JP6545758B2 - Composition comprising cellulose and dispersant - Google Patents

Description

  The present invention relates to a composition comprising cellulose and a dispersant.

Cellulose fiber is the basic skeletal material of all plants and has an accumulation of over one trillion tons on earth. In addition, cellulose fiber is a fiber having a strength of 5 times or more that of steel and a low linear thermal expansion coefficient of 1/50 of glass although it is 1/5 the weight of steel. Therefore, there is a technology in which a cellulose fiber is contained as a filler in a matrix such as a resin to impart mechanical strength (Patent Document 1). Moreover, in order to further improve the mechanical strength of cellulose fibers, cellulose fibers are fibrillated to produce cellulose nanofibers (CNF, microfibrillated plant fibers) (Patent Document 2). Similar to CNF, cellulose nanocrystals (CNC) are known as those obtained by fibrillating cellulose fibers. CNF is a fiber obtained by subjecting a cellulose fiber to processing such as mechanical disintegration, and is a fiber having a fiber width of about 4 to 100 nm and a fiber length of about 5 μm or more. The CNC is a crystal obtained by subjecting cellulose fibers to a chemical treatment such as acid hydrolysis, and is a crystal having a crystal width of about 10 to 50 nm and a crystal length of about 500 nm. These CNFs and CNCs are collectively referred to as nanocellulose. Nanocellulose has a high specific surface area (250-300 m ² / g), is lightweight and has high strength compared to steel.

  Nanocellulose has a small thermal deformation compared to glass. Nanocellulose, which has high strength and low thermal expansion, is a useful material as a sustainable resource material, for example, a composite material that achieves high strength and low thermal expansion by combining nanocellulose and a polymer material such as resin, airgel material, CNC An optically anisotropic material utilizing a chiral nematic liquid crystal phase by self-assembly of a nano-cellulose, a functional group has been introduced into nanocellulose to develop and create a highly functional material. Since nanocellulose has a large number of hydroxyl groups, it has an aspect of being less compatible with hydrophilic, highly polar, hydrophobic, non-polar, and versatile resins. In material development using nanocellulose, it is studied to improve the compatibility of nanocellulose with a versatile resin by performing surface modification of nanocellulose or introducing a functional group to nanocellulose by chemical treatment. In other words, it has been studied to improve the dispersibility of nanocellulose in general-purpose resins.

  In addition, it has been studied to improve the compatibility between the cellulose fiber and the general-purpose resin by adding a dispersant to the composition containing the cellulose fiber and the general-purpose resin. In Patent Document 3, a thermoplastic resin is prepared by blending a carbon black, an inorganic substance such as zinc oxide, a polyol, a dispersant such as castor oil hydrogenated substance, a ricinoleic acid derivative, etc. into a resin composition containing cellulose fiber and a thermoplastic resin. In the inside, cellulose fiber is dispersed. In Non-Patent Document 1, cellulose nanocrystals (cellulose nanowhiskers) are adsorbed with a surfactant to improve the organic solvent dispersibility of cellulose nanocrystals. In Non-Patent Document 2, an isotactic polypropylene composite material using a cellulose nanocrystal adsorbed with a surfactant as a reinforcing material is produced, and the tensile strength is improved about 1.4 times compared to iPP alone.

  In patent document 4, when using a cellulose as a reinforcing material of a thermoplastic resin, in order to suppress the generation | occurrence | production of the clump of a cellulose and disperse | distribute a cellulose to resin uniformly, it is hydrophilic with a cellulose fiber and specific HLB It is described to disperse the additive (low molecular weight surfactant) having the value (hydrophilic / lipophilic balance).

However, the components used as conventional dispersants can not form strong and heat / impact stability interactions with cellulose fibers, or the cellulose fibers have insufficient compatibility and affinity for the resin. Therefore, there is room for improvement on the point that aggregation of the cellulose fiber occurs in the resin, the point that the strength of the interface between the cellulose fiber and the resin is insufficient, and the like.

JP 2008-266630 A JP, 2011-213754, A JP 2012-201767 WO 2012/111408 A1

Heux et al., Langmuir, Vol. 16, No. 21, 2000, 8210-8212. Ljungberg et al., Polymer, Vol. 47, 2006, 6285-6292

  An object of the present invention is to provide a composition comprising cellulose and a dispersant, which can improve the dispersibility of cellulose to a resin.

  The present inventors have intensively studied to solve the above problems. And, the present inventors are a composition comprising cellulose and a dispersing agent, wherein the dispersing agent has a resin affinity segment A and a cellulose affinity segment B, and a block copolymer structure or gradient copolymer weight It has been found that the use of a composition having a united structure improves the dispersibility of cellulose in the resin.

  The present invention is an invention completed based on such findings and through intensive studies.

Item 1. A composition comprising cellulose and a dispersant,
A composition characterized in that the dispersing agent has a resin affinity segment A and a cellulose affinity segment B, and has a block copolymer structure or a gradient copolymer structure.

  Item 2. The composition according to item 1, wherein the cellulose is at least one selected from the group consisting of cellulose nanofibers, microfibrillated cellulose, microcrystalline cellulose, pulp, lignocellulose, and wood flour.

Item 3. The gel permeation chromatograph of the resin affinity segment A has a polystyrene equivalent number average molecular weight of 100 to 20,000, and the proportion of the resin affinity segment A in the entire dispersant is 5 to 95% by mass.
The gel permeation chromatograph of the cellulose affinity segment B is characterized in that the number average molecular weight in terms of polystyrene is 100 to 20,000, and the proportion of the cellulose affinity segment B in the entire dispersant is 5 to 95% by mass. The composition according to item 1 or 2, which is

Item 4. The polystyrene equivalent number average molecular weight in gel permeation chromatography of the dispersant is 200 to 40,000, and the molecular weight distribution index (weight average molecular weight / number average molecular weight)
Said composition is 1.0-1.6, The composition of any one of said claim | item 1-3 characterized by the above-mentioned.

Item 5. A resin composition comprising a resin and a dispersant,
A resin composition characterized in that the dispersing agent has a resin affinity segment A and a cellulose affinity segment B and has a block copolymer structure or a gradient copolymer structure.

  Item 6. 6. The resin composition according to item 5, wherein the resin is a thermoplastic resin.

Item 7. A resin composite composition comprising cellulose, a resin, and a dispersant,
A resin composite composition characterized in that the dispersant has a resin affinity segment A and a cellulose affinity segment B and has a block copolymer structure or a gradient copolymer structure.

  Item 8. 8. A resin molding material comprising the resin composite composition according to item 7.

  Item 9. 9. A resin molded body obtained by molding the resin molding material according to item 8.

  Item 10. A dispersant having a resin affinity segment A and a cellulose affinity segment B, wherein the dispersant has a block copolymer structure or a gradient copolymer structure.

Item 11. The gel permeation chromatograph of the resin affinity segment A has a polystyrene equivalent number average molecular weight of 100 to 20,000, and the proportion of the resin affinity segment A in the entire dispersant is 5 to 95% by mass.
The gel permeation chromatograph of the cellulose affinity segment B is characterized in that the number average molecular weight in terms of polystyrene is 100 to 20,000, and the proportion of the cellulose affinity segment B in the entire dispersant is 5 to 95% by mass. 11. The dispersant according to item 10, wherein

Item 12. The gel permeation chromatograph of the dispersant has a polystyrene equivalent number average molecular weight of 200 to 40,000, and a molecular weight distribution index (weight average molecular weight / number average molecular weight) of 1.0 to 1.6. Or the dispersing agent as described in 11.

  Item 13. 11. The resin affinity segment A is a segment containing a vinyl monomer unit, and the cellulose affinity segment B is a segment containing a vinyl monomer unit, according to any one of items 10 to 12 above. Dispersant as described.

  Item 14. The resin affinity segment A is a segment containing at least one monomer unit selected from the group consisting of (meth) acrylate monomers, (meth) acrylamide monomers and styrenic monomers, and the cellulose affinity segment B is 13.) The segment according to any one of items 10 to 12, which is a segment containing at least one monomer unit selected from the group consisting of an acrylate monomer, a (meth) acrylamide monomer and a styrenic monomer. Dispersant.

Item 15. A method of producing a resin composite composition, comprising
(1) mixing cellulose and a dispersing agent to obtain a composition containing cellulose and a dispersing agent;
(2) mixing the resin and the composition obtained in step (1);
Including
A method of producing a resin composite composition, wherein the dispersant has a resin affinity segment A and a cellulose affinity segment B, and has a block copolymer structure or a gradient copolymer structure.

Item 16. A method of producing a resin composite composition, comprising
(1) mixing cellulose and a dispersing agent to obtain a composition containing cellulose and a dispersing agent;
(2) mixing the resin, the dispersant, and the composition obtained in the step (1);
Including
A method of producing a resin composite composition, wherein the dispersant has a resin affinity segment A and a cellulose affinity segment B, and has a block copolymer structure or a gradient copolymer structure.

Item 17. A method of producing a resin composite composition, comprising
(1) mixing cellulose and a dispersing agent to obtain a composition containing cellulose and a dispersing agent,
(2) mixing the resin and the dispersing agent to obtain a resin composition containing the resin and the dispersing agent; and (3) obtaining the composition obtained in the step (1) and the step (2). Mixing with the cured resin composition,
Including
A method of producing a resin composite composition, wherein the dispersant has a resin affinity segment A and a cellulose affinity segment B, and has a block copolymer structure or a gradient copolymer structure.

Item 18. A method of producing a resin composite composition, comprising
(1) mixing cellulose and a dispersing agent to obtain a composition containing cellulose and a dispersing agent,
(2) mixing the resin and the dispersing agent to obtain a resin composition containing the resin and the dispersing agent; and (3) obtaining the composition obtained in the step (1) and the step (2). Mixing the cured resin composition with the resin,
Including
A method of producing a resin composite composition, wherein the dispersant has a resin affinity segment A and a cellulose affinity segment B, and has a block copolymer structure or a gradient copolymer structure.

Item 19. A method of producing a resin composite composition, comprising
(1) mixing cellulose and a dispersing agent to obtain a composition containing cellulose and a dispersing agent,
(2) mixing the resin and the dispersing agent to obtain a resin composition containing the resin and the dispersing agent; and (3) obtaining the composition obtained in the step (1) and the step (2). Mixing the cured resin composition with a dispersant,
Including
A method of producing a resin composite composition, wherein the dispersant has a resin affinity segment A and a cellulose affinity segment B, and has a block copolymer structure or a gradient copolymer structure.

Item 20. A method of producing a resin composite composition, comprising
(1) mixing cellulose and a dispersing agent to obtain a composition containing cellulose and a dispersing agent,
(2) mixing the resin and the dispersing agent to obtain a resin composition containing the resin and the dispersing agent; and (3) obtaining the composition obtained in the step (1) and the step (2). Mixing the resin composition, the resin, and the dispersant,
Including
A method of producing a resin composite composition, wherein the dispersant has a resin affinity segment A and a cellulose affinity segment B, and has a block copolymer structure or a gradient copolymer structure.

Item 21. A method of producing a resin composite composition, comprising
(1) a step of mixing a cellulose, a resin, and a dispersant to obtain a resin composite composition,
Including
A method of producing a resin composite composition, wherein the dispersant has a resin affinity segment A and a cellulose affinity segment B, and has a block copolymer structure or a gradient copolymer structure.

Item 22. A method of producing a resin composite composition, comprising
(1) mixing resin and dispersing agent to obtain a resin composition containing dispersing agent and resin; and (2) mixing cellulose and the resin composition obtained in step (1). ,
Including
A method of producing a resin composite composition, wherein the dispersant has a resin affinity segment A and a cellulose affinity segment B, and has a block copolymer structure or a gradient copolymer structure.

Item 23. A method of producing a resin composite composition, comprising
(1) mixing resin and dispersing agent to obtain a resin composition containing the dispersing agent and the resin, and (2) cellulose, resin, and the resin composition obtained in the step (1) Mixing process,
Including
A method of producing a resin composite composition, wherein the dispersant has a resin affinity segment A and a cellulose affinity segment B, and has a block copolymer structure or a gradient copolymer structure.

Item 24. A method of producing a resin composite composition, comprising
(1) a step of mixing a resin and a dispersant to obtain a resin composition containing the dispersant and the resin,
(2) mixing the cellulose, the dispersant, and the resin composition obtained in the step (1);
A method of producing a resin composite composition, wherein the dispersant has a resin affinity segment A and a cellulose affinity segment B, and has a block copolymer structure or a gradient copolymer structure.

Item 25. A method of producing a resin composite composition, comprising
(1) a step of mixing a resin and a dispersant to obtain a resin composition containing the dispersant and the resin,
(2) mixing the cellulose, the resin, the dispersant, and the resin composition obtained in the step (1);
A method of producing a resin composite composition, wherein the dispersant has a resin affinity segment A and a cellulose affinity segment B, and has a block copolymer structure or a gradient copolymer structure.

  Item 26. A method for producing a resin composite composition, comprising the step of further mixing a resin with the resin composite composition obtained by the production method according to any one of the items 15 to 25, wherein the dispersing agent A method for producing a resin composite composition, comprising: a resin affinity segment A and a cellulose affinity segment B, and having a block copolymer structure or a gradient copolymer structure.

  The composition of the present invention can improve the dispersibility of cellulose to the resin.

FIG. 5 shows the interaction of cellulose with a dispersant in the composition of the present invention. It is a figure which shows the outline | summary of the manufacturing method of the resin composite composition containing the cellulose of this invention, resin, and a dispersing agent. It is a figure which shows the outline of the block copolymer of this invention. It is a figure which shows that cellulose fiber was mixed and disperse | distributed with various organic solvents using the dispersing agent of this invention. It is a figure which shows the emulsion in water / NMP of the block copolymer of this invention. It is a figure which shows the outline | summary of the manufacturing method of the composition containing the cellulose of this invention, and a dispersing agent. It is a figure which shows that resin forms the lamella layer in the resin compound composition of this invention. It is a figure which shows that resin forms the lamella layer in the resin compound composition of this invention. It is a figure which shows that resin forms the lamella layer in the resin compound composition of this invention. It is a figure which shows the outline | summary of the manufacturing method of the resin composite composition of this invention. It is a figure which shows the outline | summary of the preparation method of the resin molding material of this invention. It is a figure which shows the preparation method of the CNF / P001 / NMP dispersion liquid of an Example. It is a figure which shows the preparation method of PE / CNF / P001 resin composition of an Example. It is a figure which shows the preparation method of PE / CNF / P001 molded object of an Example. It is a figure which shows the evaluation result of the tensile strain of the cellulose fiber-resin molding using the block copolymer of an Example. It is a figure which shows the polarization microscope image of the cellulose fiber-resin molding using the block copolymer of an Example. It is a figure which shows the analysis image by the X-ray CT scanner of the cellulose fiber-resin molding using the block copolymer of an Example. It is a figure which shows the evaluation result of the tensile strain of the cellulose fiber-resin molding using the block copolymer of an Example. It is a figure which shows the evaluation result of use of the trimix drying in the manufacture process of the cellulose fiber-resin molding using the block copolymer of invention. It is a figure which shows the analysis image by the X-ray CT scanner of the cellulose fiber-resin molding using the block copolymer of invention. It is a figure which shows the evaluation result of manufacture of the cellulose fiber-resin molding using the block copolymer of this invention. It is a figure which shows the analysis image by the X-ray CT scanner of the cellulose fiber-resin molding using the block copolymer of this invention. It is a figure which shows the polarization microscope image of the sample which manufactured the cellulose fiber-resin molding using the block copolymer of this invention by trimix drying. It is a figure which shows the preparation method of block copolymer P001 (dispersant) coating | coated CNF of this invention. It is a figure which shows the result (B) of FT-IR (A) and the frequency | count of washing | cleaning, and IR peak ratio of block copolymer P001 (dispersant) coating | coated CNF of this invention. It is a figure which shows the contact angle measurement result of block copolymer P001 (dispersant) coating | coated CNF of this invention. It is a figure which shows the photograph of the organic solvent dispersibility of block copolymer P001 (dispersant) coating | coated CNF of this invention. It is a figure which shows the nano disintegration (preparation of CR-3) by the melt-kneading of an Example. It is a figure which shows the nano disintegration (preparation of CR-4) by the low temperature kneading | mixing in water of an Example. It is a figure which shows the nano disintegration (preparation of CR-5) by low-temperature kneading | mixing in NMP of an Example. It is a figure which shows the resin elastic modulus of CR-3 of an Example, CR-4, and CR-5. It is a figure which shows observation of the pulp fiber by the hot press of the dumbbell test piece of CR-3 of an Example. It is a figure which shows observation of the pulp fiber by the hot press of the dumbbell test piece of CR-4 of an Example. It is a figure which shows observation of the pulp fiber by the hot press of the dumbbell test piece of CR-5 of an Example. It is a figure which shows the resin elastic modulus of manufacture from the pulp of an Example. It is a figure which shows the resin elasticity modulus of the dispersing agent of this invention.

(1) Composition Comprising Cellulose and Dispersing Agent The composition of the present invention comprises cellulose and a dispersing agent, and the dispersing agent has a resin affinity segment A and a cellulose affinity segment B, and is a block co-polymer. It has a polymer structure or a gradient copolymer structure.

  When the composition of the present invention is used, a specific dispersant can improve the dispersibility of cellulose in a resin. In addition, when the composition of the present invention is used, the dispersing agent coats cellulose (preferably, cellulose nanofiber (CNF), cellulose nanocrystal (CNC)) to increase the strength of the interface between cellulose and resin. it can. As a result, a resin composite composition containing cellulose, a resin, and a dispersant produced using the composition of the present invention is excellent in strength and elastic modulus.

  The dispersant contained in the composition of the present invention has a resin affinity segment A and a cellulose affinity segment B, and has a block copolymer structure or a gradient copolymer structure. The resin compatible segment A is a hydrophobic moiety and can also be described as a cellulose dispersed segment. The cellulose affinity segment B is a hydrophilic moiety and is also described as a cellulose immobilization segment. The dispersant has a block copolymer structure or a gradient copolymer structure. The dispersant is preferably an AB type diblock copolymer. The dispersant is preferably designed and synthesized by living radical polymerization (LRP).

  The interaction of the cellulose with the dispersant in the composition of the invention is shown in FIG. The dispersing agent of the present invention can mix and disperse cellulose in a solvent having low affinity to cellulose under mild conditions of normal temperature and normal pressure.

The outline | summary of the manufacturing method of the resin composite composition containing the cellulose of this invention, resin, and a dispersing agent is shown in FIG. Since the surface of the cellulose has hydroxyl groups, the cellulose is effectively coated with the cellulose affinity segment B of the dispersant. The surface of the cellulose is hydrophobized by the resin affinity segment A of the dispersant. And, on the surface, cellulose that has been hydrophobized is uniformly dispersed even in thermoplastic resins such as polyethylene (PE) and polypropylene (PP), which have very high hydrophobicity. The resin affinity segment A of the dispersant improves the strength of the interface between the cellulose and the resin. By using the composition of the present invention, aggregation of cellulose in the resin can be suppressed, and a composite material and a molded body excellent in strength and elastic modulus can be obtained.

The dispersant contained in the composition of the present invention is preferably composed of a block copolymer or a gradient copolymer containing dicyclopentenyloxyethyl methacrylate (DCPOEMA) as the resin affinity segment A, and the cellulose affinity segment B is preferably used. It is preferable to include hydroxyethyl methacrylate (HEMA) as It is preferred to prepare the composition of the present invention in a water / N-methyl pyrrolidone (NMP) based emulsion containing cellulose. By producing the composition of the present invention before mixing the cellulose and the resin (PE or the like), the cellulose does not cause aggregation in the resin.

A dispersant containing a resin affinity segment A composed of DCPOEMA and a cellulose affinity segment B composed of HEMA is also effective for resins such as PE resin, PP resin, polystyrene resin and the like.

The composition of the present invention is manufactured using an emulsion of water / N-methyl pyrrolidone (NMP) as a dispersant, and mixed with a resin (PE or the like) to carry out a defibration treatment of cellulose to form a resin composite composition. The strength of the object (resin molding material, resin molding) can be increased.

(1-1) Plant fiber used as a raw material of cellulose cellulose (or cellulose fiber) is pulp and rayon obtained from natural plant raw materials such as wood, bamboo, hemp, jute, kenaf, cotton, beet, agricultural waste, cloth And regenerated cellulose fibers such as cellophane. Examples of wood include Sitka spruce, cedar, cypress, eucalyptus, acacia and the like, and examples of paper include deinked waste paper, corrugated cardboard waste paper, magazines, copy paper and the like, but are not limited thereto. . The vegetable fiber may be used alone or in combination of two or more selected from these.

Among these, fibrillated cellulose obtained by fibrillating pulp and pulp is mentioned as a preferable raw material. As the pulp, chemical pulp (kraft pulp (KP), sulfite pulp (SP)), semi-chemical pulp (SCP) obtained by pulping plant raw materials chemically or mechanically, or both in combination ), Chemi Grand Pulp (CGP), Chemo Mechanical Pulp (CMP), Ground Pulp (GP), Refiner Mechanical Pulp (RMP), Thermo Mechanical Pulp (TMP), Chemo Thermo Mechanical Pulp (CTMP), and these pulps Deinked waste paper pulp, corrugated waste paper pulp and magazine waste paper pulp which are ingredients are mentioned as a preferable thing. These raw materials can be delignified or bleached as needed to adjust the amount of lignin in the pulp.

  Among these pulps, various kraft pulps derived from softwoods having high fiber strength (softwood unbleached kraft pulp (NUKP), softwood oxygen-exposed unbleached kraft pulp (NOKP), softwood bleached kraft pulp (NBKP)) are particularly preferable.

  The cellulose is preferably at least one selected from the group consisting of lignocellulose, cellulose nanofiber (CNF), cellulose nanocrystal (CNC), microfibrillated cellulose, pulp and wood flour.

  Pulp is mainly composed of cellulose, hemicellulose and lignin. The lignin content in the pulp is not particularly limited, but is usually about 0 to 40% by weight, preferably about 0 to 10% by weight. The measurement of lignin content can be measured by the Klason method.

  In plant cell walls, cellulose microfibrils (single cellulose nanofibers) having a width of about 4 nm are present as the smallest unit. This is the basic skeletal material (basic element) of plants. And this cellulose micro fibrils gather and form the skeleton of a plant.

  In the present invention, nanocellulose is preferably used as the cellulose fiber. In the present invention, “nanocellulose” refers to cellulose nanofibers (CNF) and cellulose nanocrystals obtained by disentangling the material (eg, wood pulp etc.) containing cellulose fibers to the nanosize level (CNC).

CNF is a fiber obtained by subjecting a cellulose fiber to processing such as mechanical disintegration, and is a fiber having a fiber width of about 4 to 200 nm and a fiber length of about 5 μm or more. The specific surface area of the CNF, preferably about 70~300m ² / g, more preferably about 70 to 250 ² / g, more preferably about 100 to 200 m ² / g. By increasing the specific surface area of CNF, when the composition is combined with a resin, the contact area can be increased, and the strength is improved. In addition, when the specific surface area is extremely high, aggregation of the resin composition in the resin is likely to occur, and a target high strength material may not be obtained. The average fiber diameter of CNF is usually about 4 to 200 nm, preferably about 4 to 150 nm, and particularly preferably about 4 to 100 nm.

As a method of disintegrating vegetable fiber and preparing CNF, the method of fibrillating cellulose fiber containing materials, such as a pulp, is mentioned. As a fibrillation method, for example, a water suspension or slurry of a cellulose fiber-containing material is subjected to mechanical abrasion by a refiner, a high pressure homogenizer, a grinder, a single or multi-screw kneader (preferably a twin-screw kneader), a bead mill, etc. A method of defibrating by crushing or beating can be used. If necessary, the above-described defibration methods may be combined and processed. As a method of these disintegration processing, Unexamined-Japanese-Patent No. 2011-213754, for example
The disintegration method etc. which were described in Unexamined-Japanese-Patent No. 2011-195738 can be used.

Further, CNC is a crystal obtained by subjecting a cellulose fiber to a chemical treatment such as acid hydrolysis, and a crystal having a crystal width of about 4 to 70 nm and a crystal length of about 25 to 3000 nm. The specific surface area of the CNC, preferably about 90~900m ² / g, more preferably about 100 to 500 m ² / g, more preferably about 100 to 300 m ² / g. By increasing the specific surface area of the CNC, when the composition is combined with the resin, the contact area can be increased, and the strength is improved. In addition, when the specific surface area is extremely high, aggregation of the resin composition in the resin is likely to occur, and a target high strength material may not be obtained. The average crystal width of CNC is usually about 10 to 50 nm, preferably about 10 to 30 nm, and particularly preferably about 10 to 20 nm. The average crystal length of CNC is usually about 500 nm, preferably about 100 to 500 nm, and particularly preferably about 100 to 200 nm.

  A known method can be adopted as a method of fibrillating plant fibers to prepare CNC. For example, chemical methods such as acid hydrolysis of the aqueous suspension or slurry of the cellulose fiber-containing material with sulfuric acid, hydrochloric acid, hydrobromic acid or the like can be used. If necessary, the above-described defibration methods may be combined and processed.

  The average value of the fiber diameter of nanocellulose (average fiber diameter, average fiber length, average crystal width, average crystal length) is an average value when measured for at least 50 or more of nanocellulose in the field of view of the electron microscope.

Nanocellulose has a high specific surface area (preferably about 200 to 300 m ² / g), is lightweight and has high strength as compared to steel. Nanocellulose also has less thermal deformation (low thermal expansion) compared to glass.

  The nanocellulose is preferably one having cellulose type I crystals and having a crystallinity degree as high as 50% or more. 55% or more of the crystallinity degree of cellulose I type of nanocellulose is more preferable, and 60% or more is still more preferable. The upper limit of the crystallinity degree of cellulose I type of nanocellulose is generally about 95% or about 90%.

  The cellulose type I crystal structure is, for example, as described in "The Dictionary of Cellulose" published by Asakura Shoten, pp. 81-86, pages 93-99, and most natural cellulose is cellulose type I. It is a crystal structure. On the other hand, cellulose fibers having a cellulose type I crystal structure, for example, cellulose fibers having a cellulose type II, III, and IV structure are derived from cellulose having a cellulose type I crystal structure. Among them, the I-type crystal structure has a high crystal elastic modulus as compared with other structures.

  In the present invention, nanocellulose having a cellulose type I crystal structure is preferred. When it is a type I crystal, when it is set as a composite material of nanocellulose and a matrix resin, a composite material with a low linear expansion coefficient and a high elastic modulus can be obtained. The fact that nanocellulose has a type I crystal structure is typical at two positions near 2θ = 14 ° to 17 ° and 2θ = 22 ° to 23 ° in the diffraction profile obtained by wide-angle X-ray diffraction image measurement. It can be identified from having a peak.

For example, ethanol is added to a slurry of nanocellulose to adjust the concentration of nanocellulose to 0.5% by weight. Next, after stirring this slurry with a stirrer, vacuum filtration (5C filter paper made by Advantec Toyo Co., Ltd.) is started quickly. Next, the obtained wet web is heated and compressed at 110 ° C. and a pressure of 0.1 t for 10 minutes to obtain a 50 g / m ² CNF sheet. Then, using an X-ray generator ("UltraX18HF" manufactured by RIGAKU Co., Ltd.), a target Cu / Kα ray, a voltage of 40 kV, a current of 300 mA, a scanning angle (2θ) of 5.0 to 40.0 °, and a step angle of 0.02 ° Under the measurement conditions, the above-mentioned CNF sheet is measured to measure the crystallinity of cellulose type I.

  The degree of polymerization of cellulose is about 500 to 10,000 for natural cellulose and about 200 to 800 for regenerated cellulose. Cellulose is a bundle of several linearly stretched celluloses formed by β-1,4 bonds, fixed by intramolecular or intermolecular hydrogen bonds, and forms crystals in the form of extended chains . Although the existence of many crystal forms of cellulose crystals has been clarified by X-ray diffraction and solid-state NMR analysis, the crystal form of natural cellulose is only Form I. From the X-ray diffraction etc., the proportion of crystalline regions in cellulose is estimated to be about 50 to 60% for wood pulp and about 70% for bacterial cellulose at a higher level. Cellulose not only has a high modulus of elasticity due to being an extended chain crystal, but also exhibits five times the strength of steel and a linear thermal expansion coefficient of 1/50 or less of glass. Conversely, breaking the crystalline structure of cellulose leads to the loss of the excellent characteristics such as high modulus and high strength of these celluloses.

Also, in general, cellulose fibers do not dissolve in water as well as common solvents. In conventional cellulose fiber modification technology, modification treatment is performed by dissolving cellulose in a mixed solution of dimethylacetamide (DMAc) / LiCl. In this way, dissolving cellulose fiber means that the solvent component strongly interacts with the hydroxyl group of the cellulose fiber and cleaves the intramolecular and intermolecular hydrogen bonds of the cellulose fiber. Cleavage of the hydrogen bond increases the flexibility of the molecular chain and greatly increases the solubility. In other words, dissolving the cellulose fiber is to break the crystal structure of the cellulose fiber. However, it has been the case that the dissolved cellulose fiber, that is, the cellulose fiber having lost crystal structure can not exhibit the characteristics such as the high elastic modulus and the high strength which are the excellent characteristics of the cellulose fiber. Thus, in the prior art, it has been very difficult to carry out the treatment of maintaining the crystal structure of the cellulose fiber and modifying the surface of the cellulose fiber.

(1-2) Dispersant The dispersant has a resin affinity segment A and a cellulose affinity segment B, and has a block copolymer structure or a gradient copolymer structure.

  A block copolymer structure is a structure in which two or more kinds of polymer chains A, B, C ... having different properties (for example, polarity etc.) are linearly bonded (for example, AB, ABA, A- B-C, etc.). An A-B type block copolymer structure in which the polymer chain A and the polymer chain B are linearly bonded is mentioned. A block copolymer structure can be obtained by utilizing known living polymerization.

  The dispersant has a resin affinity segment A and a cellulose affinity segment B, and is preferably an AB type diblock copolymer. The monomer units constituting the resin affinity segment A and the cellulose affinity segment B are preferably vinyl monomer units, and are selected from the group consisting of (meth) acrylate monomers, (meth) acrylamide monomers and styrenic monomers More preferably, it comprises at least one monomer unit. The outline of the block copolymer is shown in FIG.

  The gradient copolymer structure is, for example, a copolymer consisting of repeating units derived from two kinds of monomers A and B having different properties (for example, polarity etc.). There is a distribution gradient of repeating units such that the proportion of A units decreases and the proportion of B units increases toward the other end rich. A gradient copolymer structure can be obtained by utilizing known living polymerization.

  Since the surface of the cellulose fiber has a hydroxyl group, it is effectively coated with the cellulose affinity segment B of the AB type diblock copolymer or the AB type gradient copolymer. Moreover, the surface of a cellulose fiber is hydrophobized by the resin affinity segment A of an AB type | mold diblock copolymer or an AB type | mold gradient copolymer.

By using a dispersing agent, cellulose fibers can be mixed and dispersed in an organic solvent having inherently low affinity under mild conditions of normal temperature and normal pressure (FIG. 4).
And, the hydrophobized cellulose is uniformly dispersed even in thermoplastic resins such as PE and PP, which have very high hydrophobicity. The strength of the interface between the cellulose and the resin is improved by the dispersing agent, and aggregation of the cellulose in the resin can be suppressed. As a result, composite materials and molded bodies excellent in strength and elastic modulus can be obtained.

(1-2-1) Resin affinity segment A
The resin compatible segment A hydrophobizes the surface of cellulose via the cellulose compatible segment B. The basics of resin affinity should be similar to the structure of the target resin or have hydrophobicity close to the target resin.

  The monomer unit constituting the resin affinity segment A preferably contains at least one monomer unit selected from the group consisting of (meth) acrylate monomers, (meth) acrylamide monomers and styrenic monomers.

Resin compatible segment A is lauryl methacrylate (LMA), 4-t-butylcyclohexyl methacrylate (tert-butylcyclohexyl methacrylate; tBCHMA)
, Cyclohexyl methacrylate (CHMA), methyl methacrylate (methyl methacrylate; MMA), isobornyl methacrylate (IBOMA), dicyclopentenyloxyethyl methacrylate (DCPOEMA), dicyclopentamethacrylate Preferred is a repeating unit composed of a monomer component such as dicylopentyl methacrylate (DCPMA). The monomer component can be used alone or in combination of two or more.

Preferred monomer components are components having an alkyl group such as a component containing a branched alkyl group such as a C _n H _{2n + 1} group such as MMA or LMA, or a component containing a plurality of alkyl groups. Moreover, the component which has an unsaturated alkyl group is also preferable.

  It is possible to use a monomer component having an aromatic ring such as benzyl methacrylate, polycyclic aromatic group (such as naphthalene), and substituted aromatic group (such as o-methoxybenzyl methacrylate). Alicyclic compounds such as DCPOEM are preferred. Resin fragments having a functional group (such as a hydroxyl group or a double bond) at the end of a polyethylene end such as those having a double bond or a hydroxyl group are preferable.

  Since polylactic acid, polyamide and the like have a reactive functional group at the end, they can be the resin affinity segment A as they are.

  Preferred are small molecules such as oligoethylene, stearic acid and the like. Resin fragments having a functional group in the molecule such as MAPP (maleic acid modified PP) are preferred. It is possible to graft polymerize the cellulose affinity segment starting from the modified portion.

  The chemical structures and abbreviations of preferred repeating units (monomer components) constituting the resin affinity segment A are described below. (A) is a repeating unit of the resin affinity segment A.

  Preferred embodiments of the resin compatible segment A are shown in Table 1.

Resin compatible segment A is dicyclopentenyloxyethyl methacrylate (DCPOEMA)
It is preferable to be composed of monomer components such as block, lauryl methacrylate (LMA) block, 4-tert-butylcyclohexyl methacrylate (tBCHMA) block, and dicyclopentanyl methacrylate (DCPMA) block.

  Preferred monomer units constituting the resin affinity segment A are described below.

  Methyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tetradecyl (meth) acrylate, octadecyl (meth) Acrylate, cyclohexyl (meth) acrylate, isoboronyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, cyclodecyl (meth) acrylate, cyclodecyl methyl (meth) acrylate, tricyclodecyl (meth) acrylate, benzyl (meth) acrylate, allyl Alkyl such as (meth) acrylate, alkenyl, cycloalkyl, (meth) acrylate having an aromatic ring, and the like can be mentioned.

  Halogen element-containing (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate, octafluorooctyl (meth) acrylate, tetrafluoroethyl (meth) acrylate and the like can be mentioned.

  The polystyrene equivalent number average molecular weight in the gel permeation chromatograph of the resin affinity segment A is preferably about 100 to 20,000, more preferably about 500 to 10,000, and further preferably about 1,000 to 8,000. preferable. It is a molecular weight region that is considered to be the highest adsorption efficiency of the resin affinity segment A. The resin affinity segment A is preferably about 1,000 to 8,000 in order to exhibit resin affinity (resin compatibility) with the resin.

  The number average polymerization degree (average number of repeating units) of the resin affinity segment A is preferably about 1 to 200, more preferably about 5 to 100, and still more preferably about 10 to 50. It is a molecular weight region that is considered to be the highest adsorption efficiency of the resin affinity segment A. It is preferable that the resin affinity segment A contains at least a pentamer in order to exhibit multipoint interaction with the resin.

  It is preferable that the monomer unit which comprises the resin affinity segment A consists of a monomer unit chosen from hydrophobic monomer groups, such as a (meth) acrylate type monomer and a styrene system monomer.

(1-2-2) Cellulose affinity segment B
The cellulose affinity segment B interacts with hydroxyl groups present on the surface of cellulose by hydrogen bonding or the like. In the dispersant, the cellulose affinity segment B having a large number of hydroxyl groups, carboxyl groups, amide groups and the like is well adsorbed on the cellulose surface to form multipoint hydrogen bonds with the cellulose fiber by the polymer effect, and it is difficult to be desorbed. Ru. It is known that the zeta potential of the cellulose surface shows minus, and since the cellulose material contains hemicellulose (partly containing a unit containing a negative charge such as glucuronic acid), cationic functional groups such as quaternary ammonium The cellulose affinity segment B having a large number of salts etc. is well adsorbed to the cellulose fiber. The cellulose affinity segment B may react with hydroxyl groups present on the surface of cellulose.

  The monomer unit constituting the cellulose affinity segment B preferably contains at least one monomer unit selected from the group consisting of (meth) acrylate monomers, (meth) acrylamide monomers and styrenic monomers.

  As a cellulose affinity segment B chain, hydroxyl group (HEMA, sugar residue etc.), carboxylic acid, amide (urea, urethane, amidine etc.), cation site (quaternary ammonium salt etc.) in view of hydrogen bondability to cellulose It is preferable that it is a segment which has. Among preferred repeating units (monomer components) constituting the cellulose affinity segment B, as a hydrogen bonding monomer to cellulose, hydroxyethyl methacrylate (hydroxyethyl methacrylate; HEMA), methacrylic acid (methacrylic acid; MAA), methacrylic acid An amide (methacrylic amide; MAm), a benzylated dimethylaminoethyl methacrylate (quaternized dimethyl aminoethyl methacrylate; QDEMAEMA) and the like are preferable. The monomer component can be used alone or in combination of two or more.

The cellulose affinity segment B is preferably a segment having, for example, an isocyanate group, an alkoxysilyl group, a boric acid, and a glycidyl group, from the viewpoint of being a functional group capable of reacting with the hydroxyl group of cellulose. Among preferred repeating units (monomer components) constituting the cellulose affinity segment B, as a reactive monomer for cellulose fiber, 3-methacryloxypropyl triethoxysilane (MPE), 2-isocyanate methacrylic acid Natoethyl (methacryloyloxyethyl isocyanate; MOI), glycidyl methacrylate (GMA) and the like are preferable. The monomer component can be used alone or in combination of two or more.

  The chemical structures and abbreviations of preferable repeating units (monomer components) constituting the cellulose affinity segment B are described below. (B) interacts with the repeat unit of the cellulose affinity segment B. (C) shows the reactivity in the repeating unit of the cellulose affinity segment B.

  Preferred embodiments of the cellulose affinity segment B are shown in Table 2.

  The cellulose affinity segment B is preferably a segment containing hydroxyethyl methacrylate (HEMA).

  The polystyrene equivalent number average molecular weight in the gel permeation chromatograph of the cellulose affinity segment B is preferably about 100 to 20,000, more preferably about 500 to 10,000, and further preferably about 1,000 to 8,000. preferable. It is a molecular weight region that is considered to be the highest adsorption efficiency of the cellulose affinity segment B. In order for the cellulose affinity segment B to exhibit multipoint interaction with cellulose, it is preferably about 1,000 to 8,000.

  The number average polymerization degree (average number of repeating units) of the cellulose affinity segment B is preferably about 1 to 200, more preferably about 5 to 100, and still more preferably about 10 to 50. It is a molecular weight region that is considered to be the highest adsorption efficiency of the cellulose affinity segment B. It is preferable that the cellulose affinity segment B contains at least a 10-mer in order to exhibit multipoint interaction with cellulose.

  It is preferable that the monomer unit which comprises the cellulose affinity segment B consists of a (meth) acrylate type monomer, a (meth) acrylamide type monomer, and a styrene type monomer.

  Hydroxyl-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) Mono (meth) acrylates of polyalkylene glycols such as acrylates; (poly) ethylene glycol monomethyl ether (meth) acrylate, (poly) ethylene glycol monoethyl ether (meth) acrylate, (poly) propylene glycol monomethyl ether (meth) And glycol ether (meth) acrylates such as acrylates. Note that “poly” and “(poly)” in the above all mean n = 2 or more.

  Glycidyl group-containing (meth) acrylates such as glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, (meth) acryloyloxyethyl glycidyl ether, (meth) acryloyloxyethoxyethyl glycidyl ether; (meth) Acryloyloxyethyl isocyanate, 2- (2-isocyanatoethoxy) ethyl (meth) acrylate, and isocyanate group-containing (meth) such as ε-caprolactone of these isocyanates, monomers blocked with isocyanate by MEK oxime, pyrazole, etc. Acrylate; oxygen atom-containing cyclic (meth) acrylate such as oxetanyl methyl (meth) acrylate; dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, - containing amino groups such as butylaminoethyl (meth) acrylate (meth) acrylate and its quaternary ammonium type and the like.

  Monomers such as silicon atom-containing (meth) acrylates having a trimethoxysilyl group or a dimethyl silicone chain can also be used. Furthermore, macromonomers obtained by introducing a (meth) acrylic group at one end of an oligomer obtained by polymerizing various monomers listed above can also be used.

  When obtaining a block, an acrylic polymer obtained from a (meth) acrylate monomer having a functional group of a hydroxyl group or a carboxyl group, a (meth) acrylate having a group capable of reacting with the functional group, for example, isocyanatoethyl ( Meta) acrylate, glycidyl (meth) acrylate or the like may be reacted.

(1-2-3) Dispersant The dispersant is preferably one synthesized by living polymerization, and more preferably one synthesized by living radical polymerization.

  The dispersant is preferably a vinyl polymer. In particular, it is preferable to be composed of at least one monomer unit selected from the group consisting of (meth) acrylate monomers, (meth) acrylamide monomers and styrenic monomers.

  As the resin compatible segment A and the cellulose compatible segment B, segments obtained by means other than living radical polymerization can also be used. For example, for the resin affinity segment A, it is preferable to use an oligoethylene chain, an oligopropylene chain, a polylactic acid or the like. As the cellulose affinity segment B, polyoxyethylene (PEO), an oligosaccharide and the like are preferable. In this case, one segment is preferably synthesized by living radical polymerization, and the other block is preferably used an existing polymer, oligomer or the like.

  The cellulose affinity segment B preferably contains a functional group capable of reacting with the hydroxyl group of cellulose, such as isocyanate group, alkoxysilyl group, boric acid, glycidyl group and the like.

  The basic design of the dispersant is to have a resin affinity segment A and a cellulose affinity segment B, and an AB diblock copolymer and a gradient copolymer of AB are preferable. In addition, an ABA triblock, a graft copolymer obtained by grafting a B polymer to an A polymer, a star copolymer such as (A-B) n, and the like are also preferable.

The proportion of the resin affinity segment A in the entire dispersing agent is preferably about 5 to 95% by mass, more preferably about 20 to 95% by mass, and further preferably about 40 to 70% by mass. preferable.

The proportion of the cellulose affinity segment B in the whole dispersant is preferably about 5 to 95% by mass, more preferably about 5 to 60% by mass, and further preferably about 10 to 50% by mass. preferable.

  When the proportion of the cellulose affinity segment B is small, the effect of coating the cellulose is weakened, and when the number average molecular weight of the cellulose affinity segment B is large or the proportion in the whole is large, the solubility is deteriorated. The adsorption of cellulose particles may occur, which may cause problems in the dispersion of fine particles.

  The length of the resin affinity segment A and the cellulose affinity segment B is preferably a relatively medium molecular weight polymer of about 10 to 20 nm in total of the dispersant. The lengths of the resin affinity segment A and the cellulose affinity segment B are more preferably about 1 to 50 nm, and still more preferably about 1 to 10 nm.

The polystyrene equivalent number average molecular weight in the gel permeation chromatograph of the dispersant is preferably about 200 to 40,000, more preferably about 1,000 to 20,000, and still more preferably about 2,000 to 10,000. If the molecular weight is low, the physical properties of the article may be degraded when added to the article. Since the molecular weight is large, the solubility tends to deteriorate. For example, when it is used as a dispersing agent to make a cellulose dispersion, the remarkable effect of the present invention, that is, the ability to disperse cellulose easily becomes inferior. there is a possibility.

  The molecular weight distribution index (weight average molecular weight / number average molecular weight) of the dispersant is preferably about 1.0 to 1.6, more preferably about 1.0 to 1.5, and still more preferably about 1.0 to 1.4.

  The molecular weight distribution index (weight average molecular weight / number average molecular weight) of the dispersant represents the degree of the molecular weight distribution, and a small value indicates that the molecular weight distribution of the dispersant is narrow, that is, the uniformity of molecular weight is high. Means When the molecular weight distribution index is small, it is considered that when it is viewed on the micro side, it exhibits molecularly similar solubility, the dispersant solubility improves, and a finely dispersed dispersion state is easily given. In addition, narrow molecular weight distribution means that the dispersing agent has uniform properties due to small or large molecular weight, and the deterioration of solubility when the molecular weight is large and the influence on articles when the molecular weight is small. Will be reduced. As a result, the effect of providing the highly finely dispersed state provided by the dispersant can be further improved.

  Preferred embodiments of the dispersant are shown in Table 3.

  The dispersant is preferably an AB type block copolymer structure comprising a resin affinity segment A and a cellulose affinity segment B.

  The block copolymer is preferably designed and synthesized by living radical polymerization (LRP), and a vinyl polymer obtained by living radical polymerization is preferable.

The block copolymer is preferably added as an emulsion to a water / N-methyl pyrrolidone (NMP) -based slurry containing cellulose. The emulsion is preferably made in water / NMP (FIG. 5).

When mixing a cellulose and resin (PE etc.), aggregation of a cellulose can be suppressed by adding a block copolymer. In addition, the block copolymer of the present invention is added to a water / N-methylpyrrolidone (NMP) -based emulsion containing cellulose and a resin (such as PE), whereby the resin composition (molding The strength of the material and the molded body can be enhanced.

  The dispersant preferably has a gradient copolymer structure between the resin affinity segment A and the cellulose affinity segment B. In the gradient copolymer structure composed of the resin affinity segment A and the cellulose affinity segment B, the monomer a constituting the resin affinity segment A and the monomer b constituting the cellulose affinity segment B have different polarities 2 It is a kind of monomer. In the gradient copolymer structure, the distribution gradient of repeating units is such that the ratio of monomer a decreases and the ratio of monomer b increases from one end of the polymer chain rich in monomer a toward the other end rich in monomer b It is preferable that it is a certain structure.

(1-2-4) Method of Producing Dispersant A monomer (for example, tBCHMA or the like) to be a resin affinity segment A is dissolved in an amphiphilic solvent (for example, propylene glycol, monopropyl ether or the like) and , Subjected to living radical polymerization. Then, after a predetermined time, a monomer (for example, HEMA or the like) to be the cellulose affinity segment B is added to synthesize a block copolymer. The prepared block copolymer solution is dropped into water-containing methanol to precipitate as a solid. The catalyst and residual monomers can be removed. The obtained solid (block copolymer or gradient copolymer) is dissolved in a solvent and purified by being reprecipitated by dropping into a poor solvent (for example, acetone etc.).

  Living radical polymerization refers to a polymerization reaction in which chain transfer reaction and termination reaction do not substantially occur in the radical polymerization reaction, and the chain growth terminal retains activity even after the reaction is completed. In this polymerization reaction, the polymerization activity is maintained at the end of the formed polymer even after the completion of the polymerization reaction, and when the monomer is added, the polymerization reaction can be started again.

  The characteristics of living radical polymerization include that a polymer having an arbitrary average molecular weight can be synthesized by adjusting the concentration ratio of a monomer and a polymerization initiator, and the molecular weight distribution of the produced polymer is extremely narrow, and block co It can be applied to the synthesis of polymers, and the like. In addition, living radical polymerization may be abbreviated as "LRP", and may be called controlled radical polymerization.

  In the polymerization method of the present invention, a radically polymerizable monomer is used as a monomer. The radically polymerizable monomer refers to a monomer having an unsaturated bond capable of performing radical polymerization in the presence of an organic radical. Such unsaturated bond may be a double bond or a triple bond. That is, in the polymerization method of the present invention, any monomer conventionally known to perform living radical polymerization can be used.

  More specifically, a so-called vinyl monomer can be used. The vinyl monomer is a general term for a monomer represented by the general formula "CH2 = CR5R6".

  A monomer in which R5 is methyl and R6 is carboxylate in this general formula is referred to as a methacrylate monomer, and can be suitably used in the present invention.

  Specific examples of methacrylate monomers include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, benzyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate , N-octyl methacrylate, 2-methoxyethyl methacrylate, butoxyethyl methacrylate, methoxytetraethylene glycol methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro 2-hydroxypropyl methacrylate, tetrahydrofurfuryl methacrylate, 2- Hydroxy 3-f Roh propyl methacrylate, diethylene glycol methacrylate, polyethylene glycol methacrylate, 2- (dimethylamino) ethyl methacrylate. Methacrylic acid can also be used.

  A monomer in which R5 is hydrogen and R6 is a carboxylate in the general formula of the vinyl monomer is generally referred to as an acrylic monomer and can be suitably used in the present invention.

  Specific examples of acrylate monomers include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, t-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, benzyl acrylate, glycidyl acrylate, cyclohexyl acrylate, lauryl acrylate , N-octyl acrylate, 2-methoxyethyl acrylate, butoxyethyl acrylate, methoxy tetraethylene glycol acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-chloro 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, 2- Hydroxy 3-phenoxypropyl acrylate, diethylene glycol Call acrylate, polyethylene glycol acrylate, 2- (dimethylamino) ethyl acrylate. Also acrylic acid can be used.

  The monomer represented by the general formula of the above vinyl monomer in which R 5 is hydrogen and R 6 is phenyl is styrene, which can be suitably used in the present invention. A monomer in which R 6 is a phenyl or phenyl derivative is referred to as a styrene derivative and can be suitably used in the present invention. Specifically, o-, m-, p-methoxystyrene, o-, m-, p-t-butoxystyrene, o-, m-, p-chloromethylstyrene, o-, m-, p-chloro Styrene, o-, m-, p-hydroxystyrene, o-, m-, p-styrenesulfonic acid and the like can be mentioned. Moreover, vinyl naphthalene etc. whose R6 is aromatic are mentioned.

  The monomer whose R <5> is hydrogen and whose R <6> is alkyl in the general formula of the said vinyl monomer is an alkylene, and can be used conveniently for this invention.

  In the present invention, monomers having two or more vinyl groups can also be used. Specific examples thereof include diene compounds (for example, butadiene, isoprene and the like), compounds having two allyl groups (for example, diallyl phthalate and the like), dimethacrylates of diol compounds, and diacrylates of diol compounds.

Vinyl monomers other than those described above can also be used in the present invention. Specifically, for example, vinyl esters (eg, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl acetate), styrene derivatives other than the above (eg, α-methylstyrene), vinyl ketones (eg, vinyl methyl ketone) , Vinylhexyl ketone, methylisopropenyl ketone), N-vinyl compounds (eg, N-vinylpyrrolidone, N-vinylpyrrole, N-vinylcarbazole, N-vinylindole), (meth) acrylamides and derivatives thereof (eg, N -Isopropyl acrylamide, N-isopropyl methacrylamide, N, N-dimethyl acrylamide, N, N-dimethyl methacrylamide, N-methylol acrylamide, N-methylol methacrylamide), acrylonitrile, methacrylonitrile, maley Acids and their derivatives (eg, maleic anhydride), halogenated vinyls (eg, vinyl chloride, vinylidene chloride, tetrachloroethylene, hexachloropropylene, vinyl fluoride), olefins (eg, ethylene, propylene, 1-hexene, cyclohexene) Etc.

  These may be used alone or in combination of two or more.

  The living radical polymerization method can be applied to homopolymerization, ie to the production of homopolymers, but it is also possible to produce copolymers by copolymerization. Each of the resin affinity segment or the cellulose affinity segment may be random copolymerization.

  The block copolymer may be a copolymer in which two or more types of blocks are linked, or may be a copolymer in which three or more types of blocks are linked.

  In the case of block copolymerization consisting of two types of blocks, for example, a block copolymer can be obtained by a method including the steps of polymerizing a first block and polymerizing a second block. In this case, living radical polymerization may be used in the step of polymerizing the first block, and living radical polymerization may be used in the step of polymerizing the second block. It is preferable to use a living radical polymerization method in both the step of polymerizing the first block and the step of polymerizing the second block.

  More specifically, a block copolymer can be obtained, for example, by polymerizing the first block and then polymerizing the second block in the presence of the obtained first polymer. The first polymer can be subjected to the polymerization of the second block after isolation and purification, or the first polymer is not isolated and purified, and during or at the completion of the polymerization of the first polymer, the first polymer Block polymerization can also be carried out by adding a second monomer to the polymerization.

  Also in the case of producing a block copolymer having three types of blocks, as in the case of producing a copolymer in which two or more types of blocks are bonded, a step of polymerizing each block is performed to obtain a desired copolymer weight. You can get a union.

(1-2) Blending Ratio of Composition The content of the dispersant and the cellulose in the composition may be such that the cellulose can be dispersed.

  The cellulose can be dispersed by setting the content of the dispersant in the composition to about 50 parts by mass with respect to 100 parts by mass of the cellulose. The content of the dispersant in the composition is more preferably about 5 to 200 parts by mass, further preferably about 10 to 150 parts by mass, and further preferably 20 to 100 parts by mass with respect to 100 parts by mass of cellulose. Particular preference is given to the degree.

(2) Method of Producing a Composition Comprising Cellulose and a Dispersing Agent An outline of a method of producing a composition comprising the cellulose of the present invention and a dispersing agent is shown in FIG. It is a cellulose dispersion containing a dispersant. The specific surface area can be increased by using nanocellulose.

When cellulose (pulp, CNF, CNC, etc.) and resin (PP, PE, etc.) are mixed, cellulose and resin phase separate, and cellulose fibers precipitate. By adding the dispersant as a water / N-methylpyrrolidone (NMP) emulsion before mixing the cellulose and the resin, aggregation of the cellulose can be suppressed. In the coexistence of the dispersant emulsion, the strength of the resin composition (the molding material, the molding) can be increased by the fibrillation step of cellulose.

  The cellulose may be modified with the cellulose affinity segment B of the dispersant.

  A dispersing agent may be used to modify the cellulose in a state in which the cellulose is dispersed in a solvent, ie, in a heterogeneous solution. By performing modification treatment without dissolving cellulose, the modified cellulose can be produced while maintaining the crystalline structure of cellulose type I in the cellulose and maintaining the properties such as high strength and low thermal expansion. The modified cellulose is a cellulose that maintains the crystalline structure of cellulose type I and retains high strength and low thermal expansion performance.

(3) Composition Containing Resin and Dispersant The resin composition of the present invention comprises a resin and a dispersant, and the dispersant has a resin affinity segment A and a cellulose affinity segment B, and is a block. It has a copolymer structure or a gradient copolymer structure.

  The dispersant is as described above.

(3-1) Resin The resin component is not particularly limited, and examples thereof include thermoplastic resins and thermosetting resins.

  As the resin, it is preferable to use a thermoplastic resin from the advantage that the molding method is simple. Examples of the thermoplastic resin include olefin resins, nylon resins, polyamide resins, polycarbonate resins, polysulfone resins, polyester resins, cellulose resins such as triacetylated cellulose and diacetylated cellulose. Examples of polyamide resins include polyamide 6 (PA6, ring-opening polymer of ε-caprolactam), polyamide 66 (PA 66, polyhexamethylene adipamide), polyamide 11 (PA11, polyamide obtained by ring-opening polycondensation of undecanelactam), polyamide 12 (PA12, a polyamide obtained by ring opening polycondensation of lauryl lactam) and the like.

  As the thermoplastic resin, an olefin resin or the like is preferable from the advantage that the reinforcing effect in the case of using a resin composition can be sufficiently obtained and the advantage that it is inexpensive. Examples of olefin resins include polyethylene resins, polypropylene resins, vinyl chloride resins, styrene resins, (meth) acrylic resins, vinyl ether resins and the like. These thermoplastic resins may be used alone or in combination of two or more. Among olefin-based resins, high-density polyethylene (HDPE), low-density polyethylene (LDPE), bio-polyethylene, etc. from the advantage that sufficient reinforcement effect can be obtained in the resin composition and the advantage of low cost. Polyethylene resin (PE), polypropylene resin (PP), vinyl chloride resin, styrene resin, (meth) acrylic resin, vinyl ether resin and the like are preferable.

Also, resins obtained by adding maleic anhydride, epoxy or the like to the above-mentioned thermoplastic resin or thermosetting resin as a compatibilizer and introducing a polar group, such as maleic anhydride modified polyethylene resin, maleic anhydride modified polypropylene resin, commercially available Various compatibilizers may be used in combination. These resins may be used alone or in combination of two or more. Moreover, when using as 2 or more types of mixed resin, you may use combining a maleic anhydride modified resin and other polyolefin resin.

  When using a mixed resin in which a maleic anhydride-modified resin and another polyolefin resin are combined, the content of the maleic anhydride-modified resin is about 1 to 40 mass% in the thermoplastic resin or thermosetting resin (A). Is preferable, and about 1 to 20% by mass is more preferable. More specifically, as a specific example in the case of using as mixed resin, maleic anhydride modified polypropylene resin and polyethylene resin or polypropylene resin, maleic anhydride modified polyethylene resin and polyethylene resin, or resin such as polypropylene can be mentioned.

  Also, in addition to the components contained in the above resin composition, for example, compatibilizer; surfactant; polysaccharides such as starches and alginic acid; natural proteins such as gelatin, glue, casein etc .; tannin, zeolite, ceramics, Inorganic compounds such as metal powders; colorants; plasticizers; perfumes; pigments; flow control agents; leveling agents; conductive agents; antistatic agents; ultraviolet absorbers; ultraviolet dispersants; It is also good.

  The content ratio of the optional additive may be suitably within the range where the effect of the present invention is not impaired, but for example, about 10% by mass or less in the resin composition is preferable, and about 5% by mass or less is more preferable .

(3-2) Blending Ratio of Resin Composition The content of the dispersing agent in the resin composition may be a content that achieves the physical properties required for the cellulose-containing resin composite composition.

  The reinforcing effect by cellulose can be obtained by setting the content of the dispersant in the resin composition to about 5 parts by mass with respect to 100 parts by mass of the resin. By setting the content of cellulose to 5 parts by mass or more, a higher dispersion effect can be obtained. The content of the dispersant in the composition is preferably about 1 to 20 parts by mass, more preferably about 2 to 10 parts by mass, and further preferably 5 to 10 parts by mass with respect to 100 parts by mass of the resin. Particular preference is given to the degree.

  The resin composition of the present invention contains a resin as a matrix. In a resin composition, when it contains a dispersing agent and is mixed with a cellulose, affinity of an interface with resin can be improved.

(4) Resin Composite Composition Containing Cellulose, Resin, and Dispersant The resin composite composition of the present invention comprises cellulose, a resin, and a dispersant, and the dispersant has resin affinity segment A and cellulose affinity. It has a segment B and has a block copolymer structure or a gradient copolymer structure.

  The resin composite composition of the present invention comprises cellulose and a resin. In the resin composite composition, the resin may form a lamella layer, and the lamella layer may be laminated in a direction different from the direction of the fiber length of the cellulose (FIGS. 7 to 9).

  In addition, it has a fibrous core of uniaxially oriented resin in the same direction as the fiber length direction of cellulose, and the lamella layer of the resin is different from the fiber length direction of cellulose between cellulose and the fibrous core. It has a structure formed by laminating in the direction. It is considered that the strength of the resin composition is improved by forming a lamella layer of the resin component in the resin composition.

In the above structure, cellulose and resin are combined to form a shish kebab structure (shish kebab structure). The shish kebab structure comes from the fact that it is similar to a skewered grilled turkey meat (sashimi is boiled and kebab is meat). In the shish kebab structure of the present invention, the shishi portion is a stretched fiber of cellulose, and the kebab portion is a lamellar layer of resin (lamellar crystal, folded structure). A resin composition (a molding material, a molded object) becomes high in tensile strength and an elastic modulus by forming a shish kebab structure of cellulose and resin.

(5) Method for Producing Resin Composite Composition Containing Cellulose, Resin, and Dispersant Hereinafter, a specific method for producing the resin composite composition of the present invention will be described (FIG. 10).

Manufacturing method 1
A method of producing a resin composite composition, comprising
(1) mixing cellulose and a dispersing agent to obtain a composition containing cellulose and a dispersing agent;
(2) mixing the resin and the composition obtained in step (1);
Including
A method of producing a resin composite composition, wherein the dispersant has a resin affinity segment A and a cellulose affinity segment B, and has a block copolymer structure or a gradient copolymer structure.

  By mixing the cellulose and the dispersing agent in advance in step (1), when mixing with the resin in step (2), aggregation of the cellulose is suppressed, and the dispersibility thereof is improved, whereby the resin composite composition is obtained Performance can be improved.

Manufacturing method 2
A method of producing a resin composite composition, comprising
(1) mixing cellulose and a dispersing agent to obtain a composition containing cellulose and a dispersing agent;
(2) mixing the resin, the dispersant, and the composition obtained in the step (1);
Including
A method of producing a resin composite composition, wherein the dispersant has a resin affinity segment A and a cellulose affinity segment B, and has a block copolymer structure or a gradient copolymer structure.

  By mixing the cellulose and the dispersing agent in advance in the step (1), when mixing with the resin in the step (2), aggregation of the cellulose can be suppressed and the dispersibility can be improved. In addition, depending on the type of cellulose and resin, the performance of the resin composite composition can be improved by adding and adjusting the amount of dispersant at the time of resin mixing.

Manufacturing method 3
A method of producing a resin composite composition, comprising
(1) mixing cellulose and a dispersing agent to obtain a composition containing cellulose and a dispersing agent,
(2) mixing the resin and the dispersing agent to obtain a resin composition containing the resin and the dispersing agent; and (3) obtaining the composition obtained in the step (1) and the step (2). Mixing with the cured resin composition,
Including
A method of producing a resin composite composition, wherein the dispersant has a resin affinity segment A and a cellulose affinity segment B, and has a block copolymer structure or a gradient copolymer structure.

By mixing a cellulose and a dispersing agent beforehand by process (1), when manufacturing a resin compound composition by process (3), aggregation of a cellulose can be suppressed and the dispersibility can be improved. A dispersant is mixed in advance with the resin used in step (3) to adjust the amount of the dispersant, which contributes to the improvement of the performance of the resin composite composition. Furthermore, when an additional amount of the dispersant is predetermined, the process can be simplified by mixing it in advance with the resin.

Manufacturing method 4
A method of producing a resin composite composition, comprising
(1) mixing cellulose and a dispersing agent to obtain a composition containing cellulose and a dispersing agent,
(2) mixing the resin and the dispersing agent to obtain a resin composition containing the resin and the dispersing agent; and (3) obtaining the composition obtained in the step (1) and the step (2). Mixing the cured resin composition with the resin,
Including
A method of producing a resin composite composition, wherein the dispersant has a resin affinity segment A and a cellulose affinity segment B, and has a block copolymer structure or a gradient copolymer structure.

  Depending on the type of resin, when it is effective to mix with the resin in a high dispersant amount in step (2), the resin is added in step (3) to adjust and optimize the composition of the resin composite composition to be produced By doing this, the performance can be improved.

Manufacturing method 5
A method of producing a resin composite composition, comprising
(1) mixing cellulose and a dispersing agent to obtain a composition containing cellulose and a dispersing agent,
(2) mixing the resin and the dispersing agent to obtain a resin composition containing the resin and the dispersing agent; and (3) obtaining the composition obtained in the step (1) and the step (2). Mixing the cured resin composition with a dispersant,
Including
A method of producing a resin composite composition, wherein the dispersant has a resin affinity segment A and a cellulose affinity segment B, and has a block copolymer structure or a gradient copolymer structure.

  Depending on the type of resin, if it is effective to mix with the resin in a low dispersant amount in step (2), a dispersant is added in step (3) to adjust the composition of the resin composite composition to be produced, and optimum Performance can be improved.

Manufacturing method 6
A method of producing a resin composite composition, comprising
(1) mixing cellulose and a dispersing agent to obtain a composition containing cellulose and a dispersing agent,
(2) mixing the resin and the dispersing agent to obtain a resin composition containing the resin and the dispersing agent; and (3) obtaining the composition obtained in the step (1) and the step (2). Mixing the resin composition, the resin, and the dispersant,
Including
A method of producing a resin composite composition, wherein the dispersant has a resin affinity segment A and a cellulose affinity segment B, and has a block copolymer structure or a gradient copolymer structure.

Depending on the type of cellulose and resin, the composition of the cellulose, dispersant and resin added in step (1) and step (2) is not the optimum composition for the characteristic expression of the resin composite composition produced in step (3) In this case, it is possible to improve the performance by adding an appropriate amount of resin and dispersant in the step (3) and adjusting and optimizing the composition of the resin composite composition to be produced.

Manufacturing method 7
A method of producing a resin composite composition, comprising
(1) a step of mixing a cellulose, a resin, and a dispersant to obtain a resin composite composition,
Including
A method of producing a resin composite composition, wherein the dispersant has a resin affinity segment A and a cellulose affinity segment B, and has a block copolymer structure or a gradient copolymer structure.

  Depending on the type of the cellulose and the resin, mixing the cellulose and the resin in the presence of the dispersant improves the compatibility of the two, thereby improving the dispersibility of the cellulose and hence the improvement of the characteristics of the resin composite composition. Ru.

Manufacturing method 8
A method of producing a resin composite composition, comprising
(1) mixing resin and dispersing agent to obtain a resin composition containing dispersing agent and resin; and (2) mixing cellulose and the resin composition obtained in step (1). ,
Including
A method of producing a resin composite composition, wherein the dispersant has a resin affinity segment A and a cellulose affinity segment B, and has a block copolymer structure or a gradient copolymer structure.

  Depending on the type of the cellulose and the resin, the compatibility of the cellulose and the resin is improved by using the modified resin to which the dispersing agent is added in advance, the dispersibility of the cellulose is improved, and hence the characteristics of the resin composite composition are improved. To be realized.

Manufacturing method 9
A method of producing a resin composite composition, comprising
(1) mixing resin and dispersing agent to obtain a resin composition containing the dispersing agent and the resin, and (2) cellulose, resin, and the resin composition obtained in the step (1) Mixing process,
Including
A method of producing a resin composite composition, wherein the dispersant has a resin affinity segment A and a cellulose affinity segment B, and has a block copolymer structure or a gradient copolymer structure.

  Depending on the type of the cellulose and the resin, the compatibility of the cellulose and the resin is improved by using the modified resin to which the dispersant is added in advance, the dispersibility of the cellulose is improved, and the resin is further added in step (2). By doing this, the performance of the composite resin composition can be improved with the minimum necessary amount of dispersant.

Manufacturing method 10
A method of producing a resin composite composition, comprising
(1) a step of mixing a resin and a dispersant to obtain a resin composition containing the dispersant and the resin,
(2) mixing the cellulose, the dispersant, and the resin composition obtained in the step (1);
A method of producing a resin composite composition, wherein the dispersant has a resin affinity segment A and a cellulose affinity segment B, and has a block copolymer structure or a gradient copolymer structure.

  Depending on the type of the cellulose and the resin, the compatibility of the cellulose and the resin is improved by using the modified resin to which the dispersing agent is added in advance, the dispersibility of the cellulose is improved, and the dispersing agent is further added in step (2). By addition, interface reinforcement etc. are realized and the performance improvement of a composite resin composition is achieved.

Manufacturing method 11
A method of producing a resin composite composition, comprising
(1) a step of mixing a resin and a dispersant to obtain a resin composition containing the dispersant and the resin,
(2) mixing the cellulose, the resin, the dispersant, and the resin composition obtained in the step (1);
A method of producing a resin composite composition, wherein the dispersant has a resin affinity segment A and a cellulose affinity segment B, and has a block copolymer structure or a gradient copolymer structure.

  Depending on the type of cellulose and resin, the compatibility of cellulose and resin can be improved and the dispersibility of cellulose can be improved by using a modified resin to which a dispersant has been added in advance. In addition, according to the type of cellulose, the amount of the dispersant and the resin can be easily optimized in the step (2) to improve the performance of the composite resin composition.

Manufacturing method 12
A method for producing a resin composite composition, comprising the step of further mixing a resin with the resin composite composition obtained by the production method according to any one of the production methods 1 to 11, A method of producing a resin composite composition, wherein the agent has a resin affinity segment A and a cellulose affinity segment B and has a block copolymer structure or a gradient copolymer structure.

  The physical properties of the composite composition can be easily adjusted in a wide range by diluting the resin composite composition prepared in advance with the same or different resin. Moreover, in the resin composite composition manufactured beforehand, it is expected that the dispersibility of cellulose etc. will be improved by setting the fraction of cellulose high, and when adjusting to the cellulose concentration of the final resin composite composition Is also valid.

  At each process, each component of the above-mentioned cellulose, a dispersing agent, resin etc. can be used. The compounding amount of the dispersant to the cellulose, the compounding amount of the cellulose to the resin component, etc., the compounding amounts of the cellulose, the dispersant, the resin and the like may be set to be the above-mentioned content.

  The resin composite composition (composite material) can be prepared by mixing a cellulose and a resin using a dispersant. The cellulose affinity segment B of the dispersant and the functional group of cellulose may be reacted by chemical bonding or the like. All of the functional groups of the cellulose may be reacted with the cellulose affinity segment B of the dispersant, and a part may be reacted with the cellulose affinity segment B of the dispersant.

  As a method of mixing the cellulose and the resin component (and optional additives), a method of kneading with a kneader such as a bench roll, a Banbury mixer, a kneader, a planetary mixer, a method of mixing with a stirring blade, a revolution / rotation method The method of mixing with a stirrer etc. are mentioned.

The mixing temperature is not particularly limited. The cellulose and the resin component may be mixed without heating at room temperature or may be heated and mixed. When heating, about 40 degreeC or more is preferable, about 50 degreeC or more is more preferable, and, as for mixing temperature, about 60 degreeC or more is still more preferable. By setting the mixing temperature to about 40 ° C. or more, the cellulose and the resin component can be uniformly mixed, and the dispersant and the cellulose can be reacted.

  The resin composite composition (composite material) of the present invention is prepared by mixing a cellulose and a resin using a dispersant, so that the cellulose and the resin in the resin composition are easily mixed. In conventional resin compositions, cellulose having high hydrophilicity and plastic resin having high hydrophobicity (PP, PE, etc.) were difficult to mix. In the resin composition of the present invention, cellulose is well dispersed in a resin (dispersion medium). The strength and elastic modulus of molding materials and molded articles produced using the resin composition are high.

(6) Resin Molding Material and Resin Molded Article The resin composition (molding material, molded article) produced by the above-mentioned production method has good tensile strength and elastic modulus due to the good dispersion of nanocellulose in the resin. Get higher.

  Furthermore, the cellulose and the resin can form a shish kebab structure. Cellulose becomes a shredded portion of the stretched fiber, and resin becomes a kebab portion of a lamellar layer (lamellar crystal, folded structure). As a result, in the resin composition of the present invention, tensile strength and elastic modulus are synergistically improved.

  The resin molding material of the present invention comprises the resin composite composition.

  The resin molded body of the present invention is formed by molding the resin molding material.

  By using the composition of the present invention, a cellulose and a resin can be complexed to produce a molding material. A molded article (molded article) can be produced from the molding material of the present invention. Using the composition of the present invention, the tensile strength and elastic modulus of a molded article containing cellulose and a resin can be obtained by combining the cellulose and the resin without using a molded article containing only the resin or the composition of the present invention It shows high tensile strength and elastic modulus as compared to the obtained molded product.

  In the present invention, a resin molding material can be prepared using the composition, the resin composition and the resin composite composition (FIG. 11).

  The composition, the resin composition and the resin composite composition can be molded into a desired shape and used as a molding material. Examples of the shape of the molding material include sheets, pellets, powders and the like. The molding material having these shapes can be obtained, for example, using compression molding, injection molding, extrusion molding, hollow molding, foam molding, and the like.

  In the present invention, a molded body can be molded using the above-mentioned molding material. The molding conditions may be applied by appropriately adjusting the resin molding conditions as necessary. The molded article of the present invention can be used in fields requiring higher mechanical strength (such as tensile strength) in addition to the field of fiber reinforced plastics in which nanocellulose-containing resin molded articles have been used. For example, interior materials, exterior materials, structural materials, etc. of transportation equipment such as cars, trains, ships, airplanes, etc .; Housings such as personal computers, televisions, telephones, electrical appliances such as watches, structural materials, internal parts, etc .; Housings such as mobile communication devices, structural materials, internal parts, etc. Portable music reproducing devices, video reproducing devices, printing devices, copying devices, housings such as sporting goods, structural materials, internal parts, etc .; Building materials; Office equipment such as stationery Etc. can be effectively used as a container, container, etc.

<Example>
Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the present invention is not limited thereto.

Example
1. Dispersant (block copolymer)
(1) Block copolymer P001
A monomer (DCPOEMA) to be a resin affinity segment (A chain) was dissolved in an amphiphilic solvent (for example, propylene glycol, monopropyl ether) and subjected to living radical polymerization in the presence of a catalyst. After a predetermined time, a block copolymer was synthesized by adding a monomer (HEMA) to be a cellulose fiber affinity segment (B chain). The prepared block copolymer was dropped into water-containing methanol and precipitated as a solid. The catalyst and residual monomers were removed.

2. Preparation of Cellulose (Nanocellulose (CNF)) Softwood bleached kraft pulp (NBKP) (refiner-treated, made by Oji Paper Co., Ltd., solid content 25%) 600 g, water 19.94 kg was added to prepare a water suspension (Pulp slurry concentration: 0.75% by weight aqueous suspension). The obtained slurry was mechanically fibrillated using a bead mill (NVM-2, manufactured by Imex Co., Ltd.) (zirconia bead diameter 1 mm, bead loading 70%, rotation speed 2000 rpm, number of treatments twice). After defibration treatment, it was dewatered with a filter press.

3. Manufacture of cellulose fiber-resin molding using dispersing agent (block copolymer)
(1) Method of preparing CNF / P001 / NMP dispersion (FIG. 12)
After adding NMP (N-methyl pyrrolidone) to hydrous CNF so as to obtain an optimal water / NMP ratio (in the case of P001, 1/1 ratio), block copolymer (dispersant) emulsion (water / water) The NMP ratio depends on the dispersant: in the case of P001, a ratio of 1/1) was added (pre-added) and mixed. After a predetermined time, CNF / P001 / NMP and CNF / P are removed by distilling off water under heating (80 ° C.) and reduced pressure conditions, or removing water and NMP by filtration and pressing.
001 / NMP / water was prepared.

(2) Preparation method of PE / CNF / P001 resin composition (FIG. 13)
The CNF / P001 / NMP obtained in the above (1) was dispersed in a protic organic solvent (ethanol (EtOH)) and filtered. The nonadsorbed dispersant was quantified by gel permeation chromatography or the like. The polyethylene (PE) resin (HE 3040 and J320) was added and mixed by redispersing in a protic organic solvent. After removing the solvent by filtration, a THF solution of block copolymer (dispersant) P001 was added (post addition). After mixing, the organic solvent was removed by drying under reduced pressure. A resin composition of PE / CNF / P001 was obtained.

Mixing conditions and kneading apparatus: "TWX-15" manufactured by Technobel
· Kneading conditions: temperature = 140 ° C
Discharge = 600 g / H
Screw speed = 200 rpm

(3) Preparation method of PE / CNF / P001 molded body (FIG. 14)
After kneading the PE / CNF / P001 resin composition obtained in the above (2) with a twin-screw extruder (140 ° C. for PE, 180 ° C. for PP), injection molding (160 ° C. for PE, PP) A molded body was produced at 190 ° C.).

Injection molding conditions · Injection molding machine: "NP7 type" manufactured by Nissei Resin Co., Ltd.
Molding conditions: Molding temperature = 160 ° C. (for PE), 190 ° C. (for PP)
Mold temperature = 40 ° C
Injection rate = 50 cm ³ / sec or · Simple injection molding machine: "IMC-18D1" manufactured by Imoto Seisakusho
· Molding conditions: molding temperature = 165 ° C (in the case of PE)

  The elastic modulus and the tensile strength of the obtained test pieces were measured (load cell 5 kN) using an electro-mechanical universal tester (manufactured by Instron) at a test speed of 1.5 mm / min. At that time, the distance between supporting points was 4.5 cm.

  The evaluation result of the tensile strain of the cellulose fiber (CNF) -resin (PE) molded object using the block copolymer (P001) of this invention is shown in FIG.

  Polarized light microscope image of a cellulose fiber-resin molded product using the block copolymer (P001) of the present invention is shown in FIG. 16, and an analysis image by an X-ray CT scanner is shown in FIG. It is a block copolymer (polymer dispersant) coated CNF-PE molded body. The block copolymer (polymer dispersant) -coated CNF-PE molded product had low orientation of the molded product and reduced aggregation of CNF.

  The evaluation result of the tensile strain of the cellulose fiber (CNF) -resin (PP) molded object using the block copolymer (P001) of this invention is shown in FIG. Even in the PP resin, the block copolymer improved the dispersibility of the cellulose fiber (CNF). It has been found that the block copolymer of the present invention acts as a dispersant for cellulose fiber (CNF) PP resin.

  Trimix drying in the manufacturing process of a cellulose fiber (CNF) -resin (PE) molded product (PE / CNF / P001 molded product) using the block copolymer (P001) of the present invention can be applied. The evaluation results of cellulose fiber (CNF) -resin (PE) molded product (PE / CNF / P001 molded product) manufactured using Trimix drying are shown in Table 4 and FIG. An analysis image by the line CT scanner is shown in FIG.

  The molded bodies of CR-1 and CR-2 in Table 4 use a trimix dryer (dried under reduced pressure with stirring) in the manufacturing process. The molded body of HDPE (high density polyethylene) contains no dispersant and CNF. Therefore, regardless of drying, injection molded articles of resin were evaluated.

  It was found that CNF has good mechanical properties despite aggregation.

  CR-1 is only pre-addition. The results for CR-2 can be compared to FIG.

The evaluation result of manufacture of the cellulose fiber (pulp raw material) -resin (PE) molded object using the block copolymer (P001) of this invention is shown in FIG. It has been found that the block copolymer of the present invention acts as a dispersant for pulp materials such as PE resin and PP resin. By adding the block copolymer of the present invention to a mixture of pulp raw material and resin (PE, PP, etc.), it is expected that the pulp raw material is disintegrated to the nano level in the kneading step. After the block copolymer of the present invention is added to the pulp material, the pulp material can be nano-fibrillated.

  An analysis image of a cellulose fiber (CNF) -resin (PE) molded product using the block copolymer (P001) of the present invention by an X-ray CT scanner is shown in FIG. It was found that CNF has good mechanical properties despite aggregation. By using the block copolymer (dispersant) of the present invention, aggregation of cellulose fibers (CNF) in the resin composition was able to be suppressed.

  The observation result of the polarization microscope image of the sample which manufactured the cellulose fiber (CNF) -resin (PE) molding using the block copolymer (P001) of this invention by trimix drying is shown in FIG. Polarized light microscope images show the orientation of the resin in the resin composition. It was found that the resin component is highly oriented by using the block copolymer (dispersant) of the present invention (CR-2).

  CR-2 was found to be very strong in orientation. Moreover, the TEM observation result in (a) (b) (c) is shown to FIGS. CR-2 had a remarkable shish kebab structure. The TEM images (FIGS. 7-9) show the shish kebab structure inside the cellulose fiber-resin molded body. By using the block copolymer (dispersant) of the present invention (CR-2), the molded product had a highly developed shish kebab structure of PE. It is believed that this shish kebab structure contributes to the improvement of the mechanical properties. FIGS. 7-9 is a TEM observation image of the resin molding (CNF-PE using a block copolymer) of an Example. In the resin molded product of the example, a lamellar layer of PE was formed, and it was confirmed that the lamellar layer was regularly laminated in a direction different from the direction of the fiber length of CNF. That is, in the resin molded product of the example, it was confirmed that the crystal lamella of PE was vertically grown from the CNF surface. Further, in the resin molded product of the example, a fibrous core of PE uniaxially oriented is formed in the same direction as the fiber length direction of CNF, and the lamellar layer of PE is CNF between CNF and the fibrous core. It was also confirmed that the layers were laminated in different directions with respect to the fiber length direction. In the above structure, CNF and PE were combined to form a shish kebab structure (shish kebab structure). In the shish kebab structure, the shish part is a CNF stretched fiber, and the kebab part is a lamellar layer of PE (lamellar crystal, folded structure). The resin composition (molding material, molded body) has a tensile strength and elastic modulus increased by forming a shish kebab structure of CNF and PE. It is predicted that the formation of the lamella layer greatly contributes to the improvement of the resin reinforcement.

  The characteristics of the block copolymer P001 (dispersant) coated CNF are shown in FIGS.

  A method of preparing the block copolymer P001 (dispersant) coated CNF is shown in FIG.

  FT-IR (FIG. 25A) shows that the block copolymer (dispersant) is not washed away from the CNF surface. FIG. 25B shows the results of the number of washings and the IR peak ratio. Since the IR peak ratio is constant even after washing, it indicates that the adsorbed dispersant hardly flows out with the solvent.

  Contact angle measurements (FIG. 26) show that the block copolymer (dispersant) coated CNF is sufficiently hydrophobic.

  The organic solvent dispersible photograph (FIG. 27) shows that the block copolymer (dispersant) coated CNF can be dispersed in various solvents.

  The dispersant (block copolymer) manufactured this time is shown in Tables 5 and 6.

(4) When the experimental pulp was manufactured using the raw materials, the following three were examined, and the best mechanical properties were found in (c).

(A) Melt-kneaded nano-fibrillated sample CR-3
An ethanol suspension of ethanol-substituted pulp and dispersant P001 is mixed, and after trimix drying, the mixture is melt-kneaded (nano-fibrillation) with a resin pellet (J320) at a fiber ratio of 20%. Then dilute with resin and mold.

  The detail of nano disintegration (preparation of CR-3) by melt-kneading is shown in FIG.

(B) Nano-fibrillated sample CR-4 by low temperature kneading in water
After nano-fibrillation by low-temperature kneading with pulp, PE, dispersant, water (fiber ratio 9%), it is mixed with resin and melt-kneaded with a fiber ratio of 10%. Then molding.

  The detail of nano disintegration (preparation of CR-4) by low temperature kneading in water is shown in FIG.

(C) Nano-fibrillated sample CR-5 by low-temperature kneading in NMP
The pulp and dispersant emulsion are trimix dried to prepare a dewatered NMP suspension, and low-temperature kneading at a fiber ratio of 20%. After removing NMP with ethanol, it was mixed with resin and trimix dried to obtain a 30% masterbatch. After that, it is diluted with resin and melt-kneaded at a fiber ratio of 10% and molded.

  The detail of nano disintegration (preparation of CR-5) by low-temperature kneading in NMP is shown in FIG.

  Production from pulp achieved 3.6 times the resin modulus and 2.3 times the strength.

  The results are shown in Table 7 and FIG.

  The observation of pulp fibers by hot pressing of a dumbbell test piece is shown in FIGS.

  In CR-3, it was assumed that pulp was not observed so much and CNF was formed well, but it was inferred that fiberization was made.

  In CR-4, a large amount of pulp remained, and nano defibration was insufficient.

  CR-5 showed good formation of CNF.

  Production from pulp achieved 3.6 times the resin modulus and 2.3 times the strength (Figure 35 and Table 8).

By using the dispersant manufactured this time, it was possible to realize high resin strength by CNF. The effect of the polymeric dispersant was also observed with polypropylene (FIG. 36 and Table 9).

Dispersant 1: G002
Dispersant 2: N 001
Dispersant 3: O001
Dispersant 4: Q001
Dispersant 5: P001

EFFECT OF THE INVENTION Typical examples of the dispersant of the present invention are A having a resin affinity segment A (hydrophobic part, cellulose fiber dispersed segment) and a cellulose affinity segment B (hydrophilic part, cellulose fiber immobilized segment) Type B diblock copolymers or gradient copolymers. The dispersant can modify the surface of the cellulose while retaining the characteristics of the cellulose fiber material. When the dispersant is used, the dispersibility of the cellulose fiber in the resin can be improved. The dispersant can be used as a dispersant for cellulose fiber resin. A highly hydrophilic cellulose is surface-modified with the resin affinity segment A through the cellulose affinity segment B by the composition containing the dispersant of the present invention. And cellulose fiber can be uniformly dispersed in thermoplastics with high hydrophobicity, such as polyethylene (PE) and polypropylene (PP) especially. A resin composite composition containing cellulose prepared using a dispersant has high compatibility between cellulose and resin and high adhesive strength at the interface. A composition comprising cellulose coated with a dispersant and various resins is excellent in strength and elastic modulus. As a result, it is possible to sufficiently obtain the reinforcing effect by blending the cellulose with the resin, and to improve the tensile strength. It is possible to obtain a cellulose resin composite material and a molded body, which are excellent in strength, elastic modulus, heat resistance, and extremely low in linear thermal expansion coefficient as in an aluminum alloy. The cellulose surface-modified by the dispersant can impart high reinforcing effect (tensile strength) and elastic modulus to PP, which is difficult to be reinforced particularly by conventional chemically-modified cellulose.

  The dispersants included in the composition of the present invention are preferably designed and synthesized by living radical polymerization (LRP). By using a dispersing agent, cellulose can be mixed and dispersed in an organic solvent or resin having low affinity to cellulose under mild conditions of normal temperature and normal pressure. Since the surface of cellulose has hydroxyl groups, it is effectively coated with the cellulose affinity segment B of A-B type diblock copolymer or gradient copolymer. In addition, the surface of the cellulose is hydrophobized by the resin compatible segment A of the AB type diblock copolymer or the gradient copolymer. And, the hydrophobized cellulose is uniformly dispersed even in thermoplastic resins such as PE and PP, which have very high hydrophobicity. As a result, the strength of the interface between the cellulose and the resin is improved by the resin affinity segment A of the AB type diblock copolymer or gradient copolymer. And aggregation of the cellulose in resin can be suppressed and the composite material and molded object excellent in intensity | strength and an elastic modulus can be obtained.

The cellulose affinity segment B of the dispersant is preferably a segment containing hydroxyethyl methacrylate (HEMA). The resin compatible segment A of the dispersant is preferably a segment containing dicyclopentenyloxyethyl methacrylate (DCPOEMA).
The dispersant is preferably added as an emulsion to the water / NMP based slurry containing cellulose. When the cellulose fiber and the resin are mixed, coexistence of the dispersant emulsion can suppress aggregation of the cellulose in the resin. By defibrillating the cellulose dispersed in the resin in the coexistence of the dispersant, the strength of the resin composite composition (molding material, molded body) can be increased.

  In the resin composite composition of the present invention, the resin can form a lamella layer in the resin composition. And the lamellar layer is laminated in a direction different from the direction of the fiber length of the nanocellulose fiber. Therefore, the molded object shape | molded from the said resin composition has an effect that it is excellent in mechanical strength.

  By using the composition containing the dispersant of the present invention, superior properties such as high strength, high elastic modulus, low linear thermal expansion, etc. compared to conventional cellulose hydrophobization modifiers and cellulose dispersants etc. A composite material of a cellulose fiber resin composition having physical properties can be produced. Also, the productivity of the composite material is good.

  The composite material of the present invention is excellent in tensile strength (elastic modulus) and heat resistance (TGA, HDT), and further simplification of manufacturing process, cost reduction, and scale-up are expected for practical use. . The composite material of the present invention is useful as a member for automobiles. The composite material of the present invention is also applicable to structural materials such as housings of electric appliances such as televisions, phones and watches, housings of mobile communication devices such as mobile phones, housings of printing devices, copying machines, sports goods etc. It is useful. In addition, industries such as paper manufacturers supplying cellulose fibers, chemical companies supplying composite materials, automobiles using composite materials, home appliances, information communication, and manufacturers of sports goods can be activated.

Claims (3)

A resin composite composition comprising a dispersant, cellulose and a resin,
The dispersant is a dispersant having a resin affinity segment A and a cellulose affinity segment B, and has a block copolymer structure or a gradient copolymer structure to improve the dispersibility of cellulose in a resin And
4-t-butylcyclohexyl methacrylate (tBCHMA), isobonyl methacrylate (IBOMA), dicyclopentanyl methacrylate (DCPMA), and dicyclopentenyl oxyethyl methacrylate as monomer components that the resin compatible segment A comprises And one or more selected from the group consisting of (DCPOEMA),
As a monomer component which the cellulose affinity segment B comprises, hydroxyethyl methacrylate (HEMA), methacrylic acid (MAA), methacrylamide (MAm), benzylated dimethylaminoethyl methacrylate (QDEMAEMA), 3-methacryloxy And one or more selected from the group consisting of propyltriethoxysilane (MPE), 2-isocyanatoethyl methacrylate (MOI) and glycidyl methacrylate (GMA),
The cellulose is a nano-cellulose, wood fat complex composition. The resin composite composition according to claim 1 , wherein the resin is a thermoplastic resin. A method for producing a resin composite composition comprising a dispersant, cellulose and a resin,
(1) mixing cellulose and an N-methylpyrrolidone (NMP) emulsion of a dispersant to obtain a composition containing cellulose and a dispersant;
(2) mixing the resin and the composition obtained in step (1);
(3) including a fibrillation step of fibrillating cellulose in the presence of N-methylpyrrolidone (NMP) emulsion as a dispersant,
The dispersant is a dispersant having a resin affinity segment A and a cellulose affinity segment B, and has a block copolymer structure or a gradient copolymer structure to improve the dispersibility of cellulose in a resin And
4-t-butylcyclohexyl methacrylate (tBCHMA), isobonyl methacrylate (IBOMA), dicyclopentanyl methacrylate (DCPMA), and dicyclopentenyl oxyethyl methacrylate as monomer components that the resin compatible segment A comprises see contains one or more selected from the group consisting of (DCPOEMA),
As a monomer component which the cellulose affinity segment B comprises, hydroxyethyl methacrylate (HEMA), methacrylic acid (MAA), methacrylamide (MAm), benzylated dimethylaminoethyl methacrylate (QDEMAEMA), 3-methacryloxy A production method comprising one or more selected from the group consisting of propyltriethoxysilane (MPE), 2-isocyanatoethyl methacrylate (MOI) and glycidyl methacrylate (GMA) .

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