JP6275651B2 - COMPOSITE MATERIAL AND MOLDED BODY USING SAME - Google Patents

Description

  The present invention relates to a composite resin containing a carboxymethylated cellulose fiber and a polyolefin resin, and a molded body obtained by heat-treating the composite resin.

  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.

US Patent Application Publication No. 2008/0146701 JP 2009-19200 A International Publication No. 2011/049162

  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.

  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.

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, wherein the carboxymethyl group substitution degree 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 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):

で表される繰り返し単位を有する化合物、下記一般式（Ｂ）：

A compound having a repeating unit represented by the following general formula (B):

で表される繰り返し単位を有する化合物、下記一般式（Ｃ）：

A compound having a repeating unit represented by the following general formula (C):

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。

The composite material as described in 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 formula (I) 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). The molded object formed by heat-processing the composite material as described in any one of said 1-5 at 100-300 degreeC.

  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. 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) 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 CM-modified cellulose fiber preferably has a degree of carboxymethyl substitution per anhydroglucose unit of cellulose of 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.

  Although the manufacturing method of CM cellulose fiber is not specifically limited, It can obtain by carrying out carboxymethylation of the cellulose raw material.

(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.

(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 degree of carboxymethyl group substitution 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 the 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. In addition, the mixing ratio of the lower alcohol in a solvent is 60 to 95 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 hour to 4 hours.

(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. Moreover, it is preferable that the average fiber length of CM-ized cellulose fiber is 0.5 mm-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.

  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.

  The apparatus for defibrating is not particularly limited, and a high-speed rotating 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.

  In the composite material of the present invention, the blending amount of the CM-ized cellulose fiber is usually about 1 to 94% by mass, preferably about 2 to 92% by mass in the total amount of the composite material.

(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.

  The polymer compound having a primary amino group has a weight average molecular weight of usually about 1,000 to 1,000,000, preferably about 1200 to 700,000.

  In the present invention, the weight average molecular weight is determined by gel permeation chromatography (GPC) method (converted to PEG), GPC method (converted to pullulan) or GPC-MALLS in which a multi-angle light scattering detector is connected to a GPC column. It is a value measured by any method.

  The amino group of the polymer compound having a primary amino group may form a salt with an organic acid or an 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.

  The high molecular compound which has a primary amino group may be used individually by 1 type, and 2 or more types may be mixed and used for it. The polymer compound having a primary amino group may be synthesized by a known method, or a commercially available product may be used.

  Examples of the polymer compound having a primary amino group include the following general formula (A):

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。

The compound which has an allylamine unit represented by these as a repeating unit, and its salt are mentioned.

  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.

  However, if the amount of the repeating unit other than the repeating unit represented by the general formula (A) is too large, the number of primary amino groups per unit weight is decreased, which 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.

  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 as 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 acid salts such as toluene sulfonate, methane sulfonate, citrate and tartrate. 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.

  Examples of the polymer compound having a primary amino group include the following general formula (B):

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。

And compounds having a vinylamine unit represented by the formula (I) as a repeating unit and salts thereof.

  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). .

  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.

  However, when the amount of the repeating unit other than the repeating unit represented by the general formula (B) 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 (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 Organic acid salts such as salts, propionates, p-toluenesulfonates, methanesulfonates, citrates and tartrates can be mentioned.

  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.

  Furthermore, examples of the polymer compound having a primary amino group include the following general formula (C):

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。

The compound which has a repeating unit represented by these, and its salt are also mentioned.

  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.

  However, when 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 decreased, which 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.

  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 as 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. Organic acid salts such as salts, propionates, p-toluenesulfonates, methanesulfonates, citrates and tartrates can be mentioned.

  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.

  In the composite material of the present invention, the blending 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. About 10 parts by weight, particularly preferably about 10 to 20 parts by weight.

(3) Acid-modified polyolefin The composite material of the present invention includes an acid-modified polyolefin.

  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.

  The acid-modified polyolefin may have a molecular weight of about 10,000 to 100,000, preferably about 20,000 to 80,000 in terms of weight average molecular weight. 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.

  Examples of the maleic anhydride-modified polyolefin include maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, maleic anhydride-modified polybutadiene, maleic anhydride-modified polystyrene, maleic anhydride-modified polymethacrylate, and the like. 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.

  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.

  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.

  In the composite material of the present invention, the amount of the acid-modified polymer compound is (1) usually 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) 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 and 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. 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.

  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.

  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.

  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. 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 kneading order of the components (1) to (4) and other components is not particularly limited.

  Moreover, the mixing method of each component of said (1)-(4) and another component is not specifically limited, What is necessary is just to use a well-known method. For example, each component can be uniformly dispersed by kneading the components (1) to (4) and other components 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 of each component is not specifically limited, Usually, it is about 0-300 degreeC.

  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. 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 subjected to heat treatment (treatment such as heating, melting, kneading) is usually about 100 to 300 ° C, preferably about 110 to 250 ° C, and particularly preferably about 110 to 220 ° C.

  In general, the temperature during the heat treatment is preferably a temperature equal to or higher than the melting point of the (4) polyolefin resin contained in the composite material.

  A molded object can be made into the target shape by a well-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.

  If 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.

  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.

  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.

  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.

  Hereinafter, although an example is given and the present invention is explained still in detail, the present invention is not limited to these.

<Production 1 of carboxymethylated cellulose fiber>
To a stirrer capable of mixing pulp, 200 g by dry weight of pulp (LBKP, manufactured by Nippon Paper Industries Co., Ltd.) 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.

(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 °

(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. The absolute dry H-CMC was accurately weighed in an amount of 1.5 to 2.0 g and placed in an Erlenmeyer flask with a 300 mL 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. As an indicator, using phenolphthalein was back titrated excess NaOH with _0.1N-H 2 SO _4. 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

<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.

<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.

<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.

<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.

<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.

<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.

<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: CM-modified cellulose fiber: allylamine polymer: maleic anhydride modified polypropylene: polypropylene = 30: 6: 8: 56).

  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.

(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.

(Measurement of tensile modulus)
Measured using “Tensilon Universal Testing Machine RTG-1210” manufactured by A & D Co., Ltd.

<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.

<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.

<Comparative example 2>
The tensile strength and elastic modulus of the molded product obtained by injection molding only with the component (4) were measured.

Claims (7)

  (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.   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.   The composite material according to claim 1, wherein the acid-modified polyolefin is a maleic anhydride-modified polyolefin. The composite material according to claim 3 , wherein the maleic anhydride-modified polyolefin is maleic anhydride-modified polypropylene, and the polyolefin resin is polypropylene. The polymer compound having the primary amino group is represented by the following general formula (A):

A compound having a repeating unit represented by the following general formula (B):

A compound having a repeating unit represented by the following general formula (C):

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: and a salt thereof.   The method according to claim 1, comprising a step of kneading (1) carboxymethylated cellulose fiber, (2) a polymer compound having a primary amino group, (3) acid-modified polyolefin, and (4) polyolefin resin. The manufacturing method of the composite material of any one of Claims 1. The molded object formed by heat-processing the composite material of any one of Claims 1-5 at 100-300 degreeC.