JP6249488B2 - Modified fibrillated cellulose, fibrillated cellulose-containing resin product, and production method thereof - Google Patents

Description

  The present invention relates to modified fibrillated cellulose, fibrillated cellulose-containing resin products, and methods for producing them.

  In recent years, research on cellulose nanofibers obtained by defibrating plant fibers such as pulp has been promoted. Cellulose nanofibers are composed of polysaccharide cellulose having many hydroxyl groups on the surface, which are highly polar functional groups, and exhibit extremely high hydrophilicity. When moisture coexisting with the cellulose nanofibers is removed, the cellulose nanofibers aggregate to form a strong hydrogen bond with each other. It is difficult to separate cellulose nanofiber agglomerates linked by hydrogen bonding into individual fibers. With this, when the cellulose nanofiber is mixed with a resin or the like, the reinforcing effect derived from the high aspect ratio of the cellulose nanofiber cannot be exhibited.

  Patent Document 1 describes esterifying or etherifying hydroxyl groups on the surface of cellulose nanofibers in order to prevent strong adhesion due to hydrogen bonding between cellulose nanofibers. In Patent Document 1, 50 ml of N, N-dimethylacetamide (organic solvent) and 60 g of 1-butyl-3-methylimidazolium chloride (organic ionic liquid) are added to 2 g of filter paper, stirred, filtered, and obtained cellulose Example 2 shows acetylation of nanofibers with acetic anhydride, an esterifying agent. Patent Document 1 also shows Example 4 in which cellulose nanofibers are etherified with hexamethyldisilazane, which is a silyl etherifying agent.

JP 2011-184816 A

  However, in order to prevent strong adhesion between cellulose nanofibers, a treatment using an organic solution containing an organic solvent, an organic ionic liquid, or the like is required, and a waste liquid treatment of the organic solution is required as a post-treatment.

  In view of the above, the present invention has an object of providing a novel modified fibrillated cellulose and a resin product containing fibrillated cellulose.

The method for producing a modified fibrillated cellulose of the present invention uses the mill using a treatment medium, and the treatment medium in which the treatment medium is placed in a dispersion system containing at least water, cellulose, and a water-insoluble hydrophilic resin. , and the by fibrillating the cellulose by performing wet grinding to the dispersion to hit the water-insoluble hydrophilic resin, having aspects of producing a modified fibrillated cellulose.
The resulting modified fibrillated cellulose is stronger in the strength of products using fibrillated cellulose than when using a water-soluble resin or a hydrophobic resin as a general resin instead of a water-insoluble hydrophilic resin. It has been found that there is a significant effect of improvement. Further, when modifying the fibrillated cellulose, an organic solution containing an organic solvent or an organic ionic liquid is not required.

Here, the fibrillation described in the claims means that the fiber is torn. Fibrilized cellulose includes cellulose nanofibers and is not limited to cellulose nanofibers.
The non-water solubility described in the claims means that the measured value of the solubility of the resin is substantially zero. Specifically, under 20 ° C. and 1 atm, 100 mL of water is added to 200 mL of a beaker specified in JIS R3503-1994 (glass apparatus for chemical analysis), 0.1 g of a resin sample is added, and 10 minutes at 100 rpm or more. It is assumed that the solubility is 0 when a resin sample that has not been dissolved when stirring with a stirrer is seen. When water-soluble impurities are contained in the general-purpose resin, 1 g of the general-purpose resin is added to 200 mL of a beaker containing 100 mL of water, and a resin residue exhibiting the effect of the present invention when stirred with a stirrer at 100 rpm or more for 10 minutes or more. 1 g may be used as the resin sample.

  When a resin having a softening temperature below the boiling point of water is used for the water-insoluble hydrophilic resin, the water-insoluble hydrophilic resin is softened or melted when the resulting modified fibrillated cellulose is heated and dried, thereby fibrillating cellulose. Enters the water-insoluble hydrophilic resin and the dispersibility of the fibrillated cellulose is improved. Therefore, the manufacturing method of the modified fibrillated cellulose which can further improve the intensity | strength of a product can be provided. The softening temperature is the Vicat softening temperature specified in JIS K7206: 1999 (plastic-thermoplastic-Vicat softening temperature (VST) test method).

In the method for producing the modified fibrillated cellulose of the above-described embodiment, the treatment medium placed in the dispersion is hit against cellulose and a water-insoluble hydrophilic resin, and wet dispersion is performed on the dispersion. Thereby, since a shearing force is applied to the dispersion system, the fibrillated cellulose easily enters the water-insoluble hydrophilic resin, and the dispersibility of the fibrillated cellulose is improved. Therefore, the strength of the fibrillated cellulose-containing product can be further improved.

The method for producing a fibrillated cellulose-containing resin product of the present invention uses a mill using a treatment medium, and includes at least water, cellulose, and a water-insoluble hydrophilic resin having a softening temperature equal to or lower than the boiling point of water. The treated medium placed in a dispersion system is struck against the cellulose and the water-insoluble hydrophilic resin to perform wet pulverization on the dispersion system to obtain modified fibrillated cellulose, and the modified fibrillation It has a mode in which a fibrillated cellulose-containing resin product is produced by heating or dispersing the water-insoluble hydrophilic resin by heating a dispersion containing cellulose and drying the obtained dispersion. .
When the treatment medium is applied to the cellulose and the water-insoluble hydrophilic resin and wet pulverization is performed on the dispersion, the fibrillated cellulose and the water-insoluble hydrophilic resin are combined to form a dispersion. Aggregation of fibrillated cellulose is suppressed when drying. Accordingly, it is possible to improve the strength of the fibrillated cellulose-containing resin product.

Furthermore, in the method for producing a fibrillated cellulose-containing resin product of the present invention, a mill using a treatment medium is used, and the product is placed in a dispersion system including at least water, cellulose, and a thermoplastic water-insoluble hydrophilic resin. The treatment medium is applied to the cellulose and the water-insoluble hydrophilic resin to perform wet pulverization on the dispersion to obtain modified fibrillated cellulose, and the dispersion containing the modified fibrillated cellulose The fibrillated cellulose-containing resin product is produced by removing water from the dispersion and heating the dispersion to form the dispersion.
Furthermore, the method for producing a fibrillated cellulose-containing resin product of the present invention uses a mill using a treatment medium and puts it in a dispersion system containing at least water, cellulose, and a thermosetting water-insoluble hydrophilic resin. The treated medium is struck against the cellulose and the water-insoluble hydrophilic resin, and the dispersion is wet pulverized to obtain modified fibrillated cellulose, and the dispersion containing the modified fibrillated cellulose is obtained. It has the aspect which manufactures the fibrillated cellulose containing resin product which removed the water | moisture content from this dispersion system by heating a system, and thermosets the said water-insoluble hydrophilic resin.
Here, the removal of water includes drying, filtration, centrifugation, and the like.

Furthermore, the method for producing a fibrillated cellulose-containing resin product of the present invention is a method for producing a fibrillated cellulose-containing resin product by mixing at least a modified fibrillated cellulose obtained by the above-described method for producing a modified fibrillated cellulose and a resin. Have an aspect.
When the treatment medium is struck against the cellulose and the water-insoluble hydrophilic resin and the dispersion is mixed, the fibrillated cellulose and the water-insoluble hydrophilic resin are combined to form a fibrillated cellulose-containing resin product. Thus, aggregation of fibrillated cellulose is suppressed. Accordingly, it is possible to improve the strength of the fibrillated cellulose-containing resin product.

Furthermore, the fibrillated cellulose, at least, water-insoluble hydrophilic resin which is an acid-modified polyolefin modified by an organic acid is bonded reforming fibrillated cellulose, to improve the strength of the product when used in product Is possible.
Here, the bond means a broad bond that binds the fibrillated cellulose and the water-insoluble hydrophilic resin by interaction, and includes not only a chemical bond but also physical adsorption. The blending ratio of fibrillated cellulose and water-insoluble hydrophilic resin may be greater for fibrillated cellulose or greater for water-insoluble hydrophilic resin.
Furthermore, modified fibrillated cellulose in which fibrillated cellulose is incorporated into a water-insoluble hydrophilic resin, which is an acid-modified polyolefin modified with an organic acid, can improve the strength of the product when used in the product. .

Furthermore, the fibrillated cellulose-containing resin product formed from the above-described modified fibrillated cellulose can improve the strength.

Furthermore, the strength of the fibrillated cellulose-containing resin product in which the above-described modified fibrillated cellulose and the resin are mixed can be improved.

  Furthermore, the present invention provides a composite in which the above-described modified fibrillated cellulose is mixed, a concrete to which the above-described modified fibrillated cellulose is added, a ceramic green body to which the above-described modified fibrillated cellulose is added, and production thereof. It also has an aspect such as a method.

According to the invention which concerns on Claim 1 , the manufacturing method of the novel modified | denatured fibrillated cellulose which can improve the intensity | strength of a fibrillated cellulose containing product by simple process can be provided.
In the invention which concerns on Claim 2 , the manufacturing method of the modified fibrillated cellulose which can further improve the intensity | strength of a fibrillated cellulose containing product can be provided.
The invention according to claims 3 and 6 can provide a production method capable of improving the strength of the fibrillated cellulose-containing resin product by a simple treatment.
In the invention which concerns on Claim 7, Claim 8 , the novel modified fibrillated cellulose which can improve the intensity | strength of a fibrillated cellulose containing product can be provided.
In the inventions according to claim 9 and claim 10 , it is possible to provide a novel fibrillated cellulose-containing resin product with improved strength.

The flowchart which shows typically an example of the manufacturing method of the fibrillated cellulose containing resin product containing the manufacturing method of a modified fibrillated cellulose. The flowchart which shows another example of a manufacturing method typically. The flowchart which shows another example of a manufacturing method typically. The flowchart which shows another example of a manufacturing method typically. The figure which illustrates typically the aggregation inhibitory effect of the modification | reformation fibrillated cellulose using water-insoluble hydrophilic resin. The figure which shows typically the mode of the fibrillated cellulose of the comparative example using water-soluble resin. The figure which shows typically the mode of the fibrillated cellulose of the comparative example using hydrophobic resin. 2 is a photograph of a sheet obtained from the injection-molded body of Example 1. 2 is a photograph of a sheet obtained from the injection-molded body of Comparative Example 1.

  Embodiments of the present invention will be described below. Of course, the following embodiments are merely examples of the present invention, and all the features shown in the embodiments are not necessarily essential to the means for solving the invention.

(1) Description of a method for producing a product containing modified fibrillated cellulose:
1 to 4 schematically illustrate an example of a method for producing a fibrillated cellulose-containing resin product including a method for producing a modified fibrillated cellulose. The modified fibrillated cellulose is produced by mixing a dispersion system 10 containing at least water 11, cellulose (12, 22), and a water-insoluble hydrophilic resin 13, and modifying the fibrillated cellulose 30, 32. Is to be manufactured. Hereinafter, the example which manufactures the fibrillated cellulose containing resin products 40 and 50 as a product containing the modified fibrillated cellulose 30 and 32 is demonstrated.

(1-1) Manufacturing method example 1:
In Production Method Example 1 shown in FIG. 1, wet dispersion is performed on a dispersion system 10 including at least water 11, a cellulose raw material 12, and a water-insoluble hydrophilic resin 13, and the fibrillated cellulose 22 is at least water-insoluble and hydrophilic. The modified fibrillated cellulose 30, 32 to which the resin 13 is bonded is produced.

  In the charging step S1, the water 11, the cellulose raw material 12, the water-insoluble hydrophilic resin 13 and, if necessary, the additive 16 are weighed and put into the wet pulverizer MI1.

  As the cellulose raw material 12, woody materials, herbaceous materials, seaweed materials, bacterial materials, animal materials, and the like can be used. Woody materials include coniferous materials and hardwood materials, and include wood chips, wood powder, crushed wood, crushed wood, wood pulp, combinations thereof, and the like. Bamboo etc. may be contained in the woody material. Herbaceous materials include hemp, bagasse, rice straw, rice straw, straw, cotton, herbaceous pulp, combinations thereof, and the like. As the cellulose raw material, wood chips generated at furniture factories and construction sites, pulverized waste materials, pulverized waste materials such as furniture and building materials, etc. can be used, and may be pulped. It does not have to be converted. The cellulose raw material is not limited to a non-fibrillated raw material, but may be fibrillated cellulose or cellulose nanofiber. Fibrilization means that the cellulose fibers are torn and includes nano-order microfibrils, but is not limited to microfibrillation.

The size of the solid cellulose raw material in the case of wet pulverization may be a size that allows wet pulverization. It is preferable that the cellulose raw material is powdery because it easily fibrillates. The powder form includes granular form, fibrous form, and the like. The size of the powdery cellulose raw material is preferably 4 mm pass, more preferably 2 mm pass, further preferably 1 mm pass, and particularly preferably 500 μm pass. Here, the Xmm path means a size passing through a sieve having an opening of Xmm defined in JIS Z8801-1: 2006 (test sieve—Part 1: metal mesh sieve). Means a size passing through a sieve having an opening of X μm. In addition, the specific surface area of the fibrillated cellulose after wet pulverization is about 30 to 200 m ² / g.

  When the resin is not contained in the dispersion system 10, fibrillated cellulose aggregates when moisture is removed from the dispersion system after mixing. Since it is difficult to separate the fibrillated cellulose aggregate into individual fibers, when the fibrillated cellulose is mixed with a resin or the like, the reinforcing effect derived from the high aspect ratio of the fibrillated cellulose is not exhibited, The interface strength between the hydrophobic resin and the hydrophilic fibrillated cellulose is also low. In this technology, by mixing the water-insoluble hydrophilic resin 13 with the dispersion system 10, the reinforcing effect derived from the high aspect ratio of the fibrillated cellulose is sufficiently exhibited, and the strength of the product is improved. .

The water-insoluble hydrophilic resin 13 described above means a resin that is hydrophilic but water-insoluble.
The water-insoluble property referred to in the present invention means that the measured value of the solubility of the resin is substantially 0 as described above. When the dispersion system 10 contains only the water-soluble resin instead of the water-insoluble hydrophilic resin 13 as the resin, the strength of the product is not sufficiently improved when the dispersed fibrillated cellulose after mixing is mixed with the resin or the like. .

The hydrophilic resin referred to in the present invention means a resin having a hydrophilic group. Hydrophilic groups include carboxy group —COOH, hydroxy group —OH, amino group —NH ₂ , carbonyl group> CO, sulfo group —SO ₃ H, and the like. When the dispersion system 10 contains only a hydrophobic resin instead of the water-insoluble hydrophilic resin 13 as the resin, the fibrillated cellulose aggregates when water is removed from the mixed dispersion system, and the fibrillated cellulose is mixed with the resin or the like. The reinforcing effect derived from the high aspect ratio of fibrillated cellulose is not exhibited.

Whether or not it is a water-insoluble hydrophilic resin depends on whether or not the transmittance T (0 ≦ T ≦ 1) of a system in which a powdery resin sample is put in water is equal to or less than a threshold value Tt (0 <Tt <1). Can be distinguished by Since the hydrophobic resin floats or precipitates without dissolving in water, T> Tt. Since the water-soluble resin dissolves in water, T> Tt.
Specifically, a resin sample is added to water so that the resin concentration becomes 1% by weight, and after stirring with a stirrer at 100 rpm or more for 10 minutes or more, the stirring solution is put into a 10 mm cell for a spectrophotometer, and after 10 seconds. Assume that the transmittance T of light having a wavelength of 660 nm is measured. A blank with a transmittance of 1 is adjusted with a 10 mm cell containing ion-exchanged water. When the measured value of the spectrophotometer is absorbance A (A ≧ 0), the transmittance T is obtained from T = 10 ^−A . The threshold value Tt is preferably 0.9, more preferably 0.8, still more preferably 0.7, and particularly preferably 0.6.

  As the water-insoluble hydrophilic resin 13, an acid-modified resin obtained by adding an acid such as an organic acid to a raw material of a synthetic resin such as a thermoplastic resin can be used. Synthetic resins include rubbers and elastomers. The unsaturated acid added to the raw material of the synthetic resin includes unsaturated dicarboxylic acids or anhydrides such as maleic acid, maleic anhydride and fumaric acid, unsaturated carboxylic acids such as acrylic acid and methacrylic acid, and methyl (meth) acrylate. An alkyl ester derivative of unsaturated carboxylic acid such as 2-ethylhexyl acrylate, an unsaturated carboxylic acid or unsaturated dicarboxylic acid derivative such as mono- or diethyl ester of acrylamide or maleic acid, a combination thereof, or the like can be used. For example, when an addition polymerization is performed by adding an unsaturated dicarboxylic acid or an unsaturated carboxylic acid to the raw material of the synthetic resin before the addition polymerization, an acid-modified resin having a carboxyl group which is a hydrophilic group is obtained. Specific examples of water-insoluble hydrophilic resins include acid-modified polyolefins such as acid-modified PP (polypropylene) and acid-modified PE (polyethylene), acid-modified PS (polystyrene), acid-modified AS (acrylonitrile styrene copolymer), and amine-modified. Examples thereof include resins, chlorinated resins, polyamides, polyurethanes, and the like.

  The size of the solid water-insoluble hydrophilic resin in the case of wet pulverization may be a size that allows wet pulverization. It is preferable that the water-insoluble hydrophilic resin is in a powder form because it is easily bonded to fibrillated cellulose. The powder form includes granular form, fibrous form, and the like. The size of the powdery water-insoluble hydrophilic resin is preferably 4 mm path, more preferably 2 mm path, further preferably 1 mm path, and particularly preferably 500 μm path.

  Furthermore, one or more additives 16 that are not included in the water 11, the cellulose raw material 12, and the water-insoluble hydrophilic resin 13 may be added to the wet pulverizer MI1. Additives 16 include lubricants, fibrous materials, nucleating agents, pigments such as pigments, heat stabilizers, light stabilizers, UV absorbers, antistatic agents, fillers, plasticizers, reinforcing agents, flame retardants, flame retardants. Auxiliaries, mold release agents, fungicides, peroxides such as ketone peroxide and hydroperoxide, dispersion materials, combinations thereof, and the like can be used. Further, at least one of a hydrophobic resin and a water-soluble resin may be included in the additive 16 within a range smaller than the weight ratio of the water-insoluble hydrophilic resin 13 included in the dispersion system 10. When the wet additive pulverization is performed, the size of the solid additive 16 is preferably 4 mm path, more preferably 2 mm path, further preferably 1 mm path, and particularly preferably 500 μm path.

  The weight ratio of the cellulose raw material in the dispersion is, for example, 0.05 to 100 parts by weight (more preferably 0.5 to 70 parts by weight, still more preferably 1 to 50 parts by weight, particularly preferably 100 parts by weight of water). 2 to 20 parts by weight). When the weight ratio of the cellulose raw material is set to the above lower limit or more, the modified fibrillated cellulose can be obtained in a preferable yield. When the weight ratio of the cellulose raw material is less than or equal to the above upper limit, aggregation of the fibrillated cellulose is suppressed by water in the dispersion, and the fibrillated cellulose-containing product can have a preferable strength. The weight ratio of the water-insoluble hydrophilic resin in the dispersion is, for example, 0.1 to 10,000 parts by weight (more preferably 1 to 1000 parts by weight, still more preferably 5 to 500 parts by weight, based on 100 parts by weight of cellulose, Particularly preferably, it can be 15 to 300 parts by weight. The water-insoluble hydrophilic resin with respect to 100 parts by weight of water can be, for example, 0.1 to 100 parts by weight (more preferably 0.5 to 60 parts by weight, still more preferably 1 to 30 parts by weight). When the weight ratio of the water-insoluble hydrophilic resin is not less than the above lower limit, aggregation of the fibrillated cellulose is suppressed by water in the dispersion, and the fibrillated cellulose-containing product can have a preferable strength. When the weight ratio of the water-insoluble hydrophilic resin is not more than the above upper limit, the water-insoluble hydrophilic resin that does not bind to the fibrillated cellulose is suppressed, and the fibrillated cellulose-containing product can have a preferable strength.

  When the additive 16 is added, for example, in order to make the fibrillated cellulose-containing product have a preferable strength, the blending ratio of the additive to 100 parts by weight of the cellulose raw material is set to 100000 parts by weight or less (more preferably 100 parts by weight or less). Can do. The additive 16 with respect to 100 parts by weight of water can be, for example, 100 parts by weight or less (more preferably 50 parts by weight or less). When the additive 16 contains at least one of a hydrophobic resin and a water-soluble resin, the weight ratio of the resin in the dispersion should be less than the weight ratio of the water-insoluble hydrophilic resin in the dispersion. The amount is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, and still more preferably 10 parts by weight or less with respect to 100 parts by weight of the water-insoluble hydrophilic resin. When the weight ratio of at least one of the hydrophobic resin and the water-soluble resin is less than or equal to the above upper limit, aggregation of the fibrillated cellulose is suppressed when moisture is removed from the dispersion after mixing, and the fibrillated cellulose is replaced with a resin or the like. When mixed, the reinforcing effect derived from the high aspect ratio of fibrillated cellulose is exhibited, and the strength of the product is improved.

  The wet pulverizer MI1 uses at least one selected from a ball mill, a bead mill, a rod mill, a disk mill, a ring mill, a high-pressure homogenizer, a shear mixer, a kneader, a planetary rotary mixer, a jet mill, an attrition mill, and a high-speed mixer. be able to. These machines can apply a shearing force to the cellulose raw material to fibrillate the cellulose raw material. Wet pulverization means pulverization performed in the presence of water. A ball mill, a bead mill, a rod mill, a disk mill, and the like are mills that use the processing medium ME1. The processing medium ME1 is also called a grinding medium, and includes a ball-shaped medium, a rod-shaped medium, a bead-shaped medium, a disk-shaped medium, and the like. Therefore, the mill includes a ball mill that hits the workpiece with the ball-shaped medium placed in the dispersion, a rod mill that hits the workpiece with the rod-shaped medium placed in the dispersion, and a bead-like medium placed in the dispersion. And a bead mill that hits the disk, a disk mill that pulverizes the workpiece by rotating at least one of the two disk-shaped media with a dispersion system in between. The mill fibrillates the cellulose raw material 12 by the movement of the processing medium ME1. The strong mechanical energy from the processing medium ME1 defibrates (beats) the cellulose raw material 12 swollen with water and sufficiently fibrillates, and also refines the water-insoluble hydrophilic resin 13. For mills that use grinding media, a vibrating mill that vibrates a drum-like grinding cylinder in which grinding media is inserted and moves the grinding media inside, a mill that rotates the grinding cylinder and moves the grinding media inside, etc. There is.

As the material of the processing medium ME1, a metal such as steel or stainless steel, a ceramic such as alumina, a synthetic resin such as polyamide (nylon), or the like can be used. For the ball-shaped medium, for example, a spherical medium having a diameter of about 10 to 50 mm is used. For example, a cylindrical medium having a diameter of about 10 to 50 mm is used as the rod-shaped medium.
When the dispersion system 10 is mixed using the above-described wet pulverization apparatus MI1, shear force is applied to the dispersion system 10, so that the fibrillated cellulose 22 easily enters the water-insoluble hydrophilic resin 13 and the dispersibility of the fibrillated cellulose 22 is increased. Will improve. Therefore, when the wet pulverizer MI1 is used, the strength of the fibrillated cellulose-containing product is further improved as compared with the case where the wet pulverizer is not used.

  In the wet grinding step S2, wet grinding is performed on the dispersion system 10 including at least the cellulose raw material 12 and the water-insoluble hydrophilic resin 13. Non-fibrillated cellulose raw material is fibrillated by wet grinding. The wet pulverization time can be, for example, about 5 minutes to 24 hours, about 10 minutes to 12 hours, and the like. The wet modified fibrillated cellulose 30 is obtained by wet pulverization. Therefore, the present production method is to produce the modified fibrillated cellulose 30 by mixing the dispersion system 10 containing at least the water 11, cellulose (12, 22), and the water-insoluble hydrophilic resin 13. Become.

  The wet modified fibrillated cellulose 30 obtained after the wet pulverization can be dried in the drying step S3 as necessary. This drying can be performed by usual methods such as drying by heating at about 40 to 120 ° C., drying by blowing, drying using both heating and blowing, room temperature drying, reduced pressure drying, etc. It may be performed by any method. For example, when drying at about 60 ° C., the wet modified fibrillated cellulose may be heated for about 5 to 7 days. When vacuum drying, the wet modified fibrillated cellulose may be evacuated for about 1 to 3 days. The resulting modified fibrillated cellulose 32 is prevented from agglomerating and can be easily fibrillated into individual modified fibrillated cellulose even if it is a tumbled lump. When the fibrillated cellulose is mixed with the resin product, it is often required to dry the fibrillated cellulose. In such a case, this production method is suitable.

  The resulting modified fibrillated cellulose 30, 32 is a wood plastic reinforcing material for deck materials, a substitute for glass fiber reinforced plastic, a flame retardant engineering plastic for mechanical parts, cement, etc. It can be used as a reinforcing material for building materials, a heat insulating material, a green body additive for forming a cellular ceramic by combustion, and the like.

  FIG. 1 also shows an example in which a resin product 40 is manufactured using modified fibrillated cellulose. The resin product 40 includes a resin molded product, a paint, an adhesive, and the like. Of course, a product such as a cement building material such as a concrete product obtained by mixing the modified fibrillated cellulose 30 or 32 with cement, or a porous ceramic green body may be manufactured. In the resin product production step S4, a resin product is prepared by mixing at least one of the dried modified fibrillated cellulose 32 and the wet modified fibrillated cellulose 30, the resin 33, and, if necessary, one or more additives 36. 40 is manufactured. The obtained resin product 40 is a fibrillated cellulose-containing resin product in which at least a modified fibrillated cellulose and a resin are mixed.

  The resin 33 may be solid or liquid, and a synthetic resin such as a thermoplastic resin or a thermosetting resin can be used. Examples of the thermoplastic resin include polyolefin (polypropylene (PP), polyethylene (PE), polybutene, etc.), paraffin, polystyrene, polymethyl methacrylate, vinyl chloride, polyamide (nylon), polycarbonate, polyacetal, polybutylene terephthalate, Polyethylene terephthalate, polyethylene glycol (PEG), polyvinyl alcohol (PVA), olefinic thermoplastic elastomers, styrene thermoplastic elastomers, unsaturated monomers such as unsaturated acids as raw materials for these resins (acrylic acid, methacrylic acid, etc.) Unsaturated carboxylic acids, alkyl ester derivatives of unsaturated carboxylic acids such as methyl (meth) acrylate, 2-ethylhexyl acrylate, etc., and unsaturated dicarls such as maleic acid, maleic anhydride, fumaric acid, etc. Resin obtained by adding an acid or acid anhydride, an unsaturated carboxylic acid such as acrylamide or mono- or diethyl ester of maleic acid or a derivative of unsaturated dicarboxylic acid, etc.), a mixture thereof, or the like is used. be able to.

As the thermosetting resin, for example, an unsaturated polyester resin, an epoxy resin, a urethane resin, a silicone resin, a phenol resin, a urea resin, a melamine resin, a mixture thereof, or the like can be used. For liquid thermosetting resins, if necessary, radically polymerizable monomers such as styrene and vinyltoluene, oligomers thereof, polymerization inhibitors such as hydroquinone and p-benzoquinone, fillers (fillers), compatibilizing agents, lubricants In addition, additives such as fibrous materials, nucleating agents, pigments, antioxidants, heat stabilizers, ultraviolet absorbers, antistatic agents, and the like may be included.
Of the above-described resins, hydrophobic resins such as polyolefins and water-insoluble hydrophilic resins are preferable in that the modified fibrillated cellulose 30 and 32 are well dispersed.

  The weight ratio of the modified fibrillated cellulose to 100 parts by weight of the resin can be, for example, 1-1000 parts by weight, 2-100 parts by weight, 3-50 parts by weight, 5-30 parts by weight, and the like.

  The additive 36 may be solid or liquid, and is a colorant such as a lubricant, a fibrous material, a nucleating agent, or a pigment, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, an antistatic agent, a filler, a plasticizer. , Reinforcing agents, metal deactivators, flame retardants, flame retardant aids, mold release agents, fungicides, combinations thereof, and the like can be used. When the additive 36 is added, for example, in order to make the resin product have a preferable strength, the compounding ratio of the additive 36 with respect to 100 parts by weight of the resin can be 100 parts by weight or less (more preferably 50 parts by weight or less).

  The molding apparatus for the resin product 40 includes an injection molding machine, an extrusion molding machine, a press molding machine, a casting molding machine, and the like for molding the input material by injection molding, extrusion molding, press molding, cast molding, etc. Can be used. Further, a resin product may be formed by applying a material to an object to be coated with a brush or the like without using a molding apparatus. Further, the resin product may be formed by once pelletizing with a pellet manufacturing apparatus described in JP-A No. 2004-17502 and post-molding the formed pellet by extrusion molding or the like.

  FIG. 5 schematically shows the aggregation suppressing action of the modified fibrillated cellulose using a water-insoluble hydrophilic resin. The surface of the fibrillated cellulose 22 has many hydroxyl groups that are highly polar functional groups. Therefore, when a dispersion containing unmodified fibrillated cellulose and water is dried by an ordinary method such as heating, the fibrillated celluloses are bonded to each other by hydrogen bonding, and aggregates of fibrillated cellulose are generated. Since the fibrillated cellulose has many hydroxyl groups, the bond becomes strong, and since it is refined, the bond becomes complicated. Therefore, it is difficult to defibrate the agglomerates into individual fibrillated cellulose, and the fibrillated cellulose is not uniformly dispersed when mixed with a resin or the like. With this, the reinforcing effect derived from the high aspect ratio of fibrillated cellulose cannot be exhibited in the product. Note that drying the dispersion by a special method such as freeze-drying increases the manufacturing cost.

  According to this production method, in the dispersion system after mixing, it is considered that the hydrophilic group of the water-insoluble hydrophilic resin 13 is bonded to the hydroxyl group of the fibrillated cellulose 22 as shown in the upper part of FIG. This bond includes a broad bond that binds the fibrillated cellulose and the water-insoluble hydrophilic resin by interaction, that is, physical adsorption and chemical bond. Although the water-insoluble hydrophilic resin on the surface of the modified fibrillated cellulose has a hydrophilic group, the modified fibrillated cellulose is considered to have fewer hydrophilic groups than the hydroxyl group of the fibrillated cellulose alone. Although there is a possibility that the fibrillated celluloses are bonded to each other by hydrogen bonding in the modified fibrillated cellulose 30, it is difficult to produce aggregates of the fibrillated cellulose due to the presence of the water-insoluble hydrophilic resin bonded to the fibrillated cellulose. Conceivable. Modified fibrillated cellulose having fewer hydrophilic groups than fibrillated cellulose alone is less likely to agglomerate as shown in the middle of FIG. 5 even when dried by a normal method such as heating. Moreover, even if it becomes solid in a deciduous shape by drying, it is easy to defibrate the mass of the modified fibrillated cellulose 32 into individual modified fibrillated cellulose.

  Furthermore, the resin is generally hydrophobic, and the water-insoluble hydrophilic resin 13 and the hydrophobic resin are compatible. For this reason, when the modified fibrillated cellulose 30, 32 is mixed with the resin 33, the water-insoluble hydrophilic resin 13 and the resin 33 are easily adapted as shown in the lower part of FIG. 32 is well dispersed.

  FIG. 6 schematically shows a fibrillated cellulose in a comparative example using a water-soluble resin. In the dispersion containing water, it is considered that the hydrophilic group of the water-soluble resin is bonded to the hydroxyl group of the fibrillated cellulose as shown in the upper part of FIG. Since the water-soluble resin is bonded to the fibrillated cellulose, it is considered that even when the dispersion is dried, aggregates of the fibrillated cellulose are hardly generated as shown in the middle part of FIG. However, since the water-soluble resin and the hydrophobic resin are difficult to be used, when the fibrillated cellulose to which the water-soluble resin is bonded is mixed with a general hydrophobic resin, as shown in the lower part of FIG. The strength of the interface with the functional resin is weak and the strength of the resin product is not sufficiently improved.

  FIG. 7 schematically shows a fibrillated cellulose in a comparative example using a hydrophobic resin. In the dispersion containing water, as shown in the upper part of FIG. 7, the bond between the fibrillated cellulose and the hydrophobic resin is weak, and the fibrillated cellulose has a reduced hydroxyl group even if it adheres to the hydrophobic resin. It is in a state of being easily aggregated. For this reason, when the dispersion is dried, fibrillated cellulose aggregates as shown in the middle of FIG. In addition, since the compatibility between the hydrophobic resin in the dispersion and the resin (hydrophobic) mixed at the time of resin production is large, as shown in the lower part of FIG. 7, the fibrillated cellulose and the resin (hydrophobic) ) And the strength of the resin product is not sufficiently improved.

  On the other hand, as shown in FIG. 5, in the present production method using a water-insoluble hydrophilic resin, unlike the case of using a hydrophobic resin, the aggregate of fibrillated cellulose is suppressed, and the case of using a water-soluble resin. Differently, the bond between the resin bonded to fibrillated cellulose and the hydrophobic resin mixed at the time of making the resin product is strong, and the strength of the resin product is sufficiently improved. Further, when modifying the fibrillated cellulose, an organic solution containing an organic solvent or an organic ionic liquid is not required. Therefore, the present technology can improve the strength of a fibrillated cellulose-containing product and a method for producing a new modified fibrillated cellulose that can improve the strength of the fibrillated cellulose-containing product with a simple treatment. New modified fibrillated cellulose can be provided.

(1-2) Manufacturing method example 2:
FIG. 2 shows Production Method Example 2 of modified fibrillated cellulose. In this production method example 2, the dispersion system 101 containing at least the cellulose raw material 12 is wet-pulverized to fibrillate the cellulose raw material 12, and then the water-insoluble hydrophilic resin 13 is added at least to disperse the dispersion system 10. These are mixed to produce modified fibrillated cellulose 30 and 32 in which at least the water-insoluble hydrophilic resin 13 is bonded to the fibrillated cellulose 22. In addition, what was shown in the manufacturing method example 1 can be used for the cellulose raw material 12, the water-insoluble hydrophilic resin 13, the additives 16, 36, the wet grinding apparatus MI1, and the processing medium ME1. The blending ratio of the cellulose raw material 12, the water-insoluble hydrophilic resin 13, and the additive 16 can also be set to the ratio shown in Production Method Example 1. The drying conditions can also be the same as in Production Method Example 1. The same applies to the manufacturing method example 3 shown in FIG.

  In the charging step S1, the water 11, the cellulose raw material 12, and one or more additives 16 as required are weighed and put into the wet pulverizer MI1. In the wet pulverization step S21, the cellulose raw material 12 is fibrillated by performing wet pulverization on the dispersion system 101 containing the aforementioned materials. The wet pulverization time can be, for example, about 5 minutes to 24 hours, about 10 minutes to 12 hours, and the like. When the weight ratio of the cellulose raw material to 100 parts by weight of water is about 5 parts by weight, the dispersion system 101 containing the fibrillated cellulose 22 is in a yogurt form, that is, a slurry form in which very fine particles are dispersed.

  Thereafter, the water-insoluble hydrophilic resin 13 and, if necessary, one or more additives 16 are weighed and put into the wet pulverizer MI1. The additive 16 added in the charging step S1 and the additive 16 charged in the wet grinding step S21 may be the same type or different types. In the case where the additive 16 is added in both steps S1 and S21, the total mixing ratio of the additive 16 may be set to the mixing ratio of the additive 16 described in Manufacturing Method Example 1. In the wet pulverization step S <b> 22, wet pulverization is performed on the dispersion system 10 including at least the fibrillated cellulose 22 and the water-insoluble hydrophilic resin 13. By this wet pulverization, the water-insoluble hydrophilic resin 13 is refined. Moreover, the fibrillation of the cellulose raw material 12 may progress. The wet pulverization time can be, for example, about 5 minutes to 24 hours, about 10 minutes to 12 hours, and the like. The wet modified fibrillated cellulose 30 is obtained by wet pulverization. Therefore, in this production method, the modified fibrillated cellulose 30 is produced by mixing the dispersion system 10 containing at least the water 11, the cellulose (22), and the water-insoluble hydrophilic resin 13.

The wet modified fibrillated cellulose 30 obtained after the wet pulverization can be dried in the drying step S3 as necessary. In the resin product production step S4, the resin product 40 is produced by mixing at least one of the modified fibrillated cellulose 30, 32, the resin 33, and, if necessary, one or more additives 36. The manufacturing method example 2 can also improve the strength of the product by a simple process. Production method example 2 is suitable when the cellulose raw material is to be pulverized longer than the water-insoluble hydrophilic resin.
If a commercial product of fibrillated cellulose such as cellulose nanofiber is used, the charging step S1 can be omitted.

(1-3) Manufacturing method example 3:
The modified fibrillated cellulose production method example 3 shown in FIG. 3 is a dispersion system including at least a compound 14 after kneading a material containing at least a cellulose raw material 12 and a water-insoluble hydrophilic resin 13 to produce a compound 14. 10, wet pulverization is performed to produce modified fibrillated cellulose 30 and 32 in which at least the water-insoluble hydrophilic resin 13 is bonded to the fibrillated cellulose 22.

  In the kneading step S11, the cellulose raw material 12, the water-insoluble hydrophilic resin 13 and, if necessary, the additive 16 are weighed and added to the kneading apparatus KN1, and the material is kneaded to produce the compound 14. By kneading, the cellulose raw material 12 and the water-insoluble hydrophilic resin 13 are well adapted. Various apparatuses can be used as the kneading apparatus KN1, for example, an extruder that heats and kneads a material charged from a hopper in a cylindrical barrel to extrude an amorphous compound. In order to extrude the material in an indefinite state, the die should not be attached to the barrel head (downstream end), or the pressure of the material at the barrel head position should be 5.0 MPa or less, more preferably A die having an opening of 3.0 MPa or less, more preferably 1.0 MPa or less may be attached. The amorphous compound 14 may be dry pulverized by a pulverizer.

  In the charging step S12, the water 11, the compound 14, and, if necessary, one or more additives 16 are weighed and put into the wet pulverizer MI1. In the wet pulverization step S2, wet pulverization is performed on the dispersion system 10 containing the aforementioned materials. By this wet pulverization, the compound 14 is refined, and the cellulose raw material 12 that is well-familiar with the water-insoluble hydrophilic resin 13 is fibrillated. The wet pulverization time can be, for example, about 5 minutes to 24 hours, about 10 minutes to 12 hours, and the like. The wet modified fibrillated cellulose 30 is obtained by wet pulverization. Therefore, the present production method is to produce the modified fibrillated cellulose 30 by mixing the dispersion system 10 containing at least the water 11, cellulose (12, 22), and the water-insoluble hydrophilic resin 13. Become.

  The wet modified fibrillated cellulose 30 obtained after the wet pulverization can be dried in the drying step S3 as necessary. In the resin product production step S4, the resin product 40 is produced by mixing at least one of the modified fibrillated cellulose 30, 32, the resin 33, and, if necessary, one or more additives 36. The manufacturing method example 3 can also improve the strength of the product by a simple process. In addition, production method example 3 is expected to improve the familiarity between the fibrillated cellulose and the water-insoluble hydrophilic resin, and the familiarity between the modified fibrillated cellulose 30 and 32 and the resin 33 in the resin product 40 is expected. It is expected to improve.

(1-4) Manufacturing method example 4:
The modified fibrillated cellulose production method example 4 shown in FIG. 4 mixes a dispersion system 10 containing at least water 11, a cellulose raw material 12, and a water-insoluble hydrophilic resin 23, and removes water from the obtained dispersion system. Thus, the fibrillated cellulose-containing resin product 50 is manufactured. The obtained resin product 50 is a fibrillated cellulose-containing resin product formed from a modified fibrillated cellulose 30 in which at least a water-insoluble hydrophilic resin 23 is bonded to the fibrillated cellulose 22. In addition, what was shown in the manufacturing method example 1 can be used for the cellulose raw material 12, the additives 16, 36, the wet grinding apparatus MI1, and the processing medium ME1. The mixing ratio of the cellulose raw material 12 and the additive 16 can also be the ratio shown in Production Method Example 1. The drying conditions can also be the same as in Production Method Example 1.

  In the charging step S1 shown in FIG. 4, the water 11, the cellulose raw material 12, the water-insoluble hydrophilic resin 23 having a low softening point, and, if necessary, the additive 16 are weighed and put into the wet pulverizer MI1. The low softening point water-insoluble hydrophilic resin 23 is a thermoplastic resin having a softening temperature equal to or lower than the boiling point of water, and is preferably a low melting point water-insoluble hydrophilic resin having a melting point equal to or lower than the boiling point of water. The boiling point of water is 100 ° C. under 1 atm. Specific examples of the low softening point water-insoluble hydrophilic resin 23 include a low melting point polyolefin such as a low melting point PE, an ethylene-vinyl acetate copolymer, and the like. Examples thereof include olefin copolymer TAFMER (registered trademark) XM7070 (softening temperature: 67 ° C., melting point: 75 ° C.). The size of the solid low softening point water-insoluble hydrophilic resin in the case of wet pulverization may be any size that allows wet pulverization. The preferred size of the powdery low softening point water-insoluble hydrophilic resin is the same as that of the water-insoluble hydrophilic resin 13. The preferable blending ratio of the low softening point water-insoluble hydrophilic resin is also the same as that of the water-insoluble hydrophilic resin 13.

  In the wet pulverization step S <b> 2, wet pulverization is performed on the dispersion system 10 including at least the cellulose raw material 12 and the low softening point water-insoluble hydrophilic resin 23. The wet pulverization time can be, for example, about 5 minutes to 24 hours, about 10 minutes to 12 hours, and the like. The wet modified fibrillated cellulose 30 is obtained by wet pulverization.

Thereafter, the dispersion system containing the modified fibrillated cellulose 30 is heated and dried to produce a resin product 50 (heat drying step S5). Since the low softening point water-insoluble hydrophilic resin 23 is at least softened by heating during drying, the resin product 50 can be molded from the dispersion. If the melting point of the water-insoluble hydrophilic resin 23 is equal to or lower than the boiling point of water, the water-insoluble hydrophilic resin 23 is melted by heating during drying, and the resin product 50 can be easily shaped. For example, by putting a dispersion system in a mold that matches the shape of the resin product 50, heating the mold to remove moisture, and cooling, the product can be commercialized simultaneously with drying. The dispersion molding may be thermoforming such as cast molding, injection molding, extrusion molding, press molding, or the like, or may be performed by applying the dispersion system to the object to be coated with a brush or the like and heating. The various resin products obtained are expected to be fibrillated cellulose-containing resin products in which fibrillated cellulose with suppressed aggregation is dispersed in at least a low softening point water-insoluble hydrophilic resin 23.
From the above, production method example 4 provides a production method capable of improving the strength of a fibrillated cellulose-containing resin product by a simple treatment, and a novel fibrillated cellulose-containing resin product having improved strength. Is possible.

Even if the softening temperature of the thermoplastic water-insoluble hydrophilic resin is higher than the boiling point of water, it is possible to form a resin product from the dispersion in the heat drying step S5. In this case, if the dispersion is heated in the heating and drying step S5, first, moisture is removed from the dispersion near the boiling point of water, and then the water-insoluble hydrophilic resin is softened at a temperature equal to or higher than the softening temperature. Can be thermoformed.
Further, even if the water-insoluble hydrophilic resin is thermosetting, it is possible to form a resin product from the dispersion system in the heat drying step S5. In this case, if the dispersion is heated in the heating and drying step S5, moisture is removed from the dispersion and the water-insoluble hydrophilic resin is thermoset and can be thermoformed into a resin product shape.
Furthermore, if the water-insoluble hydrophilic resin in the dispersion has a property of solidifying by removing moisture, it can be molded into a resin product shape even if moisture is removed from the dispersion without heating. .
In any of the above production methods, a dispersion containing at least water, cellulose, and a water-insoluble hydrophilic resin is mixed, and water is removed from the resulting dispersion to obtain a fibrillated cellulose-containing resin product. It is a manufacturing method. The obtained resin product is a fibrillated cellulose-containing resin product formed from modified fibrillated cellulose in which at least a water-insoluble hydrophilic resin is bound to fibrillated cellulose.

(1-5) Modification:
Various modifications can be considered for the present invention.
For example, the step of removing moisture from the dispersion containing wet modified fibrillated cellulose is not limited to the drying step S3 and the heat drying step S5, the step of filtering the dispersion to remove the filtrate, and centrifuging the dispersion Then, the step of removing the supernatant may be used.
The order in which the raw materials are charged, such as the charging step S1, the resin product forming step S4, the wet grinding step S22, the kneading step S11, the charging step S12, is not limited. For example, in the charging step S1, the water-insoluble hydrophilic resin 13 may be charged after the cellulose raw material 12 is charged, or the cellulose raw material 12 may be charged after the water-insoluble hydrophilic resin 13 is charged. Both raw materials 12 and 13 may be charged simultaneously.

Moreover, after wet-grinding the dispersion containing water 11, water-insoluble hydrophilic resin 13 and additive 16 as necessary, cellulose raw material 12 is added with additive 16 as necessary and the dispersion is mixed. Modified fibrillated cellulose may be produced. This manufacturing method is suitable when it is desired to pulverize the water-insoluble hydrophilic resin longer than the cellulose raw material.
Furthermore, a dispersion system (dispersion system A) containing water 11, cellulose raw material 12 and additive 16 as necessary is prepared, water 11, water-insoluble hydrophilic resin 13, and additive 16 as required. A dispersion (containing Dispersion B) may be prepared, and both dispersions A and B may be mixed to produce modified fibrillated cellulose. In this production method, the dispersion condition of the fibrillated cellulose and the dispersion condition of the water-insoluble hydrophilic resin can be adjusted separately, so that the quality of the product using the modified fibrillated cellulose is expected to be improved. The

  If the dispersion system contains fibrillated cellulose and fine water-insoluble hydrophilic resin, a mixing step that does not wet pulverize may be provided instead of the wet pulverization steps S2 and S22. The size of the fine water-insoluble hydrophilic resin introduced into the dispersion is preferably 500 μm pass, more preferably 300 μm pass, further preferably 100 μm pass, and particularly preferably 50 μm pass.

(2) Example:
EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated concretely, this invention is not limited by the following examples.

[Example 1]
Cellulose powder KC Flock (registered trademark) manufactured by Nippon Paper Industries Co., Ltd. was used as the cellulose raw material. Non-water-soluble hydrophilic resins include maleic acid-modified PP resin Yumex (registered trademark) 1010 block pulverized product manufactured by Sanyo Chemical Industries Ltd. (acidity 52 mgKOH / g as defined in JIS K0070-1992, softening point 145 by ring and ball method) ° C, 100 µm pass). The transmittance described above for the water-insoluble hydrophilic resin was measured using V-670 manufactured by JASCO Corporation as a spectrophotometer, and found to be 75%. The mixing ratio of water, cellulose raw material, and water-insoluble hydrophilic resin is as follows.
Water 95 parts by weight Cellulose raw material 5 parts by weight Water-insoluble hydrophilic resin 4 parts by weight

  As the mixing device, a planetary ball mill P-5 / 4 manufactured by Fritsch was used. As a container, a pulverized container made of Fritsch alumina I was used. As the treatment medium, 25 alumina balls having a diameter of 20 mm were used. At this time, the volume ratio of the processing medium was 30%. The rotation speed was set to 200 rpm.

  First, water, a cellulose raw material, and a water-insoluble hydrophilic resin were put into a ball mill with the above-described blending weight, and shear mixing was performed for 240 minutes. When the obtained dispersion system was visually confirmed, a water-insoluble hydrophilic resin was dispersed in water. The obtained wet modified fibrillated cellulose was transferred to a dryer and dried at 60 ° C. until a constant weight was obtained, thereby preparing a dried sample.

[Comparative Example 1]
The same cellulose raw material, spectrophotometer, and mixing apparatus as in Example 1 were used. PP Novatec (registered trademark) BC03B (MFR 30 g / 10 min defined in JIS K7210: 1999, 100 μm pass) manufactured by Nippon Polypro Co., Ltd. was used as the hydrophobic resin. The transmittance described above for this hydrophobic resin was measured and found to be 93%. The mixing ratio of water, cellulose raw material, and hydrophobic resin is as follows.
Water 95 parts by weight Cellulose raw material 5 parts by weight Hydrophobic resin 4 parts by weight

  Water, cellulose, and a hydrophobic resin were charged into the ball mill at the blending weight described above, and shear mixing was performed for 240 minutes. When the obtained dispersion was visually confirmed, the hydrophobic resin was separated from the water and floated. The obtained dispersion was transferred to a dryer and dried at 60 ° C. until a constant weight was obtained, thereby preparing a dried sample.

[Production of resin product samples]
A small kneader with an injection molding machine (Xplore (registered trademark) MC5 manufactured by DSM) was used as the resin molding apparatus. The kneading temperature was set to 190 ° C., the kneading screw rotation speed was set to 100 rpm, and the kneading time was set to 5 minutes.
About the dry sample of Example 1 and Comparative Example 1, the lump was loosened with the mortar, respectively. The loose dried sample was mixed with PP (the hydrophobic resin) so that the amount of cellulose was 1% by weight, kneaded with the resin molding apparatus, and injection molded with a DSM Xplore (registered trademark) Injector. 2.5 g of the obtained injection-molded body was formed into a sheet having a thickness of about 1 mm by a hot press at 190 ° C. and trimmed into a rectangular shape.

[Test results]
FIG. 8 shows a photograph of a sheet obtained from the injection-molded article of Example 1, and FIG. 9 shows a photograph of a sheet obtained from the injection-molded article of Comparative Example 1. As shown in FIG. 9, in the sample using the hydrophobic resin, many black spots in which fibrillated cellulose aggregated were observed. On the other hand, as shown in FIG. 8, the fibrillated cellulose of the sample using the water-insoluble hydrophilic resin showed high dispersibility.
Accordingly, when a dispersion containing water, cellulose and a water-insoluble hydrophilic resin is mixed, the strength of the fibrillated cellulose-containing product can be improved.

[Example 2]
Cellulose nanofibers manufactured by Mori Machinery Co., Ltd. (dispersion containing 5 parts by weight of cellulose nanofibers with respect to 95 parts by weight of water, fiber width of cellulose nanofibers of 30 to 200 nm, ratio of cellulose nanofibers) A surface area of 150 m ² / g) was used. The same water-insoluble hydrophilic resin as in Example 1 was used. Normal Portland cement manufactured by Taiheiyo Cement Co., Ltd. was used as a dispersant (additive). The blending ratio of water, cellulose raw material, water-insoluble hydrophilic resin, and additive is as follows.
Water 95 parts by weight Cellulose raw material 5 parts by weight Water-insoluble hydrophilic resin 1 part by weight Additive 1 part by weight

  As the mixing device, a planetary ball mill P-5 / 4 manufactured by Fritsch was used. As a container, a pulverized container made of Fritsch alumina I was used. As the treatment medium, 25 alumina balls having a diameter of 20 mm were used. At this time, the volume ratio of the processing medium was 30%. The rotation speed was set to 250 rpm.

  The cellulose nanofiber-containing dispersion (total 100 parts by weight), the water-insoluble hydrophilic resin, and the additive were added to the ball mill at the blending weight described above, and shear mixing was performed for 10 minutes. When the obtained dispersion system was visually confirmed, a water-insoluble hydrophilic resin was dispersed in water.

[Comparative Example 2]
The same cellulose nanofiber-containing dispersion, additive, and mixing apparatus as in Example 2 were used. The mixing ratio of water, cellulose raw material, and additive is as follows.
Water 95 parts by weight Cellulose raw material 5 parts by weight Reinforcing agent 1 part by weight The cellulose nanofiber-containing dispersion (total 100 parts by weight) and additives were added to the ball mill with the above-mentioned blending weight, and shear mixing was performed for 10 minutes.

[Comparative Example 3]
PP Novatec (registered trademark) J107G manufactured by Nippon Polypro Co., Ltd., which is a hydrophobic resin, was prepared as a resin for preparing a resin product sample to be described later. In Comparative Example 3, shear mixing is not performed.

[Production of resin product samples]
As the resin, the hydrophobic resin prepared in Comparative Example 3 was used.
Inoue Seisakusho Trimix (registered trademark) TX-0.5 was used for the heating and kneading apparatus. As the molding machine, a small kneader with an injection molding machine (Xplore (registered trademark) MC5 manufactured by DSM) was used. The kneading temperature was set to 190 ° C., the kneading screw rotation speed was set to 30 rpm, and the kneading time was set to 5 minutes.

102 parts by weight of the wet sample of Example 2 and 93 parts by weight of the hydrophobic resin were placed in the heating and kneading apparatus (the total amount of the resin was 94 parts by weight), and dried and kneaded at 230 ° C. for 15 minutes. The obtained kneaded material was put into the above molding machine and injection molded into the shape of a dumbbell-shaped No. 8 test piece defined in JIS K6251: 2010 (vulcanized rubber and thermoplastic rubber—how to obtain tensile properties).
Further, 101 parts by weight of the wet sample of Comparative Example 2 and 94 parts by weight of the hydrophobic resin were put into the heating and kneading apparatus, and dried and kneaded at 230 ° C. for 15 minutes. The obtained kneaded material was put into the molding machine and injection molded into the shape of the dumbbell-shaped No. 8 test piece.
Further, 100 parts by weight of the hydrophobic resin of Comparative Example 3 was placed in the molding machine and injection molded into the shape of the dumbbell-shaped No. 8 test piece.

[Tensile test]
JIS K7161: 1994 (Plastics-Test methods for tensile properties Part 1: General rules) and JIS K7162: 1994 (Plastics-Test methods for tensile properties Part 2: Test conditions for molding, extrusion molding and cast plastic) The tensile strength σ _M (unit: MPa) of the test pieces (resin product samples) of Example 2 and Comparative Examples 2 and 3 was measured.

[Test results]
Table 1 shows the test results of Example 2 and Comparative Examples 2 and 3.

As shown in Table 1, the tensile strength of the test piece of Comparative Example 2 is almost the same as the tensile strength of the test piece of Comparative Example 3 that does not use the cellulose raw material. The reinforcing effect derived from the high aspect ratio of the fiber has not been demonstrated. On the other hand, the tensile strength of the test piece of Example 2 using a water-insoluble hydrophilic resin is larger than that of Comparative Examples 2 and 3, and the resin product sample of Example 2 is derived from the high aspect ratio of cellulose nanofibers. The reinforcing effect is demonstrated.
Therefore, it was confirmed that the strength of the fibrillated cellulose-containing product can be improved by mixing a dispersion containing water, cellulose and a water-insoluble hydrophilic resin.

(3) Specific examples:
Furthermore, the present invention will be described with reference to specific examples, but the present invention is not limited to the following examples.

[Comparative Example 4]
The same materials as in Example 1 are used for the cellulose raw material, the spectrophotometer, and the mixing apparatus. Polyvinyl alcohol is used for the water-soluble resin. When the above-described transmittance is measured for this water-soluble resin, it is greater than 90%. The mixing ratio of water, cellulose raw material, and water-soluble resin is as follows.
Water 95 parts by weight Cellulose raw material 5 parts by weight Water-soluble resin 4 parts by weight

  Water, cellulose, and a water-soluble resin are charged into the ball mill with the above blending weight, and shear mixing is performed for 240 minutes. The resulting dispersion is transferred to a dryer and dried at 60 ° C. until a constant weight is obtained to produce a dry sample.

[Measurement of flexural modulus of resin product samples]
For the resin molding apparatus, a small kneader with an injection molding machine (Xplore (registered trademark) MC5 manufactured by DSM) is used. The kneading temperature is set to 190 ° C., the kneading screw rotation speed is set to 100 rpm, and the kneading time is set to 5 minutes.

  For the dried samples of Example 1 and Comparative Examples 1 and 4, the lump was loosened in a mortar, and PP (PP Novatec (registered trademark) manufactured by Nippon Polypro Co., Ltd.) was used so that the amount of cellulose in the dried sample was 1% by weight. BC03B) and kneaded by the resin molding apparatus, and a resin product sample having a length of 6 mm, a width of 50 mm, and a thickness of 2 mm is injection molded. The flexural modulus of the resin product sample obtained is measured under the conditions of a test speed of 2 mm / min and a fulcrum distance L = 32 mm in accordance with JIS K7171-1994 Confirmation 2006 (Plastic—Bending Properties Test Method). It is estimated that the flexural modulus of the resin product sample of Example 1 is larger than the flexural modulus of the resin product sample of Comparative Examples 1 and 4. That is, the strength of the resin product sample of Example 1 is estimated to be greater than the strength of the resin product samples of Comparative Examples 1 and 4.

(4) Conclusion:
As described above, according to the present invention, according to various aspects, it is possible to provide a technique that can improve the strength of a fibrillated cellulose-containing product with a simple process. Needless to say, the above-described basic actions and effects can be obtained even with a technique that does not have the constituent requirements according to the dependent claims but includes only the constituent requirements according to the independent claims.

  In addition, the configurations disclosed in the embodiments and modifications described above are mutually replaced, the combinations are changed, the known technology, and the configurations disclosed in the embodiments and modifications described above are mutually connected. It is possible to implement a configuration in which replacement or combination is changed. The present invention includes these configurations and the like.

10, 101 ... dispersion system,
DESCRIPTION OF SYMBOLS 11 ... Water, 12 ... Cellulose raw material, 13 ... Water-insoluble hydrophilic resin, 14 ... Compound,
16, 36 ... additives,
22 ... fibrillated cellulose, 23 ... low softening point water-insoluble hydrophilic resin,
30, 32 ... modified fibrillated cellulose,
33 ... resin,
40, 50 ... Resin products,
KN1 ... kneading device, ME1 ... treatment medium, MI1 ... wet grinding device,
S1, S12 ... charging step, S2, S21, S22 ... wet grinding step, S3 ... drying step,
S4 ... Resin product production step, S5 ... Heat drying step, S11 ... Kneading step.

Claims (10)

Using a mill using a treatment medium, the treatment medium in a dispersion system containing at least water, cellulose, and a water-insoluble hydrophilic resin is hit against the cellulose and the water-insoluble hydrophilic resin. wet milling performed by fibrillating the cellulose, producing method of reforming fibrillated cellulose, characterized in that to produce a modified fibrillated cellulose to said dispersion Te. The method for producing modified fibrillated cellulose according to claim 1, wherein a resin having a softening temperature equal to or lower than the boiling point of water is used as the water-insoluble hydrophilic resin. Using a mill using a treatment medium, the cellulose and the non-treatment medium are placed in a dispersion containing at least water, cellulose, and a water-insoluble hydrophilic resin having a softening temperature equal to or lower than the boiling point of water. A water-soluble hydrophilic resin is applied to the dispersion to perform wet pulverization to obtain a modified fibrillated cellulose, and the dispersion containing the modified fibrillated cellulose is heated to form the water-insoluble hydrophilic A method for producing a fibrillated cellulose-containing resin product , characterized in that a fibrillated cellulose-containing resin product is produced by softening or melting a functional resin and drying the obtained dispersion .   Using the mill using the processing medium, the cellulose and the water-insoluble hydrophilicity are used as the processing medium in a dispersion containing at least water, cellulose, and a thermoplastic water-insoluble hydrophilic resin. The dispersion system is subjected to wet pulverization by hitting a resin to obtain modified fibrillated cellulose, and the dispersion system containing the modified fibrillated cellulose is heated to remove moisture from the dispersion system. A method for producing a fibrillated cellulose-containing resin product, which is characterized by producing a fibrillated cellulose-containing resin product shaped by thermoforming a resin.   Using a mill using a treatment medium, the treatment medium in a dispersion containing at least water, cellulose, and a thermosetting water-insoluble hydrophilic resin is used as the cellulose and the water-insoluble hydrophilic property. The modified fibrillated cellulose is obtained by applying wet pulverization to the dispersed system by hitting the resin, and removing the moisture from the dispersed system by heating the dispersed system containing the modified fibrillated cellulose. A method for producing a fibrillated cellulose-containing resin product, characterized by producing a fibrillated cellulose-containing resin product formed by thermosetting a water-soluble hydrophilic resin. A fibrillated cellulose-containing resin product is produced by mixing at least a modified fibrillated cellulose obtained by the method for producing a modified fibrillated cellulose according to claim 1 or 2 and a resin. A method for producing a cellulose-containing resin product. The fibrillated cellulose, at least, modified fibrillated cellulose water-insoluble hydrophilic resin which is an acid-modified polyolefin modified by an organic acid is bonded.
However, the case where a nonionic surfactant is present is excluded.   Modified fibrillated cellulose in which fibrillated cellulose is incorporated into a water-insoluble hydrophilic resin, which is an acid-modified polyolefin modified with an organic acid. A fibrillated cellulose-containing resin product formed from the modified fibrillated cellulose according to claim 7 or 8 . A fibrillated cellulose-containing resin product in which the modified fibrillated cellulose according to claim 7 or 8 and a resin are mixed at least.