molded body of the present invention is obtained by heat-treating the composite material as described later.
  • the temperature at which the composite material is heat-treated is usually about 100 to 300 ° C., preferably about 110 to 250 ° C., particularly preferably about 110 to 220 ° C.
  • the temperature during the heat treatment is usually preferably a temperature equal to or higher than the melting point of (4) polyolefin resin contained in the composite material.
  • the molded body can be formed into a desired shape by a known resin molding method.
  • a known resin molding method for example, the same method as the manufacturing method of a normal thermoplastic resin composition can be applied.
  • the obtained pellet is subjected to injection molding, die molding, or the like, and can be molded into a desired shape.
  • extrusion molding, hollow molding, foam molding, and the like can also be employed.
  • the amount of each component contained in the composite material before the heat treatment and the molded product after the heat treatment is considered to be substantially the same. That is, it can be considered that the amount of each component in the molded body of the present invention is the same as the amount of each component in the composite material.
  • CM-modified cellulose As described above, in the present invention, by using together (1) CM-modified cellulose fiber, (2) a polymer compound having a primary amino group, and (3) acid-modified polyolefin, CM-modified cellulose is used.
  • the fiber and the polyolefin resin can be uniformly dispersed in the composite material.
  • the bond strength between CM-ized cellulose fibers can be improved, and the interfacial adhesion strength between CM-modified cellulose fibers having high hydrophilicity and polyolefin resins having high hydrophobicity can be improved.
  • a polyolefin-based molded body having high strength and high elastic modulus can be obtained.
  • carboxyl group and carboxymethyl group present on the surface of CM-modified cellulose fiber are: It is considered that a part or the whole reacts and is bonded by heating. These bonds are considered to contribute to the improvement of the strength and elastic modulus of the resin material.
  • the molded article of the present invention is a glass fiber reinforced material in which the glass fiber is replaced with a CM cellulose fiber, which is lighter than the glass fiber reinforced material and reduces incineration ash at the time of disposal. It is considered possible. In addition, since it has high strength, it can be used for the housing (housing) of home appliances such as personal computers and mobile phones, office equipment such as stationery, household goods such as furniture, sports equipment, automobiles, etc. It can also be used for interiors such as dashboards, luggage storage for airplanes, structural members for transportation equipment, and building materials such as sashes in houses. Furthermore, since it is excellent in insulation, application to electrical / electronic / communication equipment can be expected.
  • the crystallinity of cellulose type I was determined by measuring the X-ray diffraction of the sample. X-ray diffraction was measured by placing a sample on a glass cell and using an X-ray diffraction measurement apparatus (LabX XRD-6000, manufactured by Shimadzu Corporation).
  • Xc ( I002c- Ia ) / I002c * 100
  • Xc degree of crystallinity of cellulose type I (%)
  • CM-DS carboxymethyl substitution
  • carboxymethylated cellulose fiber 3 Production was conducted in the same manner as in Production 1 except that the amount of sodium monochloroacetate was changed to 468 g (in terms of active ingredient).
  • the obtained carboxymethylated cellulose fiber had a degree of carboxymethyl substitution per glucose unit of 0.20, a degree of crystallinity of 73%, an average fiber diameter of 18.6 ⁇ m, and an average fiber length of 1.1 mm.
  • the obtained mixture was melted and kneaded (rotation speed: 200 rpm, temperature: 180 ° C.) with a twin-screw extruder (MFU15TW-45HG, screw diameter: 15 mm, manufactured by Technobel Co., Ltd.), and pelletized. Further, the obtained pellets were put into an injection molding machine to obtain a dumbbell-shaped molded product. The molding temperature was 190 ° C. Table 1 shows the tensile strength and tensile modulus of the obtained molded product.
  • Example 2 The same procedure as in Example 1 was performed except that the CM-converted cellulose fiber obtained in Production 2 was used.
  • Example 3 The same procedure as in Example 1 was performed except that the CM-converted cellulose fiber obtained in Production 3 was used.
  • Example 4 The same procedure as in Example 1 was performed except that the CM-converted cellulose fiber obtained in Production 4 was used.
  • Example 5 The same procedure as in Example 1 was carried out except that the CMized cellulose fiber obtained in Production 5 was used.
  • Example 6 The same procedure as in Example 1 was performed except that the CM-converted cellulose fiber obtained in Production 6 was used.
  • Example 7 The same procedure as in Example 1 was performed except that the CM-converted cellulose fiber obtained in Production 7 was used.

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Abstract

This composite material is obtained by mixing (1) a carboxymethylated cellulose fiber, (2) a polymer compound having a primary amino group, (3) an acid-modified polyolefin and (4) a polyolefin resin. This molded body is obtained by subjecting this composite material to a heat treatment.

Description

複合材料及びそれを用いた成形体COMPOSITE MATERIAL AND MOLDED BODY USING SAME
　本発明は、カルボキシメチル化セルロースファイバーとポリオレフィン樹脂とを含む複合樹脂及びこれを加熱処理して成る成形体に関する。 The present invention relates to a composite resin containing a carboxymethylated cellulose fiber and a polyolefin resin, and a molded product obtained by heat-treating the composite resin.
　セルロース系ファイバーとポリプロピレン（以下、「ＰＰ」と略記することがある)からなる複合材料は良く知られているが、ＰＰ等のポリオレフィン樹脂は疎水性が高く、一方、セルロース系ファイバーは親水性が高いため、均一に混合することが困難であった。このため、マレイン酸変性ポリプロピレン(以下、「ＭＡＰＰ」と略記することがある)を相溶化剤、又は界面補強剤として使用することが知られている(例えば、特許文献１等)。また、特許文献２の実施例には、リグニンを含有するセルロース系ファイバー、ＰＰ、及びＭＡＰＰからなる複合材料が開示されている。さらに、特許文献３の実施例には、セルロース系ファイバー、ＰＰ、ＭＡＰＰ及び特定の第１級アミノ基を有する化合物からなる複合材料が開示されている。 Composite materials composed of cellulosic fibers and polypropylene (hereinafter sometimes abbreviated as “PP”) are well known, but polyolefin resins such as PP are highly hydrophobic, while cellulosic fibers are hydrophilic. Since it is high, it was difficult to mix uniformly. For this reason, it is known to use maleic acid-modified polypropylene (hereinafter sometimes abbreviated as “MAPP”) as a compatibilizing agent or an interfacial reinforcing agent (for example, Patent Document 1). Moreover, the Example of patent document 2 is disclosing the composite material which consists of cellulose fiber containing lignin, PP, and MAPP. Furthermore, the Example of patent document 3 is disclosing the composite material which consists of a cellulosic fiber, PP, MAPP, and the compound which has a specific primary amino group.
米国特許出願公開第２００８／０１４６７０１号明細書US Patent Application Publication No. 2008/0146701 特開２００９－１９２００号公報JP 2009-19200 A 国際公開第２０１１／０４９１６２号International Publication No. 2011/049162
　特許文献１～３に記載されるような方法により、セルロース系ファイバーとＰＰとの複合材料の強度及び弾性率は幾分か向上したものの、より一層の向上が望まれる。 Although the strength and elastic modulus of the composite material of cellulosic fiber and PP are somewhat improved by the methods described in Patent Documents 1 to 3, further improvement is desired.
　本発明は、セルロース系ファイバーとポリオレフィン樹脂との均一分散性や界面相互作用を高めることで、高強度、高弾性のセルロース系ファイバーとポリオレフィン樹脂との複合材料を提供することを課題とする。 An object of the present invention is to provide a composite material of a high strength and high elasticity cellulose fiber and a polyolefin resin by enhancing the uniform dispersibility and interfacial interaction between the cellulose fiber and the polyolefin resin.
　本発明者らは、上記課題を解決するために鋭意研究を重ねた結果、セルロース系ファイバーをカルボキシメチル化することで、第１級アミノ基を有する高分子化合物のアミノ基とセルロース系ファイバーとの静電相互作用が高まり、強度、弾性率が大幅に向上したセルロース系ファイバーとポリオレフィン樹脂とを含む成形材料が得られることを見出した。本発明は、これらに限定されないが、以下を含む。
１．　（１）カルボキシメチル化セルロースファイバー、（２）第１級アミノ基を有する高分子化合物、（３）酸変性されたポリオレフィン、及び（４）ポリオレフィン樹脂を含有する複合材料。
２．　前記カルボキシメチル化セルロースファイバーは、セルロースの無水グルコース単位当たりのカルボキシメチル基置換度が０．０１～０．４０であり、且つセルロースＩ型の結晶化度が６０％以上である、上記１に記載の複合材料。
３．　前記酸変性されたポリオレフィンが、無水マレイン酸変性ポリオレフィンである、上記１または２に記載の複合材料。
４．　前記無水マレイン酸変性ポリオレフィンが、無水マレイン酸変性ポリプロピレンであり、前記ポリオレフィン樹脂が、ポリプロピレンである、上記１～３のいずれか１つに記載の複合材料。
５．　前記第１級アミノ基を有する高分子化合物が、下記一般式（Ａ）で表される繰り返し単位を有する化合物、 As a result of intensive research to solve the above-mentioned problems, the present inventors have carboxymethylated the cellulose fiber so that the amino group of the polymer compound having a primary amino group and the cellulose fiber It has been found that a molding material containing a cellulosic fiber and a polyolefin resin having an improved electrostatic interaction and greatly improved strength and elastic modulus can be obtained. The present invention includes, but is not limited to:
1. (1) Carboxymethylated cellulose fiber, (2) a polymer compound having a primary amino group, (3) acid-modified polyolefin, and (4) a composite material containing a polyolefin resin.
2. 2. The carboxymethylated cellulose fiber according to 1 above, wherein the degree of carboxymethyl group substitution per anhydroglucose unit of cellulose is 0.01 to 0.40, and the crystallinity of cellulose I type is 60% or more. Composite material.
3. 3. The composite material according to 1 or 2 above, wherein the acid-modified polyolefin is maleic anhydride-modified polyolefin.
4). 4. The composite material according to any one of 1 to 3 above, wherein the maleic anhydride-modified polyolefin is maleic anhydride-modified polypropylene, and the polyolefin resin is polypropylene.
5. The compound in which the polymer compound having the primary amino group has a repeating unit represented by the following general formula (A):
Figure JPOXMLDOC01-appb-C000004
 で表される繰り返し単位を有する化合物、下記一般式（Ｂ）：
Figure JPOXMLDOC01-appb-C000004
 A compound having a repeating unit represented by the following general formula (B):
Figure JPOXMLDOC01-appb-C000005
 で表される繰り返し単位を有する化合物、下記一般式（Ｃ）：
Figure JPOXMLDOC01-appb-C000005
 A compound having a repeating unit represented by the following general formula (C):
Figure JPOXMLDOC01-appb-C000006
 で表される繰り返し単位を有する化合物、及びこれらの塩からなる群から選ばれる少なくとも１種である、上記１～４のいずれか１つに記載の複合材料。
６．　（１）カルボキシメチル化セルロースファイバー、（２）第１級アミノ基を有する高分子化合物、（３）酸変性されたポリオレフィン、及び（４）ポリオレフィン樹脂を混練する工程を含む、上記１～５のいずれか１つに記載の複合材料の製造方法。
７．　上記１～５のいずれか１つに記載の複合材料を１００～３００℃で加熱処理してなる成形体。
Figure JPOXMLDOC01-appb-C000006
 5. The composite material according to any one of 1 to 4 above, which is at least one selected from the group consisting of a compound having a repeating unit represented by the formula: and a salt thereof.
6). (1) Carboxymethylated cellulose fiber, (2) a polymer compound having a primary amino group, (3) an acid-modified polyolefin, and (4) a step of kneading a polyolefin resin. The manufacturing method of the composite material as described in any one.
7). A molded product obtained by heat-treating the composite material according to any one of 1 to 5 above at 100 to 300 ° C.
　本発明によれば、セルロース系ファイバーのカルボキシメチル化により、セルロース系ファイバーと第１級アミノ基との静電相互作用、及び、セルロース系ファイバーと酸変性されたポリオレフィンとの界面接着性が改善され、高強度及び高弾性率の成形体を得ることができる。 According to the present invention, the carboxymethylation of the cellulosic fiber improves the electrostatic interaction between the cellulosic fiber and the primary amino group and the interfacial adhesion between the cellulosic fiber and the acid-modified polyolefin. A molded product having high strength and high elastic modulus can be obtained.
　１．複合材料
　本発明の複合材料は、（１）カルボキシメチル化セルロースファイバー（以下、「ＣＭ化セルロースファイバー」と略記することがある)、（２）第１級アミノ基を有する高分子化合物、（３）酸変性されたポリオレフィン、及び（４）ポリオレフィン樹脂を含む。 1. Composite Material The composite material of the present invention comprises (1) carboxymethylated cellulose fiber (hereinafter sometimes abbreviated as “CM cellulose fiber”), (2) a polymer compound having a primary amino group, (3 A) an acid-modified polyolefin; and (4) a polyolefin resin.
　（１）ＣＭ化セルロースファイバー
　本発明の複合材料に含有されるセルロースファイバーは、カルボキシメチル基を含む。セルロースにカルボキシメチル置換基を導入することで、セルロースファイバーと、（２）第１級アミノ基を有する高分子化合物のアミノ基との静電相互作用が大きくなる。このことによって、（１）ＣＭ化セルロースファイバー同士のネットワーク構造が補強される。また、（３）酸変性されたポリオレフィンの親水基部分が（１）ＣＭ化セルロースファイバーと、疎水基部分が（４）ポリオレフィン樹脂とそれぞれ反応して、（１）ＣＭ化セルロースファイバーと（４）ポリオレフィン樹脂との界面相互作用が補強される。ＣＭ化セルロースファイバーは、セルロースの無水グルコース単位当たりのカルボキシメチル置換度が０．０１～０．４０であることが好ましく、０．０５～０．２０であることがより好ましい。また、ＣＭ化セルロースファイバーにおけるセルロースＩ型の結晶化度は６０％以上であることが好ましく、７０％以上であることがより好ましく、８０％以上であることがさらに好ましい。なお、無水グルコース単位当たりのカルボキシメチル基置換基が０．０１より小さいと、十分に効果を発揮することができない場合がある。一方、無水グルコース単位当たりのカルボキシメチル置換基が０．４０より大きいと、ＣＭ化セルロースファイバーが膨潤あるいは溶解するため、繊維形態を維持できなくなり、ファイバーとして得られなくなる場合がある。また、セルロースＩ型の結晶化度が６０％未満であるとセルロースファイバーの強度が低下し、ポリオレフィン樹脂の補強材としての十分な補強効果が得られなくなる場合がある。 (1) CMized cellulose fiber The cellulose fiber contained in the composite material of the present invention contains a carboxymethyl group. By introducing a carboxymethyl substituent into cellulose, electrostatic interaction between the cellulose fiber and (2) the amino group of the polymer compound having a primary amino group is increased. This reinforces (1) the network structure of the CMized cellulose fibers. Further, (3) the hydrophilic group portion of the acid-modified polyolefin reacts with (1) CM-modified cellulose fiber and the hydrophobic group portion reacts with (4) polyolefin resin, respectively, and (1) CM-modified cellulose fiber and (4) Interfacial interaction with polyolefin resin is reinforced. In the CM cellulose fiber, the degree of carboxymethyl substitution per anhydroglucose unit of cellulose is preferably 0.01 to 0.40, and more preferably 0.05 to 0.20. In addition, the degree of crystallinity of cellulose type I in the CMized cellulose fiber is preferably 60% or more, more preferably 70% or more, and further preferably 80% or more. In addition, when the carboxymethyl group substituent per anhydroglucose unit is smaller than 0.01, the effect may not be sufficiently exhibited. On the other hand, when the carboxymethyl substituent per anhydroglucose unit is larger than 0.40, the CM-ized cellulose fiber swells or dissolves, so that the fiber form cannot be maintained and may not be obtained as a fiber. Further, when the crystallinity of cellulose I type is less than 60%, the strength of the cellulose fiber is lowered, and a sufficient reinforcing effect as a reinforcing material for the polyolefin resin may not be obtained.
　ＣＭ化セルロースファイバーの製造方法は特に限定されるものではないが、セルロース原料をカルボキシメチル化することによって得ることができる。 Although the production method of CM cellulose fiber is not particularly limited, it can be obtained by carboxymethylating the cellulose raw material.
　（セルロース原料）
　セルロース原料としては、植物（例えば、木材、竹、麻、ジュート、ケナフ、農地残廃物、布、パルプ（針葉樹未漂白クラフトパルプ（ＮＵＫＰ）、針葉樹漂白クラフトパルプ（ＮＢＫＰ）、広葉樹未漂白クラフトパルプ（ＬＵＫＰ）、広葉樹漂白クラフトパルプ（ＬＢＫＰ）、針葉樹未漂白サルファイトパルプ（ＮＵＳＰ）、針葉樹漂白サルファイトパルプ（ＮＢＳＰ）サーモメカニカルパルプ（ＴＭＰ）、再生パルプ、古紙等）、動物（例えばホヤ類）、藻類、微生物（例えば酢酸菌（アセトバクター））、微生物産生物等を起源とするものが知られており、本発明ではそのいずれも使用できる。好ましくは植物又は微生物由来のセルロースであり、より好ましくは植物由来のセルロースである。 (Cellulose raw material)
Examples of cellulose raw materials include plants (for example, wood, bamboo, hemp, jute, kenaf, agricultural land residue, cloth, pulp (coniferous unbleached kraft pulp (NUKP), conifer bleached kraft pulp (NBKP), hardwood unbleached kraft pulp ( LUKP), hardwood bleached kraft pulp (LBKP), softwood unbleached sulfite pulp (NUSP), softwood bleached sulfite pulp (NBSP) thermomechanical pulp (TMP), recycled pulp, waste paper, etc.), animals (for example, ascidians), Those originating from algae, microorganisms (for example, acetic acid bacteria (Acetobacter)), microbial products, etc. are known, and any of them can be used in the present invention, preferably cellulose derived from plants or microorganisms, more preferably. Is plant-derived cellulose.
　（カルボキシメチル化）
　セルロース原料のカルボキシメチル化は公知の方法を用いて行うことができ、特に限定されない。また、市販のＣＭ化セルロースファイバーを用いてもよい。本発明では、セルロースの無水グルコース単位当たりのカルボキシメチル基置換度が０．０１～０．４０であり、セルロースＩ型の結晶化度が６０％以上、好ましくは７０％以上、さらに好ましくは８０％以上となるように調整することが好ましい。その一例として次のような製造方法を挙げることができる。発底原料としてセルロースを使用する。溶媒として、３～２０重量倍の水及び／又は低級アルコール、具体的にはメタノール、エタノール、Ｎ－プロピルアルコール、イソプロピルアルコール、Ｎ－ブタノール、イソブタノール、第３級ブタノール等の単独、又は２種以上の混合媒体を使用する。なお、溶媒における低級アルコールの混合割合は、６０～９５重量％である。マーセル化剤として、発底原料の無水グルコース残基当たり０．５～２０倍モルの水酸化アルカリ金属、具体的には水酸化ナトリウム、水酸化カリウムを使用する。発底原料、溶媒、及びマーセル化剤を混合し、反応温度０～７０℃、好ましくは１０～６０℃、かつ反応時間１５分～８時間、好ましくは３０分～７時間、マーセル化処理を行う。その後、カルボキシメチル化剤（例えば、モノクロロ酢酸、モノクロロ酢酸ナトリウムなど）をグルコース残基当たり０．０５～１０．０倍モル添加し、反応温度３０～９０℃、好ましくは４０～８０℃、かつ反応時間３０分～１０時間、好ましくは１時間～４時間、エーテル化反応を行う。 (Carboxymethylation)
Carboxymethylation of a cellulose raw material can be performed using a well-known method, and is not specifically limited. Commercially available CMized cellulose fibers may also be used. In the present invention, the substitution degree of carboxymethyl group per anhydroglucose unit of cellulose is 0.01 to 0.40, and the crystallinity of cellulose type I is 60% or more, preferably 70% or more, more preferably 80%. It is preferable to adjust so that it may become above. As an example, the following manufacturing method can be mentioned. Cellulose is used as the bottoming material. As a solvent, 3 to 20 times by weight of water and / or lower alcohol, specifically, methanol, ethanol, N-propyl alcohol, isopropyl alcohol, N-butanol, isobutanol, tertiary butanol and the like alone or two kinds The above mixed medium is used. The mixing ratio of the lower alcohol in the solvent is 60 to 95% by weight. As the mercerizing agent, 0.5 to 20 times moles of alkali metal hydroxide, specifically sodium hydroxide or potassium hydroxide is used per anhydroglucose residue of the bottoming material. A bottoming raw material, a solvent, and a mercerizing agent are mixed and subjected to mercerization treatment at a reaction temperature of 0 to 70 ° C., preferably 10 to 60 ° C., and a reaction time of 15 minutes to 8 hours, preferably 30 minutes to 7 hours. . Thereafter, a carboxymethylating agent (for example, monochloroacetic acid, sodium monochloroacetate, etc.) is added at 0.05 to 10.0 times mole per glucose residue, the reaction temperature is 30 to 90 ° C., preferably 40 to 80 ° C., and the reaction is performed. The etherification reaction is carried out for 30 minutes to 10 hours, preferably 1 to 4 hours.
　（解繊）
　本発明の複合材料に含有されるＣＭ化セルロースファイバーの平均繊維径は４ｎｍ～５０μｍであることが好ましく、２００ｎｍ～５０μｍであることがより好ましく、５００ｎｍ～２０μｍであることがより一層好ましい。また、ＣＭ化セルロースファイバーの平均繊維長は、０．５ｍｍ～５．０ｍｍであることが好ましい。ＣＭ化セルロースファイバーの平均繊維径及び平均繊維長を上記範囲内に調整すると、ＣＭ化セルロースファイバーによるポリオレフィン樹脂の補強効果が高まる。 (Defibration)
The average fiber diameter of the CM-converted cellulose fiber contained in the composite material of the present invention is preferably 4 nm to 50 μm, more preferably 200 nm to 50 μm, and even more preferably 500 nm to 20 μm. Further, the average fiber length of the CMized cellulose fiber is preferably 0.5 mm to 5.0 mm. When the average fiber diameter and average fiber length of the CM-converted cellulose fiber are adjusted within the above ranges, the reinforcing effect of the polyolefin resin by the CM-converted cellulose fiber is enhanced.
　ＣＭ化セルロースファイバーの繊維径および繊維長は、透過型電子顕微鏡（ＴＥＭ）、走査型電子顕微鏡（ＳＥＭ）、またはデジタルＣＣＤ顕微鏡を用いて、代表的な繊維１００本を測定し、平均値を算出した。 The fiber diameter and fiber length of the CMized cellulose fiber were measured with 100 representative fibers using a transmission electron microscope (TEM), scanning electron microscope (SEM), or digital CCD microscope, and the average value was calculated. did.
　本発明では、ＣＭ化セルロースファイバーの繊維径及び繊維長が上記の範囲になるように、必要に応じて解繊を行う。解繊は、セルロース原料のカルボキシメチル化の後に行ってもよいし、セルロース原料を上記の範囲になるように解繊してからカルボキシメチル化を行ってもよい。解繊をする場合には、これに限定されないが、取扱い容易性から、ＣＭ化セルロースファイバーの水分散体を用いることが好ましい。 In the present invention, defibration is performed as necessary so that the fiber diameter and fiber length of the CMized cellulose fiber are in the above ranges. The defibrating may be performed after carboxymethylation of the cellulose raw material, or carboxymethylation may be performed after the cellulose raw material is defibrated to be in the above range. When defibrating, it is not limited to this, but it is preferable to use an aqueous dispersion of CM-modified cellulose fiber from the viewpoint of ease of handling.
　解繊用の装置は特に限定されず、必要に応じて、高速回転式、コロイドミル式、高圧式、ロールミル式、超音波式などの装置や、マスコロイダーを用いることができる。また、後述する他の成分との混合に際して、例えば二軸押出機（二軸混練機）中で解繊と他の成分との混合とを同時に行ってもよい。ＣＭ化セルロースファイバーを微細に解繊する場合には、前記水分散体に５０ＭＰａ以上の圧力を印加できる湿式の高圧または超高圧ホモジナイザーを用いてもよい。前記圧力は、より好ましくは１００ＭＰａ以上であり、さらに好ましくは１４０ＭＰａ以上である。また、高圧ホモジナイザーでの解繊・分散処理に先立って、必要に応じて、高速せん断ミキサーなどの公知の混合、攪拌、乳化、分散装置を用いて、上記のＣＭ化セルロースファイバーに予備処理を施してもよい。 The device for defibration is not particularly limited, and a high-speed rotation type, a colloid mill type, a high-pressure type, a roll mill type, an ultrasonic type, or a mass collider can be used as necessary. Moreover, when mixing with other components described later, for example, defibration and mixing with other components may be performed simultaneously in a twin screw extruder (a twin screw kneader). When the CMized cellulose fiber is finely defibrated, a wet high pressure or ultra high pressure homogenizer that can apply a pressure of 50 MPa or more to the aqueous dispersion may be used. The pressure is more preferably 100 MPa or more, and further preferably 140 MPa or more. In addition, prior to defibration / dispersion treatment with a high-pressure homogenizer, if necessary, the CM-modified cellulose fiber is pretreated using a known mixing, stirring, emulsifying, and dispersing device such as a high-speed shear mixer. May be.
　本発明の複合材料において、ＣＭ化セルロースファイバーの配合量は、複合材料全体量中、通常１～９４質量％程度、好ましくは２～９２質量％程度である。 In the composite material of the present invention, the blending amount of the CMized cellulose fiber is usually about 1 to 94% by mass, preferably about 2 to 92% by mass, based on the total amount of the composite material.
　（２）第１級アミノ基を有する高分子化合物
　本発明の複合材料は、分子内に第１級アミノ基を有する高分子化合物を含む。 (2) Polymer compound having primary amino group The composite material of the present invention includes a polymer compound having a primary amino group in the molecule.
　第１級アミノ基を有する高分子化合物の重量平均分子量は、通常１０００～１００万程度、好ましくは１２００～７０万程度である。 The weight average molecular weight of the polymer compound having a primary amino group is usually about 1,000 to 1,000,000, preferably about 1200 to 700,000.
　なお、本発明において、重量平均分子量は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法（ＰＥＧ換算）、ＧＰＣ法（プルラン換算）又はＧＰＣカラムに多角度光散乱検出器を接続したＧＰＣ－ＭＡＬＬＳのいずれかの方法で測定した値である。 In the present invention, the weight average molecular weight is determined by gel permeation chromatography (GPC) method (PEG conversion), GPC method (pullulan conversion) or GPC-MALLS with a multi-angle light scattering detector connected to a GPC column. It is a value measured by any method.
　第１級アミノ基を有する高分子化合物のアミノ基は、有機酸又は無機酸と塩を形成していてもよい。該アミノ基が塩を形成し得る無機酸としては、例えば、塩酸、硫酸、リン酸、ホウ酸、臭化水素酸、ヨウ化水素酸等が挙げられ、有機酸としては、例えば、ギ酸、酢酸、プロピオン酸、ｐ－トルエンスルホン酸、メタンスルホン酸、クエン酸、酒石酸等が挙げられる。 The amino group of the polymer compound having a primary amino group may form a salt with an organic acid or inorganic acid. Examples of the inorganic acid from which the amino group can form a salt include hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, hydrobromic acid, hydroiodic acid, and the like, and examples of the organic acid include formic acid, acetic acid, and the like. , Propionic acid, p-toluenesulfonic acid, methanesulfonic acid, citric acid, tartaric acid and the like.
　第１級アミノ基を有する高分子化合物は、１種を単独で使用してもよいし、２種以上を混合して使用してもよい。第１級アミノ基を有する高分子化合物は、公知の方法で合成してもよく、市販品を使用してもよい。 The polymer compound having a primary amino group may be used alone or in combination of two or more. The polymer compound having a primary amino group may be synthesized by a known method, or a commercially available product may be used.
　第１級アミノ基を有する高分子化合物としては、例えば下記一般式（Ａ）： Examples of the polymer compound having a primary amino group include the following general formula (A):
Figure JPOXMLDOC01-appb-C000007
 で表されるアリルアミン単位を繰り返し単位として有する化合物及びその塩が挙げられる。
Figure JPOXMLDOC01-appb-C000007
 The compound which has an allylamine unit represented by these as a repeating unit, and its salt are mentioned.
　一般式（Ａ）で表される繰り返し単位を有する化合物は、前記一般式（Ａ）で表される繰り返し単位の他に、他の繰り返し単位を含む共重合体、グラフト重合体であってもよい。 The compound having a repeating unit represented by the general formula (A) may be a copolymer or graft polymer containing other repeating units in addition to the repeating unit represented by the general formula (A). .
　前記一般式（Ａ）で表される繰り返し単位と結合して共重合体、グラフト重合体を形成する他の繰り返し単位としては、例えばポリアクリレート単位、ポリメタクリレート単位、ポリアクリルアミド単位、ポリジアリルアミン単位のような２級アミンを含む単位、ポリメチルジアリルアミン単位のような３級アミンを含む単位、ポリジアリルジメチルアンモニウム塩単位のような４級アンモニウム塩を含む単位等が挙げられる。各繰り返し単位の結合順は限定されず、ランダムでもブロックでもよい。 Examples of other repeating units that form a copolymer or graft polymer by combining with the repeating unit represented by the general formula (A) include polyacrylate units, polymethacrylate units, polyacrylamide units, and polydiallylamine units. Examples thereof include a unit containing a secondary amine, a unit containing a tertiary amine such as a polymethyldiallylamine unit, and a unit containing a quaternary ammonium salt such as a polydiallyldimethylammonium salt unit. The order of combining the repeating units is not limited, and may be random or block.
　ただし、一般式（Ａ）で表される繰り返し単位以外の繰り返し単位量が多くなり過ぎると、単位重量当たりの第１級アミノ基の数が減るので好ましくない。一般式（Ａ）で表される繰り返し単位を含む化合物は、一般式（Ａ）で表される繰り返し単位のみを含むホモポリマー又はその塩であることがより好ましい。 However, when the amount of the repeating unit other than the repeating unit represented by the general formula (A) is excessively increased, the number of primary amino groups per unit weight is not preferable. The compound containing the repeating unit represented by the general formula (A) is more preferably a homopolymer containing only the repeating unit represented by the general formula (A) or a salt thereof.
　一般式（Ａ）で表される繰り返し単位を有する化合物の重量平均分子量は、第１級アミノ基を有する高分子化合物として上記したように、通常１０００～１００万程度、好ましくは１２００～７０万程度である。 The weight average molecular weight of the compound having the repeating unit represented by the general formula (A) is usually about 1,000 to 1,000,000, preferably about 1200 to 700,000 as described above for the polymer compound having a primary amino group. It is.
　一般式（Ａ）で表される繰り返し単位を有する化合物の塩としては、塩酸塩、硫酸塩、リン酸、臭化水素酸塩等の無機酸塩、ギ酸塩、酢酸塩、プロピオン酸塩、ｐ－トルエンスルホン酸塩、メタンスルホン酸塩、クエン酸塩、酒石酸塩等の有機酸塩が挙げられる。一般式（Ａ）で表される繰り返し単位を有する化合物は、アリルアミン等を原料として公知の重合方法で合成することができる。市販品も入手可能である。 Examples of the salt of the compound having a repeating unit represented by formula (A) include inorganic acid salts such as hydrochloride, sulfate, phosphoric acid and hydrobromide, formate, acetate, propionate, p Organic salts such as toluenesulfonate, methanesulfonate, citrate, tartrate, etc. The compound having a repeating unit represented by formula (A) can be synthesized by a known polymerization method using allylamine or the like as a raw material. Commercial products are also available.
　また、第１級アミノ基を有する高分子化合物としては、例えば下記一般式(Ｂ)： In addition, as a polymer compound having a primary amino group, for example, the following general formula (B):
Figure JPOXMLDOC01-appb-C000008
 で表されるビニルアミン単位を繰り返し単位として有する化合物及びその塩も挙げられる。
Figure JPOXMLDOC01-appb-C000008
 And compounds having a vinylamine unit represented by the formula (I) as a repeating unit and salts thereof.
　一般式（Ｂ）で表される繰り返し単位を有する化合物は、前記一般式（Ｂ）で表される繰り返し単位の他に、他の繰り返し単位を含む共重合体、グラフト重合体であってもよい。 The compound having a repeating unit represented by the general formula (B) may be a copolymer or graft polymer containing other repeating units in addition to the repeating unit represented by the general formula (B). .
　前記一般式（Ｂ）で表される繰り返し単位と結合して共重合体、グラフト重合体を形成する他の繰り返し単位としては、ポリアクリレート単位、ポリメチルメタクリレート単位、ポリアクリルアミド単位、ポリビニルホルムアミド単位、ポリビニルアセトアミド単位、ポリジアリルアミン単位のような２級アミンを含む単位、ポリメチルジアリルアミン単位のような３級アミンを含む単位、ポリジアリルジメチルアンモニウム塩単位のような４級アンモニウム塩を含む単位等が挙げられる。各繰り返し単位の結合順は限定されず、ランダムでもブロックでもよい。 Other repeating units that form a copolymer or graft polymer by combining with the repeating unit represented by the general formula (B) include a polyacrylate unit, a polymethyl methacrylate unit, a polyacrylamide unit, a polyvinyl formamide unit, Examples include units containing secondary amines such as polyvinylacetamide units, polydiallylamine units, units containing tertiary amines such as polymethyldiallylamine units, units containing quaternary ammonium salts such as polydiallyldimethylammonium salt units, and the like. It is done. The order of combining the repeating units is not limited, and may be random or block.
　ただし、一般式(Ｂ)で表される繰り返し単位以外の繰り返し単位量が多くなり過ぎると、単位重量当たりの1級アミノ基の数が減るので好ましくない。一般式(Ｂ)で表される繰り返し単位を含む化合物は、一般式(Ｂ)で表される繰り返し単位のみを含むホモポリマー又はその塩であることがより好ましい。 However, if the amount of the repeating unit other than the repeating unit represented by the general formula (B) is too large, the number of primary amino groups per unit weight is not preferable. The compound containing the repeating unit represented by the general formula (B) is more preferably a homopolymer containing only the repeating unit represented by the general formula (B) or a salt thereof.
　一般式(Ｂ)で表される繰り返し単位を有する化合物の重量平均分子量は、第１級アミノ基を有する高分子化合物について上記したように、通常１０００～１００万程度、好ましくは１２００～７０万程度である。 The weight average molecular weight of the compound having a repeating unit represented by formula (B) is usually about 1,000 to 1,000,000, preferably about 1200 to 700,000 as described above for the polymer compound having a primary amino group. It is.
　一般式(Ｂ)で表される繰り返し単位を有する化合物の塩としては、塩酸塩、硫酸塩、リン酸塩、臭化水素酸塩、ヨウ化水素酸塩等の無機酸塩、ギ酸塩、酢酸塩、プロピオン酸塩、ｐ－トルエンスルホン酸塩、メタンスルホン酸塩、クエン酸塩、酒石酸塩等の有機酸塩が挙げられる。 Examples of the salt of the compound having the repeating unit represented by the general formula (B) include hydrochloride, sulfate, phosphate, hydrobromide, hydroiodide and other inorganic acid salts, formate salts, acetic acid And organic acid salts such as salts, propionates, p-toluenesulfonates, methanesulfonates, citrates and tartrates.
　一般式(Ｂ)で表される繰り返し単位を有する化合物は、例えばＮービニルホルムアミドやＮ－ビニルアセトアミド等のＮ置換アミド類の重合体を加水分解するか、またはポリアクリルアミドをホフマン変性する等の公知の重合方法で合成することができる。市販品も入手可能である。 The compound having a repeating unit represented by the general formula (B) can be obtained by, for example, hydrolyzing a polymer of N-substituted amides such as N-vinylformamide and N-vinylacetamide, or modifying polyacrylamide with Hoffman. It can be synthesized by a known polymerization method. Commercial products are also available.
　さらに、第１級アミノ基を有する高分子化合物としては、例えば下記一般式(Ｃ)： Furthermore, as a polymer compound having a primary amino group, for example, the following general formula (C):
Figure JPOXMLDOC01-appb-C000009
 で表される繰り返し単位を有する化合物及びその塩も挙げられる。
Figure JPOXMLDOC01-appb-C000009
 And a compound having a repeating unit represented by the formula:
　一般式(Ｃ)で表される繰り返し単位を有する化合物は、前記一般式(Ｃ)で表される繰り返し単位が直鎖上に伸びていても良いし、分岐構造を取っていても良い。また一般式(Ｃ)の他に、他の繰り返し単位を含むグラフト重合体であってもよい。 In the compound having a repeating unit represented by the general formula (C), the repeating unit represented by the general formula (C) may extend on a straight chain or may have a branched structure. In addition to the general formula (C), a graft polymer containing another repeating unit may be used.
　ただし、一般式(Ｃ)で表される繰り返し単位以外の繰り返し単位量が多くなり過ぎると、単位重量当たりの１級アミノ基の数が減るので好ましくない。一般式(Ｃ) で表される繰り返し単位を含む化合物は、一般式(Ｃ)で表される繰り返し単位のみを含むホモポリマー又はその塩であることがより好ましい。このような好ましいホモポリマー又はその塩としては、ポリエチレンイミン又はその塩が挙げられる。 However, if the amount of the repeating unit other than the repeating unit represented by the general formula (C) is too large, the number of primary amino groups per unit weight is not preferable. The compound containing the repeating unit represented by the general formula (C) is more preferably a homopolymer containing only the repeating unit represented by the general formula (C) or a salt thereof. Examples of such a preferred homopolymer or a salt thereof include polyethyleneimine or a salt thereof.
　一般式(Ｃ)で表される繰り返し単位を有する化合物の重量平均分子量は、第１級アミノ基を有する高分子化合物として上記したように、通常１０００～１００万程度、好ましくは１２００～７０万程度である。 The weight average molecular weight of the compound having a repeating unit represented by the general formula (C) is usually about 1,000 to 1,000,000, preferably about 1200 to 700,000 as described above for the polymer compound having a primary amino group. It is.
　一般式(Ｃ)で表される繰り返し単位を有する化合物の塩としては、塩酸塩、硫酸塩、リン酸塩、臭化水素酸塩、ヨウ化水素酸塩等の無機酸塩、ギ酸塩、酢酸塩、プロピオン酸塩、ｐ－トルエンスルホン酸塩、メタンスルホン酸塩、クエン酸塩、酒石酸塩等の有機酸塩が挙げられる。 Examples of the salt of the compound having a repeating unit represented by the general formula (C) include inorganic acid salts such as hydrochloride, sulfate, phosphate, hydrobromide, hydroiodide, formate, and acetic acid. And organic acid salts such as salts, propionates, p-toluenesulfonates, methanesulfonates, citrates and tartrates.
　一般式(Ｃ)で表される繰り返し単位を有する化合物は、力チオンポリマーとして知られており、アジリジンを原料として公知の重合方法で合成することができる。市販品も入手可能である。 The compound having a repeating unit represented by the general formula (C) is known as a force thione polymer, and can be synthesized by a known polymerization method using aziridine as a raw material. Commercial products are also available.
　本発明の複合材料は、上記一般式(Ａ)、(Ｂ)及び(Ｃ)で表される繰り返し単位を有する化合物、並びにこれらの塩からなる群から選ばれる少なくとも１種を含むことが好ましい。 The composite material of the present invention preferably contains at least one selected from the group consisting of compounds having repeating units represented by the general formulas (A), (B) and (C), and salts thereof.
　本発明の複合材料において、第１級アミノ基を有する高分子化合物の配合量は、(１)ＣＭ化セルロースファイバー１００質量部に対して、通常１～３０質量部程度、好ましくは５～３０質量部程度、特に好ましくは１０～２０質量部程度である。 In the composite material of the present invention, the amount of the polymer compound having a primary amino group is usually about 1 to 30 parts by mass, preferably 5 to 30 parts by mass with respect to 100 parts by mass of (1) CMized cellulose fiber. Part by weight, particularly preferably about 10 to 20 parts by weight.
　（３）酸変性されたポリオレフィン
　本発明の複合材料は、酸変性されたポリオレフィンを含む。 (3) Acid-modified polyolefin The composite material of the present invention includes an acid-modified polyolefin.
　酸変性されたポリオレフィンとしては、α、β－不飽和カルボン酸又はその酸無水物、例えば、マレイン酸、フマル酸、イタコン酸、シトラコン酸、アリルコハク酸、メサコン酸、アニコット酸、及びこれらの酸無水物等で変性されたポリオレフィンを例示することができる。特に、反応効率の点から安価に製造可能な無水マレイン酸変性ポリオレフィンが好ましい。 Examples of acid-modified polyolefins include α, β-unsaturated carboxylic acids or acid anhydrides thereof, such as maleic acid, fumaric acid, itaconic acid, citraconic acid, allyl succinic acid, mesaconic acid, annicotic acid, and acid anhydrides thereof. Examples thereof include polyolefins modified with products. In particular, maleic anhydride-modified polyolefin that can be produced at low cost is preferable from the viewpoint of reaction efficiency.
　酸変性されたポリオレフィンは、重量平均分子量で通常１万～１０万程度、好ましくは２万～８万程度の分子量のものを使用すればよい。また、酸で変性されたポリオレフィンは１種を単独で使用してもよいし、２種以上を混合して使用してもよい。酸変性されたポリオレフィンは、公知の方法で合成してもよく、市販品を使用してもよい。 The acid-modified polyolefin has a weight average molecular weight of usually about 10,000 to 100,000, preferably about 20,000 to 80,000. Moreover, the polyolefin modified with an acid may be used individually by 1 type, and 2 or more types may be mixed and used for it. The acid-modified polyolefin may be synthesized by a known method, or a commercially available product may be used.
　無水マレイン酸変性ポリオレフィンとしては、例えば、無水マレイン酸変性ポリエチレン、無水マレイン酸変性ポリプロピレン、無水マレイン酸変性ポリブタジエン、無水マレイン酸変性ポリスチレン、無水マレイン酸変性ポリメタクリレート等が挙げられる。また、エチレン、プロピレン、１－ブテン、１－ペンテン、１－ヘキセン等の直鎖状オレフィン、３－メチル－１－ブテン、３－メチル－１－ペンテン、４－メチル－１－ペンテン等の分岐状オレフィン、ブタジエン、スチレンなどを有する共重合体の無水マレイン酸変性体も挙げられる。 Examples of the maleic anhydride-modified polyolefin include maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, maleic anhydride-modified polybutadiene, maleic anhydride-modified polystyrene, and maleic anhydride-modified polymethacrylate. In addition, linear olefins such as ethylene, propylene, 1-butene, 1-pentene and 1-hexene, and branches such as 3-methyl-1-butene, 3-methyl-1-pentene and 4-methyl-1-pentene Examples thereof also include maleic anhydride-modified copolymers having a copolymer olefin, butadiene, styrene and the like.
　無水マレイン酸で変性されたポリオレフィンは、通常、後述の（４）ポリオレフィン樹脂と同様の骨格を有することが好ましい。すなわち、例えば、(４)ポリオレフィン樹脂としてポリプロピレン樹脂を用いる場合は、(３)酸で変性されたポリオレフィンとして、無水マレイン酸変性ポリプロピレンなどの酸変性ポリプロピレン樹脂を使用することが特に好ましい。 Usually, the polyolefin modified with maleic anhydride preferably has the same skeleton as (4) polyolefin resin described later. That is, for example, when (4) a polypropylene resin is used as the polyolefin resin, it is particularly preferable to use an acid-modified polypropylene resin such as maleic anhydride-modified polypropylene as the (3) acid-modified polyolefin.
　酸変性されたポリオレフィンの酸変性率は、通常０．２～１０質量％程度、好ましくは３～７質量％程度である。 The acid modification rate of the acid-modified polyolefin is usually about 0.2 to 10% by mass, preferably about 3 to 7% by mass.
　本発明の複合材料において、酸変性された高分子化合物の配合量は、（１）ＣＭ化セルロースファイバー１００質量部に対して、通常４～５０質量部程度、好ましくは１０～３０質量部程度である。 In the composite material of the present invention, the compounding amount of the acid-modified polymer compound is (1) about 4 to 50 parts by mass, preferably about 10 to 30 parts by mass with respect to 100 parts by mass of the CMized cellulose fiber. is there.
　(４)ポリオレフィン樹脂
　本発明の複合材料は、主成分としてポリオレフィン樹脂を含む。ポリオレフィン樹脂は、公知のものを使用すればよい。ポリオレフィンとしては、例えば、エチレン、プロピレン、１－ブテン、１－ペンテン、１－へキセン等の直鎖状αオレフィン、３－メチル－１－ブテン、３－メチル－１－ペンテン、４－メチル－１－ペンテン等の分岐状オレフィン、スチレン、ブタジエン、イソプレン、クロロプレン、イソブチレン、イソプレンなどの単独重合体又は共重合体、ノルボルネン骨格を有する環状ポリオレフィン等が挙げられる。 (4) Polyolefin resin The composite material of the present invention contains a polyolefin resin as a main component. A known polyolefin resin may be used. Examples of the polyolefin include linear α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl- Examples thereof include branched olefins such as 1-pentene, homopolymers or copolymers such as styrene, butadiene, isoprene, chloroprene, isobutylene and isoprene, and cyclic polyolefins having a norbornene skeleton.
　ポリオレフィン樹脂の重量平均分子量は、通常１０万～４０万程度、好ましくは２０万～３０万程度である。また、ポリオレフィン樹脂は１種を単独で使用してもよいし、２種以上を混合して使用してもよい。ポリオレフィン樹脂は、公知の方法で合成してもよく、市販品を使用してもよい。 The weight average molecular weight of the polyolefin resin is usually about 100,000 to 400,000, preferably about 200,000 to 300,000. In addition, the polyolefin resin may be used alone or in combination of two or more. The polyolefin resin may be synthesized by a known method, or a commercially available product may be used.
　本発明の複合材料において、ポリオレフィンの配合量は、複合材料全体量中、通常１～９８質量％程度、好ましくは２～９６質量％程度である。 In the composite material of the present invention, the blending amount of polyolefin is usually about 1 to 98% by mass, preferably about 2 to 96% by mass in the total amount of the composite material.
　本発明の複合材料は、（１）ＣＭ化セルロースファイバー、（２）第１級アミノ基を有する高分子化合物、（３）酸変性されたポリオレフィン、及び（４）ポリオレフィン樹脂に加えて、必要に応じて他の成分を含んでいてもよい。他の成分としては、例えば、水；水酸化ナトリウム、水駿化カリウム、水酸化マグネシウム、水酸化カルシウム等のアルカリ；クレー、タルク、炭酸カルシウム、マイ力、二酸化チタン、酸化亜鉛等の無機填料；カーボンブラック、グラファイト、ガラスフレーク等の有機填料；ベンガラ、アゾ顔料、フタロシアニン等の染料又は顔料；分散剤、滑剤、可塑剤、離型剤、難燃剤、酸化防止剤（フェノール系酸化防止剤、リン酸化防止剤、イオウ系酸化防止剤）、帯電防止剤、光安定剤、紫外線吸収剤、金属不活性剤、結晶化促進剤（造核剤）、発泡剤、架橋剤、抗菌剤等の改質用添加剤等が挙げられる。 In addition to (1) CM-modified cellulose fiber, (2) polymer compound having primary amino group, (3) acid-modified polyolefin, and (4) polyolefin resin, the composite material of the present invention Depending on the case, other components may be included. Examples of other components include water; alkalis such as sodium hydroxide, potassium hydride, magnesium hydroxide, and calcium hydroxide; inorganic fillers such as clay, talc, calcium carbonate, my strength, titanium dioxide, and zinc oxide; Organic fillers such as carbon black, graphite, glass flakes; dyes or pigments such as bengara, azo pigments, phthalocyanines; dispersants, lubricants, plasticizers, mold release agents, flame retardants, antioxidants (phenolic antioxidants, phosphorus Antioxidants, sulfur-based antioxidants), antistatic agents, light stabilizers, UV absorbers, metal deactivators, crystallization accelerators (nucleating agents), foaming agents, crosslinking agents, antibacterial agents, etc. Additives and the like.
　（１）ＣＭ化セルロースファイバー、（２）第１級アミノ基を有するアミン系高分子化合物、及び（３）酸変性されたポリオレフィンを併用することにより、（１）ＣＭ化セルロースファイバーと（４）ポリオレフィン樹脂とを複合材料中でそれぞれ均一に分散させることができ、また、高強度及び高弾性率の複合材料を得ることができる。また、このようにして得られた複合材料を加熱処理することにより、後述の通り、高強度、高弾性率のＣＭ化セルロースファイバー含有成形体を得ることができる。 By using together (1) CM cellulose fiber, (2) amine polymer compound having primary amino group, and (3) acid-modified polyolefin, (1) CM cellulose fiber and (4) The polyolefin resin can be uniformly dispersed in the composite material, and a composite material having high strength and high elastic modulus can be obtained. Moreover, by heat-treating the composite material thus obtained, a CM-containing cellulose fiber-containing molded body having high strength and high elastic modulus can be obtained as described later.
　２．複合材料の製造方法
　複合材料の製造方法は特に限定されず、（１）ＣＭ化セルロースファイバー、（２）第１級アミノ基を有する高分子化合物、（３）酸変性されたポリオレフィン、及び（４）ポリオレフィン樹脂、及び必要に応じて他の成分を混合すればよい。（１）～（４）の各成分及び他の成分の混練順序は特に限定されない。 2. Production method of composite material The production method of the composite material is not particularly limited. (1) CM-modified cellulose fiber, (2) polymer compound having primary amino group, (3) acid-modified polyolefin, and (4 ) Polyolefin resin and other components may be mixed if necessary. The order of kneading each component (1) to (4) and other components is not particularly limited.
　また、前記（１）～（４）の各成分及び他の成分の混合方法は、特に限定されず、公知の方法を用いればよい。例えば、前記（１）～（４）の各成分及び他の成分を二軸押出機（二軸混練機）等で混練することによって、各成分を均一に分散させることができる。前記の通り、本発明においては、（２）第１級アミノ基を有するアミン系高分子化合物、及び（３）酸変性されたポリオレフィンの両者を複合材料中に混合することにより、複合材料に含まれる各成分を均一に分散させることができる。各成分の混合の際の温度は特に限定されず、通常０～３００℃程度である。 Further, the mixing method of the components (1) to (4) and other components is not particularly limited, and a known method may be used. For example, the components (1) to (4) and other components can be uniformly dispersed by kneading them with a twin screw extruder (a twin screw kneader) or the like. As described above, in the present invention, (2) an amine-based polymer compound having a primary amino group and (3) an acid-modified polyolefin are both mixed into the composite material. Each component to be dispersed can be uniformly dispersed. The temperature at the time of mixing each component is not particularly limited, and is usually about 0 to 300 ° C.
　例えば、ＣＭ化セルロースファイバーを二軸押出機等で解繊して、これに前記（２）、（３）、（４）の各成分及び必要に応じて使用される水等の他の成分を加え、攪拌して本発明の複合材料を得てもよい。また、リファイナ一、二軸押出機等を用いて解繊したＣＭ化セルロースファイバーを得る際に、（２）、（３）、（４）の各成分と、必要に応じて使用される他の成分とを一緒に混合し、カルボキシルメチル化したセルロース原料の解繊によるＣＭ化セルロースファイバーの製造と各成分の攪拌とを同時に行ってもよい。 For example, CM cellulose fiber is defibrated with a twin screw extruder or the like, and each of the components (2), (3), (4) and other components such as water used as necessary are added thereto. In addition, the composite material of the present invention may be obtained by stirring. In addition, when obtaining CM-converted cellulose fibers using a refiner, a twin screw extruder, etc., each component of (2), (3), (4) and other components used as necessary The components may be mixed together, and the production of CM-modified cellulose fibers by defibration of the carboxymethylated cellulose raw material and the stirring of each component may be performed simultaneously.
　３．成形体
　本発明の成形体は、後述の通り、前記複合材料を加熱処理することによって得られる。複合材料を加熱処理（加熱、溶融、混練等の処理）する際の温度は、通常１００～３００℃程度、好ましくは１１０～２５０℃程度、特に好ましくは１１０～２２０℃程度である。 3. Molded body The molded body of the present invention is obtained by heat-treating the composite material as described later. The temperature at which the composite material is heat-treated (heating, melting, kneading, etc.) is usually about 100 to 300 ° C., preferably about 110 to 250 ° C., particularly preferably about 110 to 220 ° C.
　加熱処理する際の温度は、通常、複合材料に含まれる(４)ポリオレフィン樹脂の融点以上の温度とすることが好ましい。 The temperature during the heat treatment is usually preferably a temperature equal to or higher than the melting point of (4) polyolefin resin contained in the composite material.
　成形体は、公知の樹脂成形方法により目的とする形状にすることができる。例えば、通常の熱可塑性樹脂組成物の製造方法と同様の方法を適用することができる。例えば、複合材料を加熱、溶融、混練、ペレタイザ一等によりペレット化した後、得られたペレットを射出成形、金型成形等に供することにより、目的の形状に成形できる。その他、押出成形、中空成形、発泡成形等も採用することができる。 The molded body can be formed into a desired shape by a known resin molding method. For example, the same method as the manufacturing method of a normal thermoplastic resin composition can be applied. For example, after the composite material is pelletized by heating, melting, kneading, pelletizer or the like, the obtained pellet is subjected to injection molding, die molding, or the like, and can be molded into a desired shape. In addition, extrusion molding, hollow molding, foam molding, and the like can also be employed.
　複合材料に上記加熱処理によって蒸発する成分がほとんど含まれていなければ、加熱処理の前の複合材料と加熱処理後の成形体に含まれる各成分の量は実質的に同じであると考えられる。すなわち、本発明の成形体中の各成分の量は、前記複合材料における各成分の配合量と同じであると考えることができる。 When the composite material contains almost no component that evaporates by the heat treatment, the amount of each component contained in the composite material before the heat treatment and the molded product after the heat treatment is considered to be substantially the same. That is, it can be considered that the amount of each component in the molded body of the present invention is the same as the amount of each component in the composite material.
　上記の通り、本発明においては、（１）ＣＭ化セルロースファイバー、（２）第１級アミノ基を有する高分子化合物、及び前記（３）酸変性されたポリオレフィンを併用することにより、ＣＭ化セルロースファイバーとポリオレフィン樹脂とを複合材料中に均一に分散させることができる。また、ＣＭ化セルロースファイバー間の結合強度を向上させ、また、親水性の高いＣＭ化セルロースファイバーと疎水性の高いポリオレフィン樹脂との間の界面接着強度を向上させることができる。また、このようにして得られた複合材料を加熱処理することにより、高強度、高弾性率のポリオレフィン系成形体を得ることができる。 As described above, in the present invention, by using together (1) CM-modified cellulose fiber, (2) a polymer compound having a primary amino group, and (3) acid-modified polyolefin, CM-modified cellulose is used. The fiber and the polyolefin resin can be uniformly dispersed in the composite material. Moreover, the bond strength between CM-ized cellulose fibers can be improved, and the interfacial adhesion strength between CM-modified cellulose fibers having high hydrophilicity and polyolefin resins having high hydrophobicity can be improved. In addition, by subjecting the composite material thus obtained to a heat treatment, a polyolefin-based molded body having high strength and high elastic modulus can be obtained.
　本発明の成形体においては、（１）ＣＭ化セルロースファイバー表面に存在するカルボキシル基およびカルボキシメチル基、（２）成分中の第１級アミノ基、及び（３）成分中の酸変性部位は、加熱により一部又は全部が反応し、結合していると考えられる。これらの結合が、樹脂材料の強度、弾性率の向上に貢献していると考えられる。 In the molded article of the present invention, (1) carboxyl group and carboxymethyl group present on the surface of CM-modified cellulose fiber, (2) primary amino group in component, and (3) acid-modified site in component are: It is considered that a part or the whole reacts and is bonded by heating. These bonds are considered to contribute to the improvement of the strength and elastic modulus of the resin material.
　本発明の成形体は、既存のガラス繊維強化材料におけるガラス繊維をＣＭ化セルロースファイバーに代替したようなものであり、ガラス繊維強化材料に比して軽く、また、廃棄時の焼却灰を低減させることができると考えられる。また、高い強度を有しているので、例えば、パソコン、携帯電話等の家電製品の筐体(ハウジング)に用いることができるし、文具等の事務機器、家具等の生活用品、スポーツ用品、自動車のダッシュボード等の内装、飛行機の荷物入れ、輸送用機器の構造部材、住宅におけるサッシ等の建材等にも使用することができる。更に、絶縁性に優れるので、電気・電子・通信機器への応用が期待できる。 The molded article of the present invention is a glass fiber reinforced material in which the glass fiber is replaced with a CM cellulose fiber, which is lighter than the glass fiber reinforced material and reduces incineration ash at the time of disposal. It is considered possible. In addition, since it has high strength, it can be used for the housing (housing) of home appliances such as personal computers and mobile phones, office equipment such as stationery, household goods such as furniture, sports equipment, automobiles, etc. It can also be used for interiors such as dashboards, luggage storage for airplanes, structural members for transportation equipment, and building materials such as sashes in houses. Furthermore, since it is excellent in insulation, application to electrical / electronic / communication equipment can be expected.
　以下、実施例を挙げて本発明をさらに詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
　＜カルボキシメチル化セルロースファイバーの製造１＞
　パルプを混ぜることが出来る撹拌機に、パルプ（ＬＢＫＰ、日本製紙社製）を乾燥重量で２００ｇ、水酸化ナトリウムを乾燥重量で８８ｇ加え、パルプ固形濃度が１５％になるように水を加えた。その後、３０℃で３０分攪拌した後に７０℃まで昇温し、モノクロロ酢酸ナトリウムを１１７ｇ（有効成分換算）添加した。１時間反応した後に、反応物を取り出して中和、洗浄して、グルコース単位当たりのカルボキシメチル置換度０．０５、結晶化度８４％、平均繊維径２０．０μｍ、平均繊維長１．２ｍｍのカルボキシルメチル化したセルロースを得た。 <Production 1 of carboxymethylated cellulose fiber>
To a stirrer capable of mixing pulp, 200 g of pulp (LBKP, Nippon Paper Industries Co., Ltd.) by dry weight and 88 g of sodium hydroxide by dry weight were added, and water was added so that the pulp solid concentration was 15%. Then, after stirring for 30 minutes at 30 ° C., the temperature was raised to 70 ° C., and 117 g of sodium monochloroacetate (in terms of active ingredient) was added. After reacting for 1 hour, the reaction product was taken out, neutralized and washed to obtain a carboxymethyl substitution degree per glucose unit of 0.05, a crystallinity of 84%, an average fiber diameter of 20.0 μm, and an average fiber length of 1.2 mm. Carboxymethylated cellulose was obtained.
　（結晶化度の測定）
　セルロースＩ型の結晶化度は、試料のＸ線回折を測定することで求めた。Ｘ線回折は、試料をガラスセルに乗せ、Ｘ線回折測定装置（ＬａｂＸ　ＸＲＤ－６０００、島津製作所製）を用いて測定した。結晶化度の算出はＳｅｇａｌ等の手法を用いて行い、Ｘ線回折図の２θ＝１０°～３０°の回折強度をベースラインとして、２θ＝２２．６°の００２面の回折強度と２θ＝１８．５°のアモルファス部分の回折強度から次式により算出した。
Ｘｃ＝（Ｉ００２ｃ―Ｉａ）/Ｉ００２ｃ×１００
Ｘｃ：セルロースのＩ型の結晶化度（％）
Ｉ００２ｃ：２θ＝２２．６°の００２面の回折強度
Ｉａ：２θ＝１８．５°のアモルファス部分の回折強度 (Measurement of crystallinity)
The crystallinity of cellulose type I was determined by measuring the X-ray diffraction of the sample. X-ray diffraction was measured by placing a sample on a glass cell and using an X-ray diffraction measurement apparatus (LabX XRD-6000, manufactured by Shimadzu Corporation). The degree of crystallinity is calculated using a method such as Segal, and the diffraction intensity of 2θ = 10 ° to 30 ° in the X-ray diffraction diagram is used as a baseline, and the diffraction intensity of the 002 plane of 2θ = 22.6 ° and 2θ = It calculated from the following formula from the diffraction intensity of the amorphous portion at 18.5 °.
Xc = ( I002c- Ia ) / I002c * 100
Xc : degree of crystallinity of cellulose type I (%)
I 002c : Diffraction intensity of 002 plane at 2θ = 22.6 ° I a : Diffraction intensity of amorphous portion at 2θ = 18.5 °
　（カルボキシメチル置換度の測定方法）
　試料約２．０ｇを精秤して、３００ｍＬ共栓付き三角フラスコに入れた。硝酸メタノール１０００ｍＬに特級濃硝酸１００ｍＬを加えた液１００ｍＬを加え、３時間振とうして、カルボキシメチルセルロース塩(ＣＭＣ)をＨ－ＣＭＣにした。その絶乾Ｈ－ＣＭＣを１．５～２．０ｇ精秤し、３００ｍＬ共栓付き三角フラスコに入れた。８０％メタノール１５ｍＬでＨ－ＣＭＣを湿潤し、０．１Ｎ－ＮａＯＨを１００ｍＬ加え、室温で３時間振とうした。指示薬として、フェノールフタレインを用いて、０．１Ｎ－Ｈ２ＳＯ４で過剰のＮａＯＨを逆滴定した。カルボキシメチル置換度（ＣＭ－ＤＳ）は、次式によって算出した。
Ａ＝[（１００×Ｆ’－０．１Ｎ－Ｈ２ＳＯ４（ｍＬ）×Ｆ）×０．１]/（Ｈ－ＣＭＣの絶乾重量（ｇ））
ＣＭ－ＤＳ＝０．１６２×Ａ/（１－０．０５８×Ａ）
Ａ：Ｈ－ＣＭＣの１ｇの中和に要する１Ｎ－ＮａＯＨ量（ｍＬ）
Ｆ’：０．１Ｎ－Ｈ２ＳＯ４のファクター
Ｆ：０．１Ｎ－ＮａＯＨのファクター (Measurement method of carboxymethyl substitution degree)
About 2.0 g of the sample was precisely weighed and placed in a 300 mL conical flask with a stopper. A solution of 100 mL of special concentrated nitric acid in 1000 mL of nitric acid methanol was added, and the mixture was shaken for 3 hours to convert carboxymethylcellulose salt (CMC) to H-CMC. 1.5-2.0 g of the absolutely dry H-CMC was precisely weighed and placed in a 300 mL conical flask with a stopper. H-CMC was moistened with 15 mL of 80% methanol, 100 mL of 0.1 N NaOH was added, and the mixture was shaken at room temperature for 3 hours. Excess NaOH was back titrated with 0.1N—H 2 SO 4 using phenolphthalein as an indicator. The degree of carboxymethyl substitution (CM-DS) was calculated by the following formula.
A = [(100 × F′−0.1N—H 2 SO 4 (mL) × F) × 0.1] / (absolute dry weight of H-CMC (g))
CM-DS = 0.162 × A / (1-0.058 × A)
A: 1N-NaOH amount required for neutralizing 1 g of H-CMC (mL)
F ′: Factor of 0.1N—H 2 SO 4 F: Factor of 0.1N—NaOH
　＜カルボキシメチル化セルロースファイバーの製造２＞
　モノクロロ酢酸ナトリウムの量を１８７ｇ（有効成分換算）に変更した以外は製造１と同様に製造した。得られたカルボキシメチル化セルロースファイバーのグルコース単位当たりのカルボキシメチル置換度は０．０８、結晶化度は８３％、平均繊維径は１９．１μｍ、平均繊維長は１．１ｍｍであった。 <Production 2 of carboxymethylated cellulose fiber>
Manufactured in the same manner as in Production 1 except that the amount of sodium monochloroacetate was changed to 187 g (in terms of active ingredient). The obtained carboxymethylated cellulose fiber had a degree of carboxymethyl substitution per glucose unit of 0.08, a degree of crystallinity of 83%, an average fiber diameter of 19.1 μm, and an average fiber length of 1.1 mm.
　＜カルボキシメチル化セルロースファイバーの製造３＞
　モノクロロ酢酸ナトリウムの量を４６８ｇ（有効成分換算）に変更した以外は製造１と同様に製造した。得られたカルボキシメチル化セルロースファイバーのグルコース単位当たりのカルボキシメチル置換度は０．２０、結晶化度は７３％、平均繊維径は１８．６μｍ、平均繊維長は１．１ｍｍであった。 <Production of carboxymethylated cellulose fiber 3>
Production was conducted in the same manner as in Production 1 except that the amount of sodium monochloroacetate was changed to 468 g (in terms of active ingredient). The obtained carboxymethylated cellulose fiber had a degree of carboxymethyl substitution per glucose unit of 0.20, a degree of crystallinity of 73%, an average fiber diameter of 18.6 μm, and an average fiber length of 1.1 mm.
　＜カルボキシメチル化セルロースファイバーの製造４＞
　モノクロロ酢酸ナトリウムの量を４６８ｇ（有効成分換算）、水酸化ナトリウムを乾燥重量で１０４ｇに変更した以外は製造１と同様に製造した。得られたカルボキシメチル化セルロースファイバーのグルコース単位当たりのカルボキシメチル置換度は０．２０、結晶化度は６２％、平均繊維径は１８．５μｍ、平均繊維長は１．１ｍｍであった。 <Production 4 of carboxymethylated cellulose fiber>
Manufactured in the same manner as in Production 1 except that the amount of sodium monochloroacetate was changed to 468 g (in terms of active ingredient) and sodium hydroxide was changed to 104 g by dry weight. The obtained carboxymethylated cellulose fiber had a degree of carboxymethyl substitution per glucose unit of 0.20, a degree of crystallinity of 62%, an average fiber diameter of 18.5 μm, and an average fiber length of 1.1 mm.
　＜カルボキシメチル化セルロースファイバーの製造５＞
　製造１におけるパルプ（ＬＢＫＰ、日本製紙社製）を、パルプ（ＮＢＫＰ、日本製紙社製）に変更した以外は、製造１と同様にした。得られたカルボキシメチル化セルロースファイバーのグルコース単位当たりのカルボキシメチル置換度は０．０５、結晶化度は８４％、平均繊維径は１９．０μｍ、平均繊維長２．９はｍｍであった。 <Production 5 of carboxymethylated cellulose fiber>
The same procedure as in Production 1 was performed except that the pulp in Production 1 (LBKP, manufactured by Nippon Paper Industries Co., Ltd.) was changed to pulp (NBKP, manufactured by Nippon Paper Industries Co., Ltd.). The obtained carboxymethylated cellulose fiber had a degree of carboxymethyl substitution per glucose unit of 0.05, a degree of crystallinity of 84%, an average fiber diameter of 19.0 μm, and an average fiber length of 2.9 mm.
　＜カルボキシメチル化セルロースファイバーの製造６＞
　製造５で得たカルボキシメチル化したセルロースを、高圧ホモジナイザーで処理し、平均繊維径１．２μｍ、平均繊維長２．５ｍｍに調整した。 <Production 6 of carboxymethylated cellulose fiber>
The carboxymethylated cellulose obtained in Production 5 was treated with a high-pressure homogenizer and adjusted to an average fiber diameter of 1.2 μm and an average fiber length of 2.5 mm.
　＜カルボキシメチル化セルロースファイバーの製造７＞
　製造５で得たカルボキシメチル化セルロースファイバーを、マスコロイダーで処理し、平均繊維径１．１μｍ、平均繊維長１．２ｍｍに調整した。 <Production 7 of carboxymethylated cellulose fiber>
The carboxymethylated cellulose fiber obtained in Production 5 was treated with a mass collider to adjust the average fiber diameter to 1.1 μm and the average fiber length to 1.2 mm.
　＜実施例１＞
　製造１で得られたＣＭ化セルロースファイバー（成分（１））、アリルアミン重合体（日東紡株式会社製：商品名「ＰＡＡ（登録商標）－１５Ｃ」）（成分（２））、無水マレイン酸変性ポリプロピレン（三洋化成工業株式会社製：商品名「ユーメックス（登録商標）１０１０」）（成分（３））、及びポリプロピレン（株式会社プライムポリマー製：商品名「プライムポリプロ（登録商標）Ｊ１０５」）（成分（４））を添加してミキサーにて１５分間攪拌した（各々の成分の固形分比（質量比）は次の通りである。ＣＭ化セルロースファイバー：アリルアミン重合体：無水マレイン酸変性ポリプロピレン：ポリプロピレン＝３０：６：８：５６）。 <Example 1>
CMized cellulose fiber obtained in Production 1 (component (1)), allylamine polymer (manufactured by Nittobo Co., Ltd .: trade name “PAA (registered trademark) -15C”) (component (2)), maleic anhydride modified Polypropylene (manufactured by Sanyo Chemical Industries, Ltd .: trade name “Yumex (registered trademark) 1010”) (component (3)), and polypropylene (manufactured by Prime Polymer Co., Ltd .: trade name “Prime Polypro (registered trademark) J105”) (component) (4)) was added and stirred for 15 minutes in a mixer (solid content ratio (mass ratio) of each component is as follows: CMized cellulose fiber: allylamine polymer: maleic anhydride modified polypropylene: polypropylene = 30: 6: 8: 56).
　得られた混合物を二軸押出機（ＭＦＵ１５ＴＷ－４５ＨＧ、スクリュー直径：１５ｍｍ、株式会社テクノベル製）で溶融、混練（回転数２００ｒｐｍ、温度１８０℃）した後、ペレット化した。更に得られたペレットを射出成型機に投入しダンベル型の成型物を得た。成形温度は１９０℃とした。得られた成型物の引張強度及び引張弾性率を表１に示す。 The obtained mixture was melted and kneaded (rotation speed: 200 rpm, temperature: 180 ° C.) with a twin-screw extruder (MFU15TW-45HG, screw diameter: 15 mm, manufactured by Technobel Co., Ltd.), and pelletized. Further, the obtained pellets were put into an injection molding machine to obtain a dumbbell-shaped molded product. The molding temperature was 190 ° C. Table 1 shows the tensile strength and tensile modulus of the obtained molded product.
　（引張強度の測定）
　ＪＩＳ　Ｋ７１６１（プラスチックの引張り試験方法）に基づき１ＢＡ形試験片（ダンベル型厚さ２ｍｍ）を用いて測定した。 (Measurement of tensile strength)
Based on JIS K7161 (plastic tensile test method), a 1BA type test piece (dumbbell thickness 2 mm) was used for measurement.
　（引張弾性率の測定）
　株式会社エー・アンド・デイ製「テンシロン万能試験機ＲＴＧ－１２１０」を用いて測定した (Measurement of tensile modulus)
Measured using “Tensilon Universal Testing Machine RTG-1210” manufactured by A & D Co., Ltd.
　＜実施例２＞
　製造２で得られたＣＭ化セルロースファイバーを用いた以外は実施例１と同様に行った。 <Example 2>
The same procedure as in Example 1 was performed except that the CM-converted cellulose fiber obtained in Production 2 was used.
　＜実施例３＞
　製造３で得られたＣＭ化セルロースファイバーを用いた以外は実施例１と同様に行った。 <Example 3>
The same procedure as in Example 1 was performed except that the CM-converted cellulose fiber obtained in Production 3 was used.
　＜実施例４＞
　製造４で得られたＣＭ化セルロースファイバーを用いた以外は実施例１と同様に行った。 <Example 4>
The same procedure as in Example 1 was performed except that the CM-converted cellulose fiber obtained in Production 4 was used.
　＜実施例５＞
　製造５で得られたＣＭ化セルロースファイバーを用いた以外は実施例１と同様に行った。 <Example 5>
The same procedure as in Example 1 was carried out except that the CMized cellulose fiber obtained in Production 5 was used.
　＜実施例６＞
　製造６で得られたＣＭ化セルロースファイバーを用いた以外は実施例１と同様に行った。 <Example 6>
The same procedure as in Example 1 was performed except that the CM-converted cellulose fiber obtained in Production 6 was used.
　＜実施例７＞
　製造７で得られたＣＭ化セルロースファイバーを用いた以外は実施例１と同様に行った。 <Example 7>
The same procedure as in Example 1 was performed except that the CM-converted cellulose fiber obtained in Production 7 was used.
　＜比較例１＞
　カルボキシメチル化していないパルプ（ＬＢＫＰ、日本製紙社製）を用いた以外は実施例１と同様に行った。 <Comparative Example 1>
This was carried out in the same manner as in Example 1 except that non-carboxymethylated pulp (LBKP, manufactured by Nippon Paper Industries Co., Ltd.) was used.
　＜比較例２＞
　成分（４）のみで射出成型して得られた成型物の引張強度及び弾性率を測定した。 <Comparative Example 2>
The tensile strength and elastic modulus of the molded product obtained by injection molding only with the component (4) were measured.
Figure JPOXMLDOC01-appb-T000010
  
Figure JPOXMLDOC01-appb-T000010
  

Claims (7)

  1. （１）カルボキシメチル化セルロースファイバー、（２）第１級アミノ基を有する高分子化合物、（３）酸変性されたポリオレフィン、及び（４）ポリオレフィン樹脂を含有する複合材料。 (1) Carboxymethylated cellulose fiber, (2) a polymer compound having a primary amino group, (3) acid-modified polyolefin, and (4) a composite material containing a polyolefin resin.
  2. 前記カルボキシメチル化セルロースファイバーは、セルロースの無水グルコース単位当たりのカルボキシメチル基置換度が０．０１～０．４０であり、且つセルロースＩ型の結晶化度が６０％以上である、請求項１に記載の複合材料。 The carboxymethylated cellulose fiber has a carboxymethyl group substitution degree per anhydroglucose unit of cellulose of 0.01 to 0.40 and a crystallinity of cellulose I type of 60% or more. The composite material described.
  3. 前記酸変性されたポリオレフィンが、無水マレイン酸変性ポリオレフィンである、請求項１または２に記載の複合材料。 The composite material according to claim 1, wherein the acid-modified polyolefin is a maleic anhydride-modified polyolefin.
  4. 前記無水マレイン酸変性ポリオレフィンが、無水マレイン酸変性ポリプロピレンであり、前記ポリオレフィン樹脂が、ポリプロピレンである、請求項１～３のいずれか１項に記載の複合材料。 The composite material according to any one of claims 1 to 3, wherein the maleic anhydride-modified polyolefin is maleic anhydride-modified polypropylene, and the polyolefin resin is polypropylene.
  5. 前記第１級アミノ基を有する高分子化合物が、下記一般式（Ａ）：
    Figure JPOXMLDOC01-appb-C000001
     で表される繰り返し単位を有する化合物、下記一般式（Ｂ）：
    Figure JPOXMLDOC01-appb-C000002
     で表される繰り返し単位を有する化合物、下記一般式（Ｃ）：
    Figure JPOXMLDOC01-appb-C000003
     で表される繰り返し単位を有する化合物、及びこれらの塩からなる群から選ばれる少なくとも１種である請求項１～４のいずれか１項に記載の複合材料。     The polymer compound having the primary amino group is represented by the following general formula (A):
    Figure JPOXMLDOC01-appb-C000001
     A compound having a repeating unit represented by the following general formula (B):
    Figure JPOXMLDOC01-appb-C000002
     A compound having a repeating unit represented by the following general formula (C):
    Figure JPOXMLDOC01-appb-C000003
     The composite material according to any one of claims 1 to 4, which is at least one selected from the group consisting of a compound having a repeating unit represented by the formula: and a salt thereof.
  6. （１）カルボキシメチル化セルロースファイバー、（２）第１級アミノ基を有する高分子化合物、（３）酸変性されたポリオレフィン、及び（４）ポリオレフィン樹脂を混練する工程を含む請求項１～５のいずれか１項に記載の複合材料の製造方法。 6. The method according to claim 1, comprising the step of kneading (1) carboxymethylated cellulose fiber, (2) a polymer compound having a primary amino group, (3) an acid-modified polyolefin, and (4) a polyolefin resin. The manufacturing method of the composite material of any one of Claims 1.
  7. 請求項１～６のいずれか１項に記載の複合材料を１００～３００℃で加熱処理してなる成形体。 A molded product obtained by heat-treating the composite material according to any one of claims 1 to 6 at 100 to 300 ° C.
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