WO2016010016A1 - Derivatized cnf, method for producing same, and polyolefin resin composition - Google Patents

Abstract

[Problem] To provide: derivatized CNF that makes it possible to negate the high hydrophilicity of hydrated CNF and impart the same with hydrophobicity, thereby improving compatibility with hydrophobic resins such as polyolefins, and enabling redispersion in hydrophobic solvent even when completely dried, the derivatized CNF reducing the effects of moisture during kneading with plastics, reducing transportation costs, and the like; a method for producing the same; and a resin composition having exceptional environmental characteristics, little reduction of impact strength, high rigidity even with low specific gravity, and an exceptional molded appearance through the use of biomass material. [Solution] The present invention is a resin composition having exceptional environmental characteristics, little reduction of impact strength, high rigidity even with low specific gravity, and an exceptional molded appearance through the use of a biomass material comprising: 0.5-10 mass% of (A) derivatized CNF having an average thickness of 10-200 nm, obtained by a production method for dispersing hydrated CNF together with potassium carbonate in an aprotic polar solvent such as DMSO, adding at least one vinyl organic acid, e.g., one among vinyl acetate, vinyl benzoate, and vinyl laurate, then adding vinyl organic acid, reacting for two or more hours at 70-80°C, preferably for two hours at 80°C, and recovering and drying the reaction product after the end of the reaction; and 99.5-90 mass% of (B) a polyolefin resin.　

Description

Derivatized CNF, process for producing the same, and polyolefin resin composition

The present invention relates to derivatized CNF and a method for producing the same.
From another point of view, the present invention relates to a polyolefin resin composition that is excellent in environmental characteristics by use of a biomass material, has a small decrease in impact strength, has a low specific gravity, a high rigidity, and an excellent molded appearance.

In recent years, biomass materials have attracted attention from the viewpoint of environmental protection, and natural-derived organic fillers and composite materials with biopolymers have begun to be used as materials for automobiles, OA and electric / electronic fields. In addition, for the purpose of improving mechanical strength such as rigidity and heat resistance, a method of adding an inorganic filler such as glass fiber to a resin composition has been studied. However, since these inorganic fillers need to be added in a large amount, there are problems that the specific gravity of the molded article is increased, and the residue that becomes dust at the time of incineration or disposal is increased, which imposes a burden on the environment. On the other hand, naturally-derived cellulose nanofibers (hereinafter referred to as CNF) have a low environmental impact, and are expected to be used as plastic reinforcements due to their characteristics.
However, CNF has a large number of hydroxyl groups in its molecule and is known to be extremely hydrophilic. Therefore, self-aggregation occurs in a hydrophobic environment or in a dry state. As a result, it is not easy to knead CNF and resin between polypropylene (PP), polyethylene (PE), polystyrene (PS), etc., which are extremely hydrophobic and are generally thermoplastic resins. Conventionally, composites in which CNF and polypropylene (PP) or polyethylene (PE) are kneaded have not exhibited the expected mechanical strength characteristics. Therefore, there has been a demand for a technique that can sufficiently disperse CNF in a hydrophobic environment.

Generally, when a hydrophobic substituent is introduced into CNF to impart hydrophobicity, the reaction is performed in a non-aqueous solvent. However, in the case of CNF, the hydrophilicity is extremely high due to the influence of a hydroxyl group present on a high specific surface area. Therefore, it is difficult to remove water from the nanofibers, which requires complicated operations such as solvent replacement in multiple stages and dehydration by overheating, or the need to carry out a substitution reaction after nanofiguring in an organic solvent. It was.

There are various preparations of nanofibers to be fibrillated in an aqueous medium. For example, the underwater facing collision method (hereinafter referred to as ACC method), which is a physical preparation method of CNF, is also disclosed in Patent Document 1. In this way, the fine particles dispersed in water are introduced into two nozzles and sprayed from the corresponding nozzles under high pressure to collide against each other in water. This method uses only water in addition to natural cellulose fibers, and is a nano-miniaturization method by cleaving only the interaction between fibers, so there is no structural change of the cellulose molecule and the degree of polymerization decreases with cleavage. It is possible to obtain a nano-miniaturized product with a minimum of. In addition to this, CNF can be mechanically produced in an aqueous medium by treatment with a blender stirring, a grinder, a microfluidizer, a high-pressure homogenizer or the like described in Patent Document 6 and Patent Document 7.

Generally, when the CNF aqueous suspension is dried, a strong aggregate is formed by the interaction between the CNFs and cannot be redispersed in water or a hydrophobic solvent. That is, CNF having a high aspect ratio (= high reinforcing effect) has the property of re-solidifying and not dispersing again when dried, and must be handled in a gel state, that is, in a water-containing state.

As seen in Non-Patent Document 1 to Non-Patent Document 3, a method of laurylating or acetylating starch, pulp or wood flour using vinyl acetate in an aqueous solution is widely known. In addition, as shown in Non-Patent Document 4, a method of hydrophobizing cellulose using chlorinated fatty acid is also known.
Patent Documents 2 and 3 provide fiber composite materials having excellent characteristics. A fiber composite material characterized by containing CNF modified with a substituent having a carboxyl group and an acyl group and a resin is described.
Patent Document 4 provides a method for producing a CNF dispersion that can be suitably used for complexing with a wide range of organic solvent-soluble polymer materials. A step of dispersing CNF having a carboxylate type group in an aqueous solvent to prepare a CNF aqueous dispersion, a step of substituting the group from a carboxylate type to a carboxylate amine salt type of an amine having an organic group, and And a method for producing a CNF dispersion characterized in that it comprises a step of dispersing CNF having a carboxylic acid amine salt type group in an organic solvent.
Patent Document 5 has an average degree of polymerization of 600 or more and 30000 or less, an aspect ratio of 20 to 10,000, an average diameter of 1 to 800 nm, an X-ray diffraction pattern having an Iβ type crystal peak, and a hydroxyl group. CNFs are described that are chemically modified with a modifying group.
Regarding resin compositions, the prior art is known as follows.
In Patent Document 8, jute is used as a natural organic filler in order to blend an aliphatic polyester and a natural organic filler into an aromatic polycarbonate resin to obtain a resin composition having excellent mechanical properties and flame retardancy. A technique in which a fiber or rayon fiber is combined with a resin composition is described.
In Patent Document 9, (A) 99 to 60% by mass of a polycarbonate resin and (B) 1 to 40% by mass of cellulose fibers having an average fiber diameter of 5 to 50 μm and an average fiber length of 0.03 to 1.5 mm. (C) A polycarbonate resin composition containing 1 to 10 parts by mass of a terpene compound with respect to 100 parts by mass of a resin mixture, and is excellent in environmental characteristics by using a biomass material, and has a low specific gravity and high rigidity and a molded appearance. In addition, a resin composition having excellent thermal stability and good flame resistance is described.
Patent Document 10 discloses a composition containing cellulose and a dispersant, the dispersant having a resin affinity segment A and a cellulose affinity segment B, and a block copolymer structure or a gradient copolymer. A composition manufacturing technique characterized by having a structure is described.
Patent Document 11 describes a technique for producing a hydrophilic nanofiber composite material, in which the hydroxyl group of a hydrophilic nanofiber having a hydroxyl group is solvated with a hydrophilic organic solvent and mixed with molten plastic. Yes.
Patent Document 12 describes a dispersion in which both CNF and resin are uniformly dispersed in a dispersion medium, and a resin composition in which CNF is uniformly contained in the resin.

JP 2005-270891 A JP2011-105799A JP2011-148914A JP2012-021081 JP 2013-44076 JP 2010-216021 WO2011118746 JP 2010-215791 A WO / 2013/133228 JP2014-162880 JP2013-170241A JP2013-166818A

Although the acetylation method is widely known as described in Non-Patent Document 1 to Non-Patent Document 3, acetylation cannot sufficiently secure hydrophobicity for CNF, and polyolefin such as polypropylene having high hydrophobicity. There is a problem that it is necessary to impart stronger hydrophobicity in order to disperse uniformly in the resin.
As seen in Non-Patent Document 4, a method of hydrophobizing cellulose using chlorinated fatty acid is also known, but a non-aqueous reaction is required and there is a problem that a reaction containing water cannot be performed.

The fiber composite material of Patent Document 2 is a nanofiber obtained by oxidizing a hydroxyl group to a carboxyl group, and then dehydrated and then esterified using an acid anhydride, and a non-aqueous reaction is performed. Yes. In the fiber composite material of Patent Document 3, cellulose is modified under anhydrous conditions, and the degree of substitution is as high as 1.5 to 3.0. According to Non-Patent Document 4, the degree of substitution exceeds 0.55. Sufficient strength cannot be realized because the physical strength of nanofibers is reduced. In the above Patent Documents 2 and 3, since acid anhydrides or acid chlorides are used, anhydrous conditions are essential. Patent Document 4 manufactures CNF by changing the hydroxyl group of cellulose (glucose residue) to a carboxyl group, forms a highly hydrophobic amine and a carboxyl group salt, and imparts hydrophobicity to the nanofiber. CNF obtained by a conventional defibrating method cannot be processed. CNF of Patent Document 5 is acetylated with acetic anhydride at the same time as nanofiber pretreatment using an ionic liquid, and the resulting product is homogenized and nanonized, increasing the hydrophobicity and heat resistance of the nanofibers That's it. The CNF obtained by the ACC method cannot be treated, and generally the derivatization reaction is performed in an anhydrous manner. When CNF is handled in a water-containing state, the reactivity is significantly lowered. Moreover, since an expensive ionic liquid is used, it is difficult to use industrially at present.
Although various attempts have been made for resin compositions as described above, satisfactory results have not been obtained in any case. The resin composition obtained in Patent Document 8 has a large reduction in impact strength, an insufficient molded appearance, a large coloration, and insufficient thermal stability during molding. Although the resin composition described in Patent Document 9 is said to have a low specific gravity, the specific gravity (g / cm 3) exceeds 1.20 in all examples, and the specific gravity is larger than that of water. It does not fully meet the problem of weight reduction. Regarding the combination with the olefin resin described in Patent Document 10, CNF cannot be dispersed unless a maleic anhydride-modified resin is used in combination, and even if used together, there are many aggregates of 10 μm or more. Cellulose is chemically modified, and unmodified cellulose cannot be used. Furthermore, terpene resins are not used. Even at the strength level, the elastic modulus is improved, but the impact strength is remarkably lowered. In the technique described in Patent Document 11, it is necessary to solvate with a lower aliphatic alcohol and replace the solvent, and the nanofiber in a water-containing state cannot be used directly. Furthermore, terpene resins are not used. In the technique described in Patent Document 12, micro-level aggregates are present, and CNF is prepared by a bead mill, which lowers the degree of polymerization. Moreover, the maleic acid modified resin is used together. Furthermore, terpene resins are not used.
In general, when trying to reinforce a polyolefin-based resin with CNF, highly hydrophilic CNF aggregates in a highly hydrophobic polyolefin resin, and a sufficient reinforcing effect cannot be obtained. Further, there is a problem that transparency is greatly lowered due to the resulting aggregate.

The present invention provides a derivatized CNF in which a hydroxyl group present on the CNF surface is esterified and a method for producing the same. In contrast to the above-described problems in the prior art, such derivatized CNF maintains the crystal structure and does not impair the mechanical properties, while canceling the high hydrophilicity that water-containing CNF had, such as polyethylene and polypropylene. Compatibility with hydrophobic resins such as polyolefins is improved. Further, it can be completely dried, and the influence of moisture during kneading and transportation costs can be reduced.
From another point of view, in view of the above problems in the prior art, the present invention is a resin that is excellent in environmental characteristics due to the use of biomass material, has a low decrease in impact strength, has a low specific gravity, high rigidity, and excellent molded appearance. A composition is provided. The composite resin is imparted with a higher reinforcing effect and transparency. Here, the polyolefin-CNF composite resin of the present invention is produced by using a surface-hydrophobized CNF instead of CNF as a reinforcing material, and compounding with polyolefin by high-speed stirring mixing and biaxial extrusion kneading.
As a result of intensive studies, the present inventors have found the following. That is, if hydrogen bonding by hydroxyl groups present on the CNF surface is inhibited, aggregation in a hydrophobic environment during kneading of the polyolefin resin can be prevented, and the mechanical strength characteristics of the composite resin can be improved. Alternatively, if this hydrogen bond is inhibited and at the same time hydrophobicity is imparted, the compatibility with a hydrophobic resin such as polyolefin can be increased, and the mechanical properties of the composite resin can be further improved. As a result, the above-mentioned problems can be solved by blending a specific amount of derivatized CNF having a specific average fiber diameter and average fiber length and imparted hydrophobicity as a biomass material into the polyolefin resin.

First, the present invention is a method for hydrophobizing CNF using vinyl organic acid, and for example, surface modification of esterifying hydroxyl groups exposed on the surface of CNF using vinyl acetate, vinyl benzoate, vinyl laurate or the like. It is a technique.
That is, in the method for producing derivatized CNF of the present invention, organic acid vinyl is added to a solution in which hydrous CNF is dispersed in a hydrophilic organic solvent, and a precipitate is generated in the reaction solution after completion of the reaction, and the precipitate is recovered and dried. It is characterized by that. Or you may extract and collect | recover with hydrophobic organic solvents, such as toluene. When dehydrating while maintaining the nanostructure of CNF, it involves a complicated operation. By mixing water-containing CNF and an organic solvent, a hydrophobic derivative can be easily maintained while maintaining the nanostructure of CNF in the reaction solution. CNF can be dissolved uniformly.
In the method for producing derivatized CNF of the present invention, water-containing CNF is added to an organic solvent having sufficient dispersibility with respect to CNF together with potassium carbonate, organic acid vinyl is added, and the reaction product after completion of the reaction is recovered. And drying.

From still another aspect, the present invention relates to the following polyolefin resin composition. That is, (A) an average thickness of 10 to 200 nm, derivatized CNF obtained by derivatizing a polysaccharide with a high-pressure water stream and derivatized CNF 1 to 10% by mass, and (B) a polyolefin resin 99 to 90% by mass. This is a polyolefin resin composition. Here, the derivatized CNF may be hydrophobically derivatized with an organic acid vinyl, and examples thereof include derivatized CNF which is hydrophobically derivatized with vinyl laurate. Further, (A) the CNF is preferably obtained by colliding high pressure water of about 50 to 400 MPa with a polysaccharide in a water mixture of 0.5 to 10% by mass. Furthermore, the polyolefin can be polypropylene, polyethylene, polybutadiene, polyisoprene, and this technology is not only applicable to polyolefins, but can also be applied to other general-purpose plastics that can be molded at 300 ° C. or lower. . In the case of 300 ° C. or higher, decomposition of cellulose occurs.
The method for producing a composite resin of the present invention is characterized in that a hydrophobic derivatized CNF swollen with an organic solvent is melt-kneaded after a pretreatment step of stirring at high speed with a polyolefin.

According to the method for producing derivatized CNF of the present invention, the high hydrophilicity of CNF can be canceled and hydrophobicity can be imparted. The derivatized CNF of the present invention obtained by the method for producing the derivatized CNF of the present invention can be completely dried, has improved compatibility with a hydrophobic resin such as polyolefin, and has water content during kneading with plastic. Impact and transportation costs can be reduced.

It is a conceptual diagram of an example of the manufacturing (defibration process) apparatus of CNF. It is a conceptual diagram which expands and shows a part of CNF manufacturing (defibration process) apparatus in FIG. It is a key map of the manufacture (defibration processing) device of CNF in other examples. It is a conceptual diagram of the manufacture (defibration process) apparatus of CNF in another example. It is a SPM image after nano-processing (defibration processing) of CNF, a indicates A defibration, b indicates C defibration, and the scale is set to 2.5 μm in length and width. It is a photograph which shows the toluene extraction result of various derivatization reaction liquids, and acetylation, benzylation, 2-ethylhexylation, laurylation CNF is shown from the left. SEM observation image (5000 times) of CNF in the laurylation reaction solution toluene extract. It is a photograph showing the water repellency of various esterified CNF dry sheets. From the left, acetylated, benzylated, 2-ethylhexylated, laurylated CNF. The figure which shows the difference in the laurylation reactivity by a different defibration degree and a water content. The figure which shows the difference in the laurylation reactivity by temperature. Shows the state of laurylated CNF dispersion in a nonpolar solvent, A: appearance of toluene and decalin dispersion, B: SEM observation diagram of fibers in toluene dispersion (× 5,000), C: in decalin dispersion SEM observation figure (* 5,000) of a fiber. The difference in laurylation reactivity depending on the ratio of potassium carbonate and CNF in the reaction system containing 1.5% of CNF is shown, ●: water content of reaction system 6%, ○: water content of reaction system 10%. Infrared absorption spectra of acetylated CNF, laurylated CNF, lauryl-acetylated CNF. X-ray crystal diffraction spectra of CNF before and after hydrolysis and various derivatized CNFs. Relationship between reaction time, weight increase rate and substitution rate in laurate esterification reaction. The figure which shows the tensile strength characteristic of composite resin, such as PE-CNF and LauCNF. The figure which shows the bending strength characteristic of composite resin, such as PE-CNF and LauCNF. The microscope picture of the polypropylene composite resin sheet of this invention which knead | mixed 5% CNF (left) or laurylated CNF (right). Light transmittance of polypropylene and a laurylated CNF-containing polypropylene composite resin film obtained by the present invention. Effects of laurylated CNF or composite resin of CNF and PP obtained by the present invention on mechanical strength properties, circles: elastic modulus, diamonds: maximum stress, triangles: maximum point strain, black (left graph) : Laurylated CNF blend, white (right graph) : CNF blend. Variations in tensile and bending elastic moduli of laurylated CNF composite polyethylene resins having different compounding ratios, solid line: tensile elastic modulus, broken line: bending elastic modulus, black coating: laurylated CNF compound, white: CNF compound.

Hereinafter, the production method of the derivatized CNF of the present invention will be described in detail.

First, a method for preparing CNF will be described. In the present invention, examples of CNF include polysaccharide-derived CNF including natural plants such as wood fiber, bamboo fiber, sugarcane fiber, seed hair fiber, and leaf fiber. These CNFs may be used alone or in combination of two or more. May be used in combination. As the polysaccharide, it is preferable to use pulp having an α-cellulose content of 60% to 99% by mass. If the purity is α-cellulose content 60% by mass or more, the fiber diameter and fiber length can be easily adjusted, and entanglement between fibers can be suppressed, and the α-cellulose content less than 60% by mass is used. Compared to the case, the thermal stability at the time of melting is high, the impact strength is not lowered, the coloration suppressing effect is good, and the effect of the present invention can be further improved. On the other hand, when 99% by mass or more is used, it becomes difficult to defibrate the fibers to the nano level.

CNF in the present invention is obtained by fibrillating polysaccharides with a high-pressure water stream.解 Degradation of polysaccharides by high-pressure water flow is carried out by colliding high-pressure water of about 50-400 MPa against polysaccharides in a water mixture of 0.5-10% by mass. This can be performed using, for example, the CNF manufacturing apparatus 1 shown in FIG. The CNF manufacturing apparatus 1 includes a polysaccharide slurry supply path 3 that is a first liquid medium supply path arranged so as to be able to supply a polysaccharide slurry to one chamber 2 and a non-polysaccharide slurry that is, for example, water. And a second liquid medium supply path 4 that is circulated through the chamber 2. In one chamber 2, there is provided an orifice injection unit 5 that performs orifice injection of the non-polysaccharide slurry in the second liquid medium supply path 4 in a direction intersecting the polysaccharide slurry supply direction from the polysaccharide slurry supply path 3. The polysaccharide slurry supply path 3 is configured such that the polysaccharide slurry can be circulated through the one chamber 2.

The polysaccharide slurry supply path 3 and the second liquid medium supply path 4 have a mutual intersection 6 in one chamber 2.
The polysaccharide slurry supply path 3 is a polysaccharide slurry supply unit, and is configured by arranging a tank 7 and a pump 8 for storing the polysaccharide slurry in the circulation path 9, while the second liquid medium supply path 4 is a tank 10, a pump 11, a heat The exchanger 12 and the plunger 13 are arranged in the liquid medium supply path 4 which is a circulation path.

The non-polysaccharide slurry is, for example, water, and is initially stored in the tank 10, and then the nano-sized polysaccharide stored in the tank 10 through the intersection 6 with the operation of the CNF manufacturing apparatus 1 is operated. Those in a state where they are contained at a concentration corresponding to the degree are also referred to generically.

As shown in FIG. 2, the circulation path 9 of the polysaccharide slurry supply path 3 is arranged so as to penetrate the chamber 2, and the non-polysaccharide slurry can be injected through the orifice in a direction crossing the polysaccharide slurry supply path 3 so as to penetrate the circulation path 9. In addition, the orifice injection port 14 of the orifice injection unit 5 connected to the plunger 13 of the second liquid medium supply path 4 opens inside the chamber 2. A discharge port 15 of the chamber 2 is provided at a position facing the orifice injection port 14 of the chamber 2, and a circulation path of the second liquid medium supply path 4 is connected to the discharge port 15 of the chamber 2, so that the second liquid state A medium supply path 4 is configured.

On the other hand, the circulation path 9 of the polysaccharide slurry supply path 3 is formed using, for example, a vinyl hose, a rubber hose or the like, and the one-way valve 16 opened only in the direction of the chamber 2 on the entry side of the circulation path 9 into the chamber 2. Is attached. Furthermore, a one-way valve 17 that is opened only in the direction of discharge from the chamber 2 is attached to the exit side of the circulation path 9 from the chamber 2. In addition, an air suction valve 18 is attached to the circulation path 9 between the chamber 2 and the one-way valve 17, and the air suction valve 18 is opened only in the direction of sucking air from the outside into the circulation path 9.

According to the above CNF manufacturing apparatus, CNF is manufactured as follows.
The non-polysaccharide slurry is circulated through the second liquid medium supply path 4 through the chamber 2. Specifically, the non-polysaccharide slurry in the tank 10 is circulated through the liquid medium supply path 4 by passing through the heat exchanger 12 and the plunger 13 using the pump 11. On the other hand, the polysaccharide slurry is circulated through the polysaccharide slurry supply path 3 through the chamber 2. Specifically, the polysaccharide slurry in the tank 7 is circulated through the circulation path 9 formed using a vinyl hose, a rubber hose, or the like, using the pump 8.

Thereby, the non-polysaccharide slurry circulating in the second liquid medium supply path 4 is orifice-injected with respect to the polysaccharide slurry circulating in the polysaccharide slurry supply path 3 and flowing in the chamber 2. Specifically, high-pressure water is supplied from the plunger 13 to the orifice injection port 14 connected to the plunger 13, and this is orifice-injected from the orifice injection port 14 toward the circulation path 9 at a high pressure of about 50 to 400 MPa.

As a result, the non-polysaccharide that has passed through the inside of the circulation path 9 in a direction crossing the circulation path 9 through the through holes 26a, b formed in advance in the circulation path 9 formed using, for example, a vinyl hose or a rubber hose The slurry is discharged toward the discharge port 15 of the chamber 2 while entraining the polysaccharide slurry circulating in the circulation path 9 and flows into the second liquid medium supply path 4. As a result, the non-polysaccharide slurry is circulated again in the second liquid medium supply path 4.
In the process of repeating the above process, the polysaccharide in the polysaccharide slurry supply path 3 and the polysaccharide in the non-polysaccharide slurry circulating in the second liquid medium supply path 4 are gradually defibrated. Thus, CNF having a high degree of defibration according to the application can be obtained.

In addition, as a method for preparing CNF by defibrating polysaccharides with a high-pressure water stream, a dispersion liquid in which raw fibers are dispersed in a solvent is treated with a homogenizer equipped with a crushing type homovalve sheet described in JP 2012-36518 A. There is a homogenization method. As shown in FIG. 3, according to this homogenization treatment method, when the raw material fiber 101 pumped through the homogenizer at a high pressure passes through the small diameter orifice 102 which is a narrow gap, the wall surface of the small diameter orifice 102 (particularly the impact ring 103). And microfibrillation having a uniform fiber diameter is performed by being subjected to shear stress or cutting action.

Furthermore, as a method for defibrating polysaccharides with a high-pressure water stream to obtain CNF, there is an underwater facing collision method described in JP-A-2005-270891. This is because natural cellulose fibers suspended in water are introduced into two nozzles (FIG. 4: 108a, 108b) facing each other in the chamber (FIG. 4: 107), and jetted and collided from these nozzles toward one point. This is a technique (FIG. 4). According to this technique, the suspension water of natural microcrystalline cellulose fibers (for example, funacell) is collided oppositely, the surface is nanofibrillated and peeled off, and the affinity with water as a carrier is improved. In particular, it becomes possible to reach a state close to dissolution. The device shown in FIG. 4 is of a liquid circulation type, and has a tank (FIG. 4: 109), a plunger (FIG. 4: 110), two opposing nozzles (FIG. 4: 108a, 108b), and heat as necessary. An exchanger (FIG. 4: 111) is provided, and fine particles dispersed in water are introduced into two nozzles and sprayed from the nozzles (FIG. 4: 108a, 108b) facing each other under high pressure to collide against each other in water. In this method, only water is used in addition to natural cellulose fibers, and only the interaction between the fibers is cleaved. CNF can be obtained in a minimized state.

The CNF obtained as described above has a solid content concentration in an aqueous dispersion state of 20% or more, so that the familiarity with the dispersant is improved and it is difficult to produce an aggregate. Therefore, it can disperse | distribute efficiently with respect to polyolefin resin. When the solid content concentration is less than 20%, the compatibility with a dispersant having a hydrophobic property in a part of the structure is poor, and it is easy to generate aggregates between CNFs. It becomes a factor of deterioration of dispersibility. Furthermore, a decrease in the resin temperature during kneading results in non-uniform shearing force during kneading, which is an undesirable obstacle to uniform dispersion during the kneading process. Furthermore, since the temperature rise of the kneading apparatus is hindered, a loss of heat energy is caused.

The method for producing a derivatized CNF of the present invention is characterized in that an organic acid vinyl is added to cellulose fiber, and for example, an organic acid vinyl such as vinyl acetate, vinyl benzoate and vinyl laurate is added to hydrous CNF. There exists an aspect which adds at least 1 or more.
Thus, in order to hydrophobize CNF, when vinyl ester is used, CNF can be esterified even if it contains water.

CNF may be obtained by nano-miniaturization of a fibrous polysaccharide by physical treatment, and the ACC method can be applied as this physical treatment.
The CNF obtained by this ACC method is obtained by cleaving only the interaction between fibers and performing nano-miniaturization. As a result, the chemical modification is not performed, the cellulose molecular structure is damaged and the degree of polymerization is reduced. On the other hand, it was obtained only in a state suspended in water, and this was a factor that hindered utilization. However, according to the method for producing derivatized CNF of the present invention, CNF obtained in a suspended state in water can be hydrophobized as it is, so that the industrial applicability of CNF obtained by the ACC method or the like is dramatically improved. Can be improved.
Pulp can be used as the fibrous polysaccharide, and as the pulp, woody plants such as hardwoods and conifers, chemical pulps made from herbaceous plants such as bamboo and bamboo, mechanical pulps and waste paper can be used.

Water-containing CNF is obtained, for example, by ACC treatment of bamboo BKP with the required number of passes, press dewatering, and has a water content of 90% or less, but is not limited to this, pulp obtained from woods and plants CNF prepared by mechanical processing such as a grinder or a homogenizer can also be used. Further, the water content may be 90% or less by a method such as centrifugation or dry concentration. However, if the water content exceeds 90%, the amount of water brought into the reaction system becomes excessive, and the production efficiency decreases, so that industrial production is difficult. The water content is preferably 85% or less, more preferably 80% or less.

Along with potassium carbonate, such water-containing CNF is added to an organic solvent capable of being sufficiently dispersible, and then at least one of organic acid vinyls such as vinyl acetate and vinyl benzoate and vinyl laurate is added, The reaction is performed at 100 ° C. for 2 hours or longer, preferably at 80 ° C. for 2 hours. After the reaction is complete, the product is recovered and dried.
Potassium carbonate works as a reaction catalyst, but a buffering effect that keeps the inside of the reaction system alkaline is important. If there is a certain concentration or more, the effect can be sufficiently maintained. However, from the viewpoint of improving the substitution rate by derivatization, the amount of potassium carbonate added is preferably about 5 to 30% in terms of the CNF ratio. Reaction efficiency is good when carried out at a CNF ratio of about 20%.
As a result of esterification with vinyl laurate, hydrophobic CNF dispersible in a hydrophobic solvent such as toluene or decalin can be synthesized. In addition, when laurylating CNF produced under the same conditions from bleached kraft pulp derived from hardwoods, conifers, and bamboo, bamboo has the highest reaction efficiency.

It is possible to uniformly and efficiently modify the surface of cellulose by adding CNF to an organic solvent capable of being sufficiently dispersible. Such organic solvents include N-methylpyrrolidone (hereinafter referred to as NMP), dimethylacetamide (hereinafter referred to as DMAc), dimethylformamide (hereinafter referred to as DMF), dimethyl sulfoxide (hereinafter referred to as DMSO) and the like. There are ionic polar solvents, and especially DMSO dissolves highly hydrophobic derivatized CNF in addition to high dispersibility of CNF. That is, laurylation of CNF proceeds in various hydrous nonionic polar solvents, but the reaction efficiency is highest when DMSO is used.

The dispersibility of this CNF in an organic solvent can be confirmed visually. For example, when press-dehydrated nanofibers are dispersed in DMSO (about 90%), they are dispersed well.

By dispersing CNF in DMSO at a stirable concentration so that the water content in the reaction vessel is 6% or less, adding potassium carbonate at 20 wt% of CNF, and reacting at a reaction system temperature of 80 ° C. or more for 2 hours. A derivatized CNF having a substitution degree of 0.4 to 0.55 can be obtained. In other words, good results can be obtained for the esterification reaction if the reaction temperature is 80 ° C. or higher. Further, after the reaction, derivatized CNF having good dispersibility can be obtained by aggregating with water, filtering and drying. Alternatively, it can be extracted with toluene, concentrated and dried.
CNF esterification can sufficiently impart hydrophobicity even with a water content of about 10%, but the reaction efficiency increases as the amount of water in the reaction system decreases.

In addition, toluene can be used as a model of molten polypropylene (PP) or polyethylene (PE). By verifying whether CNF can be easily dispersed in toluene from a dry state, it can be predicted whether it can be in a good kneaded state with polypropylene (PP) or polyethylene (PE). .

Furthermore, the dried laurylated CNF can be redispersed in toluene. It can also swell and disperse in decahydronaphthalene (polyolefin resin solvent).

According to the crystal structure analysis of cellulose, the number of primary hydroxyl groups protruding on the cellulose crystal surface is 0.5 per glucose unit, and it can be replaced by TEMPO oxidation treatment that selectively oxidizes only the primary hydroxyl group (C-6 position) on the CNF surface. The degree is around 0.5. When the degree of substitution is 0.5 or more, there is a possibility that the molecular bond of cellulose is broken.
From the analysis result of non-crystallinity in Non-Patent Document 4, reaction conditions such that the degree of substitution is 0.4 to 0.55 are preferable in order to achieve both sufficient crystallinity and hydrophobicity.

[(A) Derivatized CNF having an average thickness of 10 to 200 nm and derivatized CNF obtained by defibrating a polysaccharide with a high-pressure water stream] The content of derivatized CNF obtained by the above method is 1 to 10 Mass% is preferred. If it is less than 1% by mass, the effect of improving the mechanical properties such as the elastic modulus is not sufficiently exhibited, and if it exceeds 10% by mass, the impact strength and the like are greatly reduced and excessive costs are required.

[(B) Thermoplastic Resin] The (B) thermoplastic resin of the present invention is the main component of the composite resin composition of the present invention, but the molded product obtained by molding the composition has a rigidity and resistance to resistance. Mechanical properties such as impact properties, molding processability, solvent resistance, heat resistance, and other characteristics need to be expressed well. In addition to polyolefin, examples of the thermoplastic resin include vinyl chloride resin, styrene resin, (meth) acrylic resin, vinyl ether resin, etc. In the case of polyolefin resin, the reinforcing effect by the derivatized CNF of the present invention is particularly remarkable. is there.

The polyolefin resin is preferably a polyolefin resin obtained by homopolymerization or copolymerization of one or more monomers selected from α-olefins having 2 to 6 carbon atoms in view of the above-described characteristics. However, an α-olefin having 7 or more carbon atoms can also be used as a comonomer within a range that does not hinder the above-mentioned characteristic expression.

Examples of polyolefin resins include ethylene homopolymers, homopolymers of α-olefins having 2 to 6 carbon atoms such as propylene, butene-1, pentene-1, hexene-1, and 4-methylpentene-1, and ethylene. Examples of the copolymer include α-olefin copolymers having 3 to 6 carbon atoms, copolymers of two or more α-olefins having 2 to 6 carbon atoms, and ionomer resins.

The copolymer may be a random or block copolymer.
Also, a mixture of various polyolefin resins such as polyethylene resin and polypropylene resin can be used.
Among polyolefin-based resins, polypropylene-based resins mainly composed of propylene are excellent in rigidity, impact resistance, solvent resistance, and heat resistance, and therefore can be used particularly suitably for the composite resin composition of the present invention.

Specific examples of the polypropylene resin include a block composed of a propylene homopolymer, a propylene-ethylene copolymer, a propylene-butene copolymer, and a copolymer of propylene and ethylene and / or the above α-olefin. Examples thereof include copolymers, random copolymers, and modified polypropylene having a polar functional group.

Among olefin-based resins, high-density polyethylene (HDPE), low-density polyethylene (LDPE), and biopolyethylene are advantageous because they can provide a reinforcing effect when used as a resin composition, have flexibility, and are inexpensive. Examples thereof include polyethylene resin (PE) and polypropylene resin (PP).

Further, as the component (B), a polymer alloy obtained by blending the above-described polyolefin resin with rubber as exemplified below may be used.
Specific examples of such rubber include ethylene-propylene-nonconjugated diene copolymer rubber, ethylene-butene-1 copolymer rubber, ethylene-hexene copolymer rubber, ethylene-octene copolymer rubber, polybutadiene, and styrene-butadiene. Block copolymer rubber, styrene-butadiene copolymer rubber, partially hydrogenated styrene-butadiene-styrene block copolymer rubber, styrene-isoprene block copolymer rubber, partially hydrogenated styrene-isoprene block copolymer rubber, polyurethane rubber, styrene graft Ethylene-propylene-nonconjugated diene copolymer rubber, styrene-graft-ethylene-propylene copolymer rubber, styrene / acrylonitrile-graft-ethylene-propylene-nonconjugated diene copolymer rubber, styrene / acrylonitrile-graft- Styrene - propylene copolymer rubber and the like.
The rubber content in the polymer alloy is preferably 50% by mass or less from the viewpoint of adding new characteristics to the characteristics of the polyolefin resin.

[Polyolefin Resin Composition] Examples of the method for producing the polyolefin resin composition of the present invention include a method of melt-kneading each component by a conventionally known method.
For example, after each component is dispersed and mixed by a high speed mixer represented by a tumble mixer, a Henschel mixer, a ribbon blender, or a super mixer, a method of melt kneading with an extruder, a Banbury mixer, a roll or the like is appropriately selected.

CNF which is a biomass material as a resin composition can suppress the cohesiveness of cellulose by using CNF having a specific average fiber diameter and average fiber length, and can suppress a decrease in impact strength. Furthermore, since CNF can improve rigidity while having a lower specific gravity than inorganic fibers such as glass fibers, it can be a resin composition having high rigidity and low specific gravity.

The CNF in the present invention has an average thickness of 10 to 200 nm, and is obtained by fibrillating polysaccharides with a high-pressure water stream.
The average thickness was measured by a field emission scanning electron microscope JSM-7001FTTLS manufactured by JEOL Ltd.
By defibration to an average thickness of 10 to 200 nm, it is possible to obtain a resin composition having fluidity, little impact strength reduction, low specific gravity, high rigidity, and excellent molded appearance.
If the average thickness is less than 10 nm, the dehydrating property is deteriorated, so that it is difficult to increase the solid concentration, which is not preferable.
When the average thickness exceeds 200 nm, fibers having a fiber width of several tens of μm where defibration has not progressed are included, and fluidity is remarkably lowered and dispersibility is deteriorated.

The molding method using the polyolefin resin composition of the present invention is not particularly limited, and molding methods such as injection molding, injection compression molding, blow molding, vacuum molding, extrusion molding, and hollow molding can be applied.
Since the molded article using the polyolefin resin composition of the present invention has the above-mentioned properties, for example, OA equipment, information / communication equipment, fiber material, film material, coating film, paint component, automobile component or building material field Etc. can be suitably used.

In the present invention, by blending CNF as a biomass material with a polyolefin resin, the impact strength is hardly lowered, and the rigidity can be increased to a low specific gravity (MPa), and the surface roughness can be increased. Is a resin composition that is excellent in molded appearance and further improved in CNF dispersibility.

In the performance evaluation described in the following examples, the polyolefin resin composition of the present invention generally satisfies the following performance in terms of the tensile elastic modulus (MPa) and tensile elongation (%) of the molded product obtained, and has a molded appearance. It has the feature of being excellent.

Hereinafter, the present invention will be described more specifically with reference to examples.

With reference to the reaction method of Chemical Formula 1, which is an esterification reaction of starch, derivatization by surface modification treatment of CNF was performed as Examples 1 to 4 using a partially modified method. CNF used was crude CNF (rCNF) made with ACC and containing ~ 300 nm fibers.
5 mL of a mixed solution of 94% DMSO / 6% water (v / v) containing 1.5% (w / v) rCNF and potassium carbonate (vs. pulp weight 20%) was stirred at room temperature until a good dispersion was obtained. . After dispersion, heat to 70 ° C, add vinyl acetate, vinyl laurate, vinyl benzoate, vinyl 2-ethylhexanoate so as to be equivalent to 1.2 mol per anhydroglucose unit (AGU), and seal for 2 hours. Reacted at 70 ° C.
After completion of the reaction, a part of the reaction solution was taken and mixed with double the amount of toluene, and the hydrophobicity of the reaction product was simply evaluated. Further, water was added to the remaining reaction solution to stop the reaction, followed by filtration and water washing twice and acetone washing three times, and water was removed with a hot air drier. The obtained dry sheet was observed for water repellency.

The state when toluene is added to the solution at the end of the reaction is shown in FIG. Non-derivatized CNF (without vinyl derivatization), vinyl acetate, derivatized CNF with vinyl benzoate does not cause CNF migration to toluene, and only when derivatized with vinyl laurate is the toluene layer (upper layer) Therefore, laurylated CNF can be recovered by toluene extraction. When the toluene extraction layer of the laurylated derivatization reaction solution is collected and dried and observed by SEM, it is found that a large amount of fibers of about 300 nm are contained, and the fiber width tends to be thicker than rCNF used as a raw material. (FIG. 7).

The results of weighing the derivatized product after drying are shown in Table 2. When the estimated substitution degree (DS) was calculated from the weight increase rate (WPG), vinyl acetate showed the highest derivatization rate, followed by vinyl benzoate and vinyl laurate. This is considered to be due to the difference in reactivity due to the bulkiness of the substituents or hydrophobicity. The reason why the reactivity of vinyl 2-ethylhexanoate is particularly low is considered to be due to steric hindrance. Further, in the observation result of water repellency of the dried derivatized CNF sheet (FIG. 8), laurylated CNF has the highest water repellency and the contact angle exceeds 90 °. Thus, laurylation can impart the highest hydrophobicity to CNF.

[Example 5]
Laurylated CNF was produced in the same manner as in Example 4. However, the amount of potassium carbonate was 20% relative to CNF, and the amount of water in the reaction system or the reaction temperature was changed. In addition to CNF (rCNF) similar to that in Example 4, CNF (fCNF) having a smaller fiber diameter was also used. The reaction time was 2 hours.

FIG. 11 shows the rate of weight increase in a DMSO solution having a water content of 6 to 10 vol% at a reaction temperature of 80 ° C. In all moisture concentration regions, fCNF is more reactive than rCNF, and the specific surface area is expected to affect the reactivity. In other words, it is assumed that the hydroxyl group on the fiber surface is mainly derivatized in this reaction system. It became the result. On the other hand, it became clear that the rate of weight increase gradually decreased as the amount of water in the reaction system increased. However, even in the case of DS0.25 having the smallest WPG, the addition of water produced aggregates, so that the hydrophobization proceeded. The lower the water content is, the higher the reactivity is. On the other hand, even if the water content is about 10%, the hydrophobicity of CNF proceeds sufficiently.

The weight increase rate when the reaction temperature is set from 70 ° C. to 100 ° C. is shown in FIG. At 80 ° C. and 100 ° C., there is no significant difference in the weight increase rate, and the reactivity is equivalent. On the other hand, the weight increase rate decreased by about 35% at 70 ° C. compared to the case of 80 ° C. or higher. The reaction temperature should just be 80 degreeC or more.

A state in which laurylated CNF having an estimated substitution degree of about 0.5 is dispersed in toluene and decalin at a concentration of 1% is shown in FIG. 12A, and the results of SEM observation of each dispersion state are shown in FIGS. 12B and 12C. It was well dispersed in toluene. In addition, even the decalin dispersion is cloudy but is sufficiently well dispersed by visual observation. When the dispersion state of laurylated CNF in the dispersion is observed by SEM, although fiber aggregation tendency is somewhat observed in decalin, the fibers can be observed independently with either solvent, so that the degree of substitution is about 0.5. CNF can be dispersed in toluene and decalin. Both toluene and decalin are known to dissolve polyolefin resins, and particularly hot decalin dissolves polypropylene, so that laurylated CNF can be uniformly dispersed in polypropylene.

[Example 6]
Laurylated CNF was synthesized in the same manner as in Example 4. However, fCNF was used, the water content in the system was 6% or 10%, and the reaction temperature was 80 ° C. Moreover, it reacted by changing the amount of potassium carbonate. The reaction time was 2 hours.

In both cases where the water content is 6% or 10%, the weight increase rate is the maximum when the potassium carbonate addition ratio is 20% in terms of the CNF ratio, and the reactivity gradually decreases in the potassium carbonate concentration region beyond that. On the other hand, in the concentration region of less than 20%, the rate of increase in weight also decreases rapidly depending on the decrease in the concentration of potassium carbonate (FIG. 12).

In the study of acetylation of cellulose nanocrystals (CNC) in anhydrous DMF (Cetin et. Al. (2009) Acetylation of celluloses with vinylacetate unundermoderate conditions. Double AGU moles and potassium carbonate 33% by weight are added and the degree of substitution is about 0.35 after 2 hours of reaction. In spite of the fact that the preceding example is anhydrous and more organic vinyl acid is used, the present invention provides a higher degree of substitution than the preceding example. It has been improved.

[Example 7]
In the same manner as in Example 4, laurylated CNF was synthesized using DMSO, DMF, DMAc, and NMP as solvents. Also, laurylated CNF was synthesized using fCNF produced from kraft pulp derived from hardwood (LB), conifer (NB), and bamboo (BB). Potassium carbonate was 20% relative to CNF, the reaction temperature was 80 ° C., the water content was 6%, and the reaction time was 2 hours.

Table 2 summarizes the rate of increase in specific weight, assuming that the rate of increase in weight when LB-CNF was laurylated in DMSO was 100%. When various aprotic polar solvents were used, the reactivity of DMF, DMAc, and NMP was about one-third that of DMSO. Any solvent including DMSO is a nonionic polar solvent used for dissolving cellulose. However, except DMSO, all solvents are amine solvents and have a carbonyl oxygen and nitrogen atom resonance structure, both of which are more hydrophobic than DMSO. There are differences such as high. Differences in reactivity can be attributed to such differences in properties.

On the other hand, when the laurylation reactivity to CNF prepared from bleached kraft pulp derived from conifers and bamboo (NB and BB) is compared with that of LB, the reactivity is slightly lower in NB, and the reactivity is similar in BB. high.

[Example 8]
In the same manner as in Example 1, acetylated CNF was synthesized. However, the amount of water in the reaction system was 5%.

[Example 9]
In the same manner as in Example 4, laurylated CNF was synthesized. However, the amount of water in the reaction system was 5%.

[Example 10]
In the same manner as in Example 9, CNF derivatization with vinyl laurate was performed for 1.5 hours, and then vinyl acetate was continuously added and reacted for an additional 1.5 hours to obtain lauryl-acetylated CNF. .

[Example 11]
Various derivatized CNFs (acetylated CNF, laurylated CNF, lauryl-acetylated CNF) produced in Examples 8 to 10 and non-derivatized CNF were converted into dry powders after washing by Soxhlet extraction, and infrared absorption spectra were obtained. It was measured.

The infrared absorption spectrum is shown in FIG. In acetylated CNF (AceCNF), in addition to the typical infrared absorption spectrum of cellulose, absorption derived from C═O stretching near 1750 cm ⁻¹ is observed. Further, the absorption derived from the stretching of the methyl group near 1380 cm ^-1 derived from the acetyl group and the —CO— stretching near 1240 cm ^-1 was clearly observed, and it was confirmed that the acetyl substitution was performed. In laurylated CNF (LauCNF), a new peak attributable to alkane stretch in the range of 3000-2800cm ^-1 it has been two occurrences, also, a peak derived from C = O stretch was confirmed around 1750 cm ^-1. From these, it was shown that La CNF is laurylated. Lauryl-acetylated CNF (LauAceCNF) shows almost the same spectrum as laurylated CNF. However, since absorption is observed in the vicinity of 1240 cm ⁻¹ , an acetyl group is also given, and it is considered that both lauryl group and acetyl group are introduced into CNF.

[Example 12]
Various derivatized CNFs or CNFs were washed with methanol several times and solvent-replaced in advance. Subsequently, this was hydrolyzed in methanol containing 0.5% NaOH at 50 ° C. for 2 hours. Derivatized CNF, CNF and various CNFs after hydrolysis were dried and powdered and subjected to an X-ray diffraction test using a powder X-ray diffractometer. From the X-ray diffraction diagram, the specific crystallinity (CrI) was calculated from the diffraction intensities of 2θ = 18.5 ° and 22.5 ° by the Segal method.

FIG. 14 shows X-ray diffraction spectra of various derivatized CNFs and CNFs before and after hydrolysis. The spectrum of derivatized CNF is greatly changed from that of cellulose type I crystals, and it is difficult to obtain an accurate specific crystallinity (before hydrolysis). However, when X-ray diffraction analysis of derivatized CNF after hydrolysis was performed, all samples showed almost similar spectra, and all retained cellulose I-type crystals (after hydrolysis). Even if CNF is hydrolyzed, the degree of crystallinity does not change, and hydrolyzing treatment in a 0.5% NaOH methanol solution at 50 ° C. for 2 hours does not affect the cellulose crystal form. In addition, each hydrolyzed derivatized CNF is equivalent to or slightly lower than CNF of CrI = 63 to 66%, and the surface hydrophobicization of CNF by this method is a reaction to the cellulose fiber surface, The crystal part is hardly affected (Table 3).

[Example 13]
To 75 mg of CNF, 1.2 times mole of vinyl laurate was added as AGU and reacted at 70 ° C. for 1.5 to 6 hours. FIG. 15 shows the change over time in the degree of substitution estimated from the change in weight at that time. The substitution reaction was almost completed from 1 hour to 1.5 hours after the start of the reaction, and then the degree of substitution gradually improved.

Next, an Example is concretely demonstrated about the invention regarding the composition of derivatized CNF and polyolefin resin.

[Example 14]
The micronized nanocellulose retains a high specific surface area, and at the same time has extremely high hydrophilicity due to the influence of hydroxyl groups exposed on the surface, and thus is easily aggregated by hydrogen bonding.
Therefore, the high hydrophilicity causes aggregation in a highly hydrophobic resin such as polyolefin, and the strength property cannot be sufficiently exhibited. Therefore, in order to solve the problem, the surface of the nanocellulose fiber is esterified to impart hydrophobicity and improve dispersibility in the polyolefin, thereby improving the reinforcing function for the polyolefin.

CNF was created by the underwater facing collision method. In addition, nanofibers (CNFfine) with further miniaturization were also prepared. CNF and CNFfine were laurylated according to [Example 1] to [Example 10] (LauCNF and LauCNFfine), and the degree of substitution of hydroxyl groups by laurylation was 0.45 (± 0.01).

Water-containing CNF or acetone-derivatized CNF was premixed with medium density polyethylene (Lupolen 3621 MRM, PE) so that the cellulose part was 5% or 10%. The premixing of the hydrous CNF here may be carried out by hand, or a fluid mixer, a high-speed stirring mixer, or the like may be used. In the premixing of the acetone-containing CNF, the acetone may be suspended together with PE and stirred well, and then the acetone may be distilled off, or may be premixed using a fluid mixer as in the case of the water-containing CNF. Good.

In the premixing, PE and derivatized CNF may be mixed uniformly, but once the derivatized CNF is dried, a strong aggregate is formed and redispersion becomes extremely difficult. As a result, derivatized CNF is agglomerated in a large amount even by twin-screw extrusion kneading, and the strength is adversely affected. Therefore, drying of the derivatized CNF must be avoided.

The mixture with the premixed PE had a screw system used for a twin-screw extruder (Toyo Seiki, Labo Plast Mill) having a diameter of Φ25 mm and an effective length (screw length L to diameter D ratio) of 30. From the obtained composite resin pellets, a dumbbell test piece 1BA and a strip-shaped test piece were prepared using a small injection molding machine (Nissei Plastic Industries, NPX7-1F). The test piece was allowed to stand for 4 days or more at a temperature of 23 ° C. and a humidity of 50%, and then subjected to analysis of mechanical properties. Using Ez-LX manufactured by Shimadzu Corporation, the tensile strength test (10 mm / min) was measured using a dumbbell test piece 1BA, and the bending strength test (2 mm / min) was measured using a strip-shaped test piece.

FIG. 15 shows the tensile strength of the composite resin of CNF or derivatized CNF and PE, and FIG. 16 shows the bending strength. Statistical comparison of composite resin (PE + 10% CNF) with 10% CNF blended with PE and composite resin (PE + 10% CNFfine) with 10% CNFfine by t-test results in maximum tensile stress, flexural modulus, maximum bending PE + 10% CNF was significantly higher in stress (p <0.05), but no significant difference was observed in tensile modulus, tensile and bending maximum strain. On the other hand, when a composite resin (PE + 5% CNF) containing 5% CNF in PE and PE + 10% CNF is compared, PE + 10% CNF has a significantly higher strength in terms of maximum tensile stress, flexural modulus, and maximum bending stress. PE + 5% CNF showed a significantly higher value only with tensile strain.

Comparing the strength of PE + 5% and 10% CNF and the composite resin (PE-5% LauCNF) in which PE is mixed with LauCNF so that the CNF part is 5%, PE + 5% LauCNF is more than PE + 10% CNF composite resin. The tensile modulus, maximum tensile stress, and maximum bending strain showed significantly high strength characteristics, and PE + 10% CNF exhibited significantly high elongation at the maximum tensile strain, bending modulus, and maximum bending modulus. Compared with PE + 5% CNF, PE + 5% LauCNF showed significantly better properties in terms of tensile modulus, maximum tensile stress, flexural modulus, and maximum bending stress. Further, only with respect to the maximum tensile strain, PE + 5% CNF showed a better value. In the case of PE + 10% CNFfine and PE + 5% LauCNFfine, PE + 5% LauCNFfine shows high strength at the maximum tensile stress and maximum bending stress, and there is no significant difference (p = 0.07), but the tensile elastic modulus is higher in LauCNFfine. There was a trend. Regarding the maximum tensile strain, PE + 5% CNFfine showed significantly better elongation. In addition, when PE + 5% LauCNF is compared with PE + 5% LauCNFfine, only significant differences are observed in the maximum tensile and bending stresses. LauCNF has higher strength and tends to decrease in strength due to miniaturization as in the case of no derivatization. It was seen.

Thus, as a result of comparing the strength of the composite resin containing 5% of LauCNF with that of CNF, the reinforcement effect on PE by laurylating CNF is equal to or greater than the flexural modulus, tensile modulus, maximum tension and The bending stress is twice or more. On the other hand, the maximum tensile strain is reduced by laurylation, giving strong and hard properties. In addition, the strength of CNF as a raw material also affects the strength of LauCNF.

[Example 15]
Kneading with polyolefin resin ○ Mixing before kneading with polyolefin resin Laurylated CNF swollen with acetone was mixed with polyolefin using FM mixer (FM10C / I, Nippon Coke Industries, Ltd.). In the case of polypropylene (PP), 5 wt% of maleic acid-modified PP (TOYOBO Co., LTD.) Was mixed, but in the case of polyethylene (PE), it was not mixed.

○ Kneading The mixture with PE or PP mixed before was subjected to a twin screw extruder (Toyo Seiki, Labo Plast Mill). The screw system had a diameter of 25 mm and an effective length (screw length L to diameter D ratio) of 30. From the obtained composite resin pellets, a dumbbell test piece 1BA and a strip-shaped test piece were prepared using a small injection molding machine (Nissei Plastic Industries, NPX7-1F). The test piece was allowed to stand for 4 days or more at a temperature of 23 ° C. and a humidity of 50%, and then subjected to analysis of mechanical properties.

A composite resin sheet having a thickness of about 150 μm was prepared. Aggregates in the sheet were observed with an optical microscope (DSX500, OLYMPUS). Further, the light transmission spectrum was measured with a visible-infrared spectrophotometer (integrated sphere, UV-2600, Shimadzu Corporation).

○ Strength measurement A strength test was performed using Ex-LX manufactured by Shimadzu Corporation. The tensile strength test (10 mm / min) was measured using a dumbbell specimen 1BA, and the three-point bending strength test (2 mm / min) was measured using a strip-shaped specimen.

(result)
The microscope observation photograph of the composite resin (PP) sheet prepared using CNF and laurylated CNF is shown in FIG. In the CNF-blended PP composite resin sheet, CNF was not sufficiently dispersed, and many aggregates of about 500 μm were confirmed. On the other hand, almost no aggregate was observed in the laurylated CNF-containing PP composite resin sheet.

○ Light transmittance of the PP composite resin sheet containing light-transmitting laurylated CNF was observed, and in the visible region, light transmittance equivalent to that of polypropylene was obtained when blended with 5% laurylated CNF. However, the light transmission was maintained at about 90%. In the ultraviolet region, it was observed that the light transmittance tended to decrease greatly depending on the blending ratio of laurylated CNF (FIG. 18).

○ Reinforcing effect on polypropylene (PP) The results of tensile properties of polypropylene composite resin are shown in FIG.
First, in the maximum stress (comparison between ◆ and ◇), laurylated CNF showed a high maximum tensile stress at all compounding ratios. Next, the elastic modulus (comparison between ● and ○) showed an elastic modulus of 5% or more of CNF product when 1.5% of laurylated product was blended. In addition, the strain (comparison between ▲ and △) tended to decrease due to blending, but the strain reduction rate was small compared to unmodified CNF.

When the blending ratio of laurylated CNF was in the range of 0.5 to 1.5%, the reinforcing effect was shown depending on the blending ratio. However, no reinforcement effect on the tensile modulus was observed even when blended more than that. The 3% blending point showed the highest reinforcing effect, and the strength of the composite resin was about 150% in terms of tensile modulus and about 110% in terms of maximum tensile stress, relative to polypropylene. The strength characteristics were almost the same as when 1.5% was blended. Even when 0.5% is blended, both the modulus of elasticity and the maximum stress are significantly higher than those of polypropylene (the p value is <0.05, so a significant difference is recognized at a significance level of 5%), and the modulus of elasticity is about 120%.

When the blending ratio was increased to 5% or more, although the reinforcing effect for polypropylene was sufficiently maintained, the reinforcing effect tended to gradually decrease. Also, the transparency of the composite resin film was lowered from 5% to 10%. For these reasons, the blending ratio of laurylated CNF is preferably less than 5%. Further, a blending ratio of 3% or less is desirable from the viewpoint of cost effectiveness.

[Example 16]
○ Reinforcing effect on polyethylene (PE) When the reinforcing effect of laurylated CNF on PE was compared with that of CNF, the same or better reinforcing effect could be obtained at a low concentration by both tensile and bending elastic moduli (Fig. 20).

The tensile and bending properties are shown for the reinforcing effect on PE (tensile: solid line, bending: broken line). As for the tensile modulus, a reinforcing effect was observed when 0.5% of laurylated CNF was blended. In addition, a reinforcing effect was observed in the flexural modulus from the time of blending 1.5%. However, unlike the case of polypropylene, when 7.5% of laurylated CNF was added, the tensile modulus did not fluctuate (decrease) greatly even when the tensile modulus took the maximum value and the blending rate was 10%. . The laurylated CNF 7.5% blended polypropylene composite resin showed a value of 155% in terms of tensile modulus and 135% in terms of maximum tensile stress relative to polyethylene. The maximum point strain was 75%. On the other hand, the reinforcing effect of the flexural modulus increased depending on the blending concentration until 10% was blended. The flexural modulus at this blending concentration was 155% of polyethylene and the maximum bending stress was 130%.

Claims (15)

1. A method for producing derivatized CNF, comprising a step of reacting an organic acid vinyl with water-containing cellulose nanofiber (hereinafter referred to as CNF) and recovering the product after completion.
2. The water-containing CNF is a water-containing CNF obtained by converting a 0.5 to 10 mass% polysaccharide water mixture into high-pressure water of 50 to 400 MPa and spraying and colliding from a plurality of locations. A process for producing a derivatized CNF according to claim 1.
3. The production of derivatized CNF according to any one of claims 1 to 2, wherein the reaction is a reaction with a water content in a reaction vessel of 10% or less and a reaction system temperature of 70 ° C or more. Method.
4. The method for producing derivatized CNF according to any one of claims 1 to 3, wherein the reaction is a reaction having a reaction time of 1 hour or more.
5. The derivatized CNF according to any one of claims 1 to 4, wherein the organic acid vinyl is selected from the group consisting of vinyl acetate, vinyl benzoate, vinyl 2-ethylhexanoate and vinyl laurate. Manufacturing method.
6. 6. The reaction according to claim 1, wherein the reaction is a reaction in which the water-containing CNF dispersed in an organic solvent is performed between potassium carbonate and an organic acid vinyl. Method for producing derivatized CNF.
7. The method for producing derivatized CNF according to claim 6, wherein the organic solvent is an aprotic polar solvent.
8. The organic solvent is selected from the group consisting of dimethyl sulfoxide (hereinafter referred to as DMSO), dimethylformamide (hereinafter referred to as DMF), N, N-dimethylacetamide (hereinafter referred to as DMA) and N-methylpyrrolidone (hereinafter referred to as NMP). The method for producing derivatized CNF according to any one of claims 6 to 7, wherein:
9. The method for producing derivatized CNF according to any one of claims 6 to 8, wherein the amount of potassium carbonate added is 5 to 30% by mass in terms of CNF.
10. The method for producing derivatized CNF according to any one of claims 1 to 9, wherein the derivatized CNF has a substitution degree of 0.25 to 0.55.
11. (A) 0.5 to 10% by mass of the derivatized CNF obtained by the production method according to any one of claims 1 to 10 and (B) 99.5 to 90% by mass of a polymer compound synthetic resin. A polymer compound synthetic resin composition characterized by that.
12. 12. The polymer compound synthetic resin composition according to claim 11, wherein the derivatized CNF is derivatized CNF having an average thickness of 10 to 200 nm.
13. The polymer compound synthetic resin composition according to any one of claims 11 to 12, wherein the polymer compound synthetic resin is a thermoplastic resin.
14. The polymer compound synthetic resin composition according to claim 13, wherein the thermoplastic resin is a polyolefin resin.
15. The method includes a step of stirring the derivatized CNF obtained by the production method according to any one of claims 1 to 10 swollen with an organic solvent with the thermoplastic resin at a high speed, and then melt-kneading. A method for producing the polymer compound resin composition.
    

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