JP2018080415A - Modified cellulose and resin composition prepared therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition or complex containing cellulose fiber of high water-filterability, when recovering cellulose fiber.SOLUTION: A composition contains non-fibrous anionized polysaccharides, a cationizing agent, and cellulose fiber.SELECTED DRAWING: None

Description

  The present invention relates to a modified cellulose and a resin composition using the same.

  Cellulose fibers constituting wood pulp and the like have long been used as a naturally derived renewable raw material for applications such as paper, clothes and packaging materials. Cellulose fibers are polysaccharides and usually do not exist as molecules, and have a multilayer structure such as cellulose microfibrils (MFC) in which the cellulose molecules are aggregated, microfibril bundles in which the MFCs are aggregated, and aggregates thereof. Yes.

  In addition, a technology for obtaining cellulose nanofibers (CNF) defibrated to nano size by subjecting cellulose fibers to mechanical treatment and / or chemical treatment has been developed. CNF is a fiber having a fiber width of about 4 to 100 nm and a fiber length of about 5 μm or more, and is attracting attention as a composite material for resin having a low specific gravity and a high strength. CNF is usually obtained by subjecting cellulose fibers to mechanical treatment in an aqueous medium.

  Cellulose fibers are lightweight, strong, and have a low linear thermal expansion. Therefore, a technique has been developed in which cellulose fibers are blended in a matrix such as a resin to increase the mechanical strength of the resin composition. However, since the cellulose fiber has a hydroxyl group and has high hydrophilicity, it has an aspect inferior in compatibility with a hydrophobic resin.

  CNF obtained after defibration to the nano level in water also contains a large amount of hydroxyl groups and is extremely hydrophilic. A network is formed between the CNFs, and the viscosity and water retention of the CNF slurry are very high. Therefore, it took a long time to drain the CNF from the aqueous dispersion (slurry) by filtration or the like. Further, once the CNF after the drainage was dried, it aggregated due to hydrogen bonds between the CNFs, and it was difficult to redisperse CNF uniformly. For this reason, it has also been difficult to combine highly hydrophilic CNF in the resin.

  Thus, attempts have been made to improve the compatibility between cellulose fiber or CNF and resin by introducing functional groups into cellulose or CNF by chemical treatment (Patent Documents 1 and 2).

  Further, the present applicant has developed a modified CNF obtained by neutralizing the cationic group of cationic CNF with an anionic additive (Patent Document 3). According to this technique, the drainage time at the time of recovery of the modified CNF is shortened, and the modified CNF is uniformly dispersed in the resin, and a highly modified modified CNF-containing resin composition can be obtained.

  The above prior art is a technique using a hydrophobic cellulose fiber or CNF obtained by directly introducing a hydrophobic group into a hydrophilic group of cellulose fiber or CNF.

JP 2010-106251 A JP 2011-047084 JP Patent No. 5150792

  An object of the present invention is to provide a composition containing cellulose fiber and CNF having high drainage when recovering cellulose fiber and CNF, or a composite containing cellulose fiber and CNF.

  Another object of the present invention is to provide a composition containing cellulose fibers or a composite containing cellulose fibers, in which the dispersibility of the cellulose fibers in the resin is good. That is, the dispersibility of the cellulose fiber is good in the resin composition.

  An object of this invention is to provide the resin molding which contains the composition containing a composition containing a cellulose fiber, or a cellulose fiber, and shows high intensity | strength.

  The present inventors have found that the above problem can be solved by neutralizing cellulose fibers surface-treated with non-fibrous anionized polysaccharide with a cationizing agent.

  The inventors of the present invention shorten the drainage time when recovering cellulose fibers from an aqueous medium by first surface-treating the cellulose fibers with a non-fibrous anionized polysaccharide and then neutralizing with a cationizing agent. I found out. The present inventors have found that the cellulose fibers, or cellulose nanofibers (CNF) obtained by further defibrating them, are uniformly dispersed in the resin, and resin compositions containing these cellulose fibers and CNF. It has been found that the resin molded body prepared from the product has increased strength.

Item 1.
A composition comprising a non-fibrous anionized polysaccharide, a cationizing agent, and cellulose fibers.

  A composition comprising a complex of a non-fibrous anionized polysaccharide and a cationizing agent, and cellulose fibers.

  A composition comprising an anionic cellulose fiber comprising a non-fibrous anionized polysaccharide and a cellulose fiber, and a cationizing agent.

Item 2.
A composition comprising a neutralized product of a non-fibrous anionized polysaccharide and a cationizing agent, and cellulose fibers.

Item 3.
Item 3. The composition according to Item 1 or 2, wherein the non-fibrous anionized polysaccharide is carboxymethyl cellulose.

Item 4.
The cationizing agent is a dispersion of an alkyl ketene dimer with a cationic dispersant, a cationic polystyrene resin, a cationic fatty acid derivative, a cationic poly (meth) acrylic resin, a cationic polyester resin, a cationic polyolefin resin, a cationic poly Item 4. The composition according to any one of Items 1 to 3, which is at least one component selected from the group consisting of an ether resin, a cationic polyurethane resin, and a quaternary ammonium compound.

Item 5.
Item 5. The composition according to Items 1 to 4, wherein the cellulose fiber is CNF.

Item 6.
Item 6. The resin composition comprising the composition according to items 1 to 5 and a resin.

Item 7.
A molded article formed by molding the resin composition according to Item 6.

Item 8.
It is a manufacturing method of the composition of the said items 1-5,
(1) treating cellulose fibers with non-fibrous anionized polysaccharide, and
(2) a step of treating the cellulose fiber obtained in step 1 with a cationizing agent,
Manufacturing method.

Item 9.
A complex in which a neutralized product of a non-fibrous anionized polysaccharide and a cationizing agent is adsorbed on cellulose fibers.

Item 10.
A method for producing a composite, comprising:
(1) treating cellulose fibers with non-fibrous anionized polysaccharide, and
(2) a step of treating the cellulose fiber obtained in step 1 with a cationizing agent,
Manufacturing method.

Item 11.
Item 11. The production method according to Item 10, wherein the complex is a complex in which a neutralized product of a non-fibrous anionized polysaccharide and a cationizing agent is adsorbed on cellulose fibers.

  According to the present invention, it is possible to obtain a composition containing cellulose fiber (or CNF) and a composite containing cellulose fiber (or CNF), which can significantly reduce the drainage time when recovering cellulose fiber (or CNF). That is, these compositions and composites contain cellulose fibers (or CNF) that have a reduced drainage treatment time, drying treatment time, and the like for cellulose fibers (or CNF) and have high drainage.

  As a result, the energy consumed in the production of a composition containing these cellulose fibers or a composite containing cellulose fibers is reduced. Compared with untreated cellulose fiber and CNF, when the composition containing the cellulose fiber (or CNF) of the present invention or the composite containing cellulose fiber (or CNF) is used, the dispersibility of the cellulose fiber and CNF in the resin Is good. That is, in the resin composition, cellulose fibers (or CNF) are uniformly dispersed in the resin.

  The resin molded body prepared using the resin composition containing the cellulose fiber (or CNF) has improved strength as compared with the case where untreated cellulose fiber or CNF is used.

It is a figure showing the aspect of this invention. It is a figure showing the aspect of this invention.

  Hereinafter, embodiments for carrying out the present invention will be described in detail.

  Hereinafter, the cellulose nanofiber is also referred to as CNF.

(1) Composition and composite The composition of the present invention comprises a non-fibrous anionized polysaccharide, a cationizing agent, and cellulose fibers. The composition of the present invention is a composition comprising a neutralized product of a non-fibrous anionized polysaccharide and a cationizing agent, and cellulose fibers. The composition can be produced by treating cellulose fibers with a non-fibrous anionized polysaccharide and then with a cationizing agent.

  In the composite of the present invention, a neutralized product of a non-fibrous anionized polysaccharide and a cationizing agent is adsorbed on cellulose fibers.

  The cellulose fiber contained in the composition or composite may be CNF.

  When the cellulose fiber is CNF, it can be produced by treating the cellulose fiber with a non-fibrous anionized polysaccharide, then treating with a cationizing agent, and further defibrating the obtained cellulose fiber. The composition or composite can also be produced by directly using CNF as a raw material, treating it with a non-fibrous anionized polysaccharide, and then treating with a cationizing agent.

  Cellulose fiber or CNF is treated with non-fibrous anionized polysaccharide to form a complex of cellulose fiber or CNF and non-fibrous anionized polysaccharide. In this composite, cellulose fibers or CNF fibrous cellulose (polysaccharide) and non-fibrous anionized polysaccharide polysaccharide interact with each other by intermolecular forces such as hydrogen bonds and van der Waals forces. That is, cellulose fiber or CNF fibrous cellulose (polysaccharide) and non-fibrous anionized polysaccharide polysaccharide are familiar.

  Due to this action, this composite has a structure in which the anionic functional group of the non-fibrous anionized polysaccharide appears on the surface of the cellulose fiber or CNF via the nonfibrous anionized polysaccharide. . It can also be said that they are connected in the order of cellulose fiber or CNF, polysaccharide of non-fibrous anionized polysaccharide, and anionic functional group of non-fibrous anionized polysaccharide.

  This is a cellulose fiber or CNF (complex) treated with a non-fibrous anionized polysaccharide, which is anionized as a whole complex. Thereby, the anionic complex of cellulose fiber or CNF and a non-fibrous anionized polysaccharide has high solubility in an aqueous solution and good dispersibility in the aqueous solution.

  Cellulose fibers or CNF (complex) treated with non-fibrous anionized polysaccharide are then treated with a cationizing agent to form a composition or complex. In this composition or composite, the anionic functional group of the non-fibrous anionized polysaccharide and the anionic functional group of the cationizing agent appearing on the surface of the cellulose fiber or CNF are intermolecular. They interact with each other by force. That is, the anionic functional group of the non-fibrous anionized polysaccharide and the anionic functional group of the cationizing agent are familiar.

  By this action, in the cellulose fiber or CNF contained in the composition or the composite, first, (i) on the surface of the cellulose fiber or CNF, the anion of the non-fibrous anionized polysaccharide via the polysaccharide of the non-fibrous anionized polysaccharide Sexual functional groups appear. This is a cellulose fiber or CNF (complex) treated with a non-fibrous anionized polysaccharide. And (ii) the anionic functional group of the non-fibrous anionized polysaccharide present on the surface of the complex, through the cationic functional group of the cationizing agent, the resin part (or monomer part) of the cationizing agent ) Appears. Cellulose fiber or CNF, polysaccharide of non-fibrous anionized polysaccharide, anionic functional group of non-fibrous anionized polysaccharide, cationic functional group of cationizing agent, resin part (or monomer part) of cationizing agent And it can be said that they are connected.

  This can be expressed as the composition of the present invention containing a neutralized product of a non-fibrous anionized polysaccharide and a cationizing agent and cellulose fibers.

  Moreover, the composite_body | complex of this invention can represent that the neutralized material of a non-fibrous anionized polysaccharide and a cationizing agent has adsorb | sucked to the cellulose fiber.

  The cellulose fiber or CNF contained in the composition or composite of the present invention is neutralized as a whole. Thereby, the cellulose fiber or CNF contained in a composition or a composite_body | complex becomes small in aqueous solution, and drainage becomes high. As a result, the cellulose fibers and / or CNF contained in the composition or composite are greatly reduced in the drainage time when recovered from an aqueous solution.

  Cellulose fibers are highly suitable for subsequent defibration because of their high drainage.

  The resin composition contains cellulose fiber or CNF and a resin. The resin composition can be molded to produce a molded body.

  Cellulose fibers or CNF generally have a resin part (or monomer part) of the cationizing agent on the surface. The resin part (or monomer part) of the cationizing agent appearing on the surface of this cellulose fiber or CNF, and the resin (matrix material), such as hydrophobic interaction, hydrogen bond, dipole interaction, van der Waals force, etc. They interact with each other due to intermolecular forces. That is, the resin part (or monomer part) of the cationizing agent and the resin (matrix material) are familiar.

  Due to this action, in the resin composition, cellulose fiber or CNF, polysaccharide of non-fibrous anionized polysaccharide, anionic functional group of non-fibrous anionized polysaccharide, cationic functional group of cationizing agent, cationizing agent It can also be said that the resin part (or monomer part) and the resin are connected in this order. Hydrophobic interactions are acting on the resin.

  As a result, the cellulose fibers or modified CNF are well dispersed in the resin. When a resin molded body is produced using this resin composition, the resin molded body has good strength.

  The non-fibrous anionized polysaccharide is preferably a component having a cellulose structure having an anionic functional group.

  The cationizing agent is preferably a component having a cationic functional group, easily compatible with the resin, and easily dispersed in the resin composition.

(1-1) Cellulose fiber is generally a long and slender thread-like substance (solid), and is a component whose width is so thin that it cannot be directly measured with the naked eye and whose length is infinite compared to the width. The fiber is generally made of a chain polymer material. A fiber generally has a large intermolecular force, a high glass transition point, and good crystallinity. The fiber generally has a large surface area and the molecules are oriented in the fiber direction.

  The raw material of the cellulose fiber is not particularly limited. Cellulose fibers are plant fibers, and cellulose fibers produced using pulp as a raw material are preferable. Cellulose, which is a polysaccharide, usually does not exist as a molecule, and has a multilayer structure such as cellulose microfibril (MFC) in which the cellulose molecules are aggregated, microfibril bundles in which the MFCs are aggregated, and aggregates thereof.

  The pulp is preferably a plant fiber produced using plant materials such as wood, bamboo, hemp, jute, kenaf, cotton, beet, agricultural wastes, and cloth as raw materials. As the wood that is the raw material of the pulp, sitka spruce, cedar, cypress, eucalyptus, acacia and the like are preferable. Pulp is obtained by pulping a plant material chemically and / or mechanically. Pulp is mainly composed of cellulose, hemicellulose and lignin. The lignin content in the pulp is usually about 0 to 40% by weight, preferably about 0 to 10% by weight. The lignin content can be measured by the Klason method.

  The cellulose fibers are preferably regenerated cellulose fibers such as rayon and cellophane. A commercial item can be used for a cellulose fiber, for example, KC flock (Nippon Paper Chemical Co., Ltd.) can be used.

(1-2) CNF
Cellulose nanofibers (CNF) are cellulose fibers obtained by defibrating cellulose fibers and reducing the fiber diameter to the nanosize level. CNF is a nano filler derived from natural raw materials, and is a composite material for resin having a low specific gravity and a high strength.

  In general, CNF is made of a cellulose fiber-containing material (water (Suspension or slurry) is mechanically ground and / or beaten to produce defibrated or refined.

  It can also be produced by a known method such as the method described in JP-A-2005-42283.

  CNF can also be produced using microorganisms (for example, acetic acid bacteria (Acetobacter) and the like).

  CNF can also use a commercial item, for example, can use serisch (Daicel Chemical Industries Ltd.) etc.

  The CNF may be treated with an alkali solution (for example, an alkali metal hydroxide aqueous solution, ammonia water or the like).

  CNF first forms the cellulose fiber-containing material into a shape (for example, powder, fiber, sheet, etc.) that enables efficient alkaline solution treatment using a refiner, ball mill, cutter mill, etc. Then, this processed product is obtained by grinding and / or beating with a known defibrating or refining technique used for the production of CNF, generally a high-pressure homogenizer, a medium stirring mill, a stone mill, a grinder, etc. Can do.

  The average fiber diameter of CNF is preferably about 4 nm to 800 nm, more preferably about 4 nm to 400 nm, and still more preferably 4 nm to 100 nm.

  CNF is a fiber having a very long fiber length with respect to the fiber diameter. The average fiber length of CNF is preferably about 5 times or more of the fiber diameter, more preferably about 10 times or more, and further preferably about 20 times or more. The average fiber length of CNF is preferably about 50 nm to 200 μm, more preferably about 100 nm to 50 μm.

The specific surface area of CNF is preferably about 70 to 300 m ² / g. When the specific surface area of CNF is large, the contact area with the resin increases when the composition is combined with the resin. Thereby, the intensity | strength of the resin composition containing CNF can be improved.

  CNF has a high specific surface area, is lightweight and has high strength. CNF has low thermal deformation (low thermal expansion).

  The average value of the CNF fiber diameter and the average fiber length (average fiber diameter and average fiber length) are calculated by measuring at least 50 CNFs in the field of view of the electron microscope.

(1-3) Non-fibrous anionized polysaccharide Non-fibrous anionized polysaccharide is a polysaccharide that does not have a fibrous structure. Non-fibrous solid, that is, solid having no fibrous structure, is, for example, a solid whose length is not so long with respect to its width, or isotropic solid that does not depend on a certain direction. Represents.

  The non-fibrous anionized polysaccharide is preferably a polysaccharide having a carboxymethyl group present in the polysaccharide main chain.

  The non-fibrous anionized polysaccharide is preferably carboxymethyl cellulose or a sodium salt thereof.

  As the non-fibrous anionized polysaccharide, it is preferable to use at least one component selected from the group consisting of these non-fibrous anionized polysaccharides. That is, these non-fibrous anionized polysaccharides may be used alone or in combination of two or more.

  The amount of anionic groups in the non-fibrous anionized polysaccharide is preferably about 0.5 to 1.5 per anhydroglucose.

(1-4) Cationizing agent A cationizing agent is an additive having a cationic group. For example, an aqueous solvent dispersion obtained by emulsifying and dispersing an alkyl ketene dimer with a cationic dispersion, a cationic polystyrene resin, a cationic fatty acid derivative, a cationic poly (meth) acrylic resin, a cationic polyester resin, a cationic polyolefin resin, Cationic polyether resins, cationic polyurethane resins, quaternary ammonium compounds and the like can be mentioned. Among these, a quaternary ammonium compound and a cationic acrylic resin are preferable.

Quaternary ammonium compound The quaternary ammonium compound preferably has a long-chain aliphatic hydrocarbon group or aromatic hydrocarbon group. Examples of such quaternary ammonium compounds include dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, behenyltrimethylammonium chloride, didecyldimethylammonium chloride, dioleyldimethylammonium chloride, tetradecyldimethylbenzylammonium chloride, and the like. Can be mentioned.

Cationic poly (meth) acrylic resin A water-soluble or water-dispersible resin having a cationic group and a (meth) acrylic skeleton is preferred. The structure of the (meth) acrylic resin has a resin affinity segment A and a cationic group segment B, each of which has a random structure, a block copolymer structure, or a gradient copolymer structure. You may do it.

  The block copolymer structure is a structure (for example, A-B, A-B-A, A-B-C, etc.) in which two or more kinds of polymer chains A, B, C,... Having different properties (for example, polarity) are linearly bonded. Examples thereof include an AB block copolymer structure in which the polymer chain A and the polymer chain B are linearly bonded. A block copolymer structure can be obtained by utilizing known living polymerization.

  Gradient copolymer structure is an example of a copolymer consisting of repeating units derived from two types of monomers A and B with different properties (such as polarity). From the end of the polymer chain rich in A unit, B unit It is a structure with a distribution gradient of repeating units such that the proportion of the A unit decreases and the proportion of the B unit increases as it goes to the other end rich in. By using known living polymerization, a gradient copolymer structure can be obtained.

  As monomer components of resin affinity segment A, methyl (meth) acrylate, ethyl (meth) acrylate, 2-methoxyethyl methacrylate, propyl (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, 4-t-butylcyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, isoboronyl (meth) ) Acrylate, trimethylcyclohexyl (meth) acrylate, cyclodecyl (meth) acrylate, cyclodecylmethyl (meth) acrylate, tricyclodecyl (meth) acrylate, dicyclope Butenyl oxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate, allyl (meth) acrylate, styrene and the like. The resin affinity segment A may be composed of one kind of the above-mentioned monomers, or may be composed of two or more kinds.

  Examples of the monomer component of the cationic group segment B include cationic unsaturated monomers.

  The cationic group segment B may be composed of one kind of cationic unsaturated monomer, or may be composed of two or more kinds.

  Examples of the cationic unsaturated monomer include compounds having an unsaturated bond and a primary to tertiary amino group in one molecule and salts thereof, compounds having a quaternary ammonium salt, and compounds having a primary amide group. It is done.

  Examples of the unsaturated monomer having a primary amino group include allylamine and methallylamine.

  Examples of the unsaturated monomer having a secondary amino group include diallylamine and dimethallylamine.

  Monomers having a tertiary amino group include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and N, N- Dialkylaminoalkyl (meth) acrylates such as diethylaminopropyl (meth) acrylate, dialkylaminoalkyl (meth) acrylamides such as N, N-dimethylaminoethyl (meth) acrylamide, and N, N-dimethylaminopropyl (meth) acrylamide, Examples include 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 1-vinylimidazole, and the like.

  As these unsaturated monomers having a primary to tertiary amino group, salts thereof can also be used. Examples of the salts include inorganic salts such as hydrochloride and sulfate, and organic acid salts such as formate and acetate.

In addition, in the monomer having a tertiary amino group,
An unsaturated monomer having the secondary amino group;
Alkyl halides such as methyl chloride, methyl bromide, (meth) allyl chloride, benzyl chloride, and benzyl bromide, alkyl sulfates such as dimethyl sulfate and diethyl sulfate, alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide, styrene oxide, There is also a monomer converted to an acid salt of a tertiary amine by reaction with epichlorohydrin and a glycidyl group-containing compound such as glycidyl trialkylammonium chloride, 3-chloro-2-hydroxypropyltrimethylammonium chloride, monochloroacetic acid, etc. Can be mentioned.

  Examples of unsaturated monomers that are quaternary ammonium salts include diallyldimethylammonium chloride, dimethallyldimethylammonium chloride, diallyldiethylammonium chloride, diethyldimethallylammonium chloride, and the like.

  Further, the unsaturated monomer that is a quaternary ammonium salt also includes an unsaturated monomer obtained by a reaction between the unsaturated monomer having the tertiary amino group and a quaternizing agent. . Quaternizing agents include alkyl halides such as methyl chloride, methyl bromide, (meth) allyl chloride, benzyl chloride, and benzyl bromide, alkyl sulfates such as dimethyl sulfate and diethyl sulfate, ethylene oxide, propylene oxide, and butylene oxide. Examples include alkylene oxide, styrene oxide, epichlorohydrin, and glycidyl group-containing compounds such as glycidyl trialkylammonium chloride, 3-chloro-2-hydroxypropyltrimethylammonium chloride, and sodium monochloroacetate.

4 after quaternization may be ion exchanged using ion exchange resin or the like, for example, or a carboxylate chloride ions or the like after conversion into a hydroxide ion, or _{^{NTf - (CF 3 SO 3 -}} ), PF It may be converted to a counter anion such as ₆ ⁻ or BF ₄ ⁻ .

Unsaturated monomers that are quaternary ammonium salts synthesized using these quaternizing agents include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meta ) Acryloyloxypropyldimethylbenzylammonium chloride, 2-hydroxy-3- (meth) acryloyloxypropyltrimethylammonium chloride, and the like.
The reaction with the quaternizing agent may be performed after polymerizing the unsaturated monomer having a tertiary amino group.

  Examples of the compound having a primary amide group include (meth) acrylamide.

  The cationic (meth) acrylic resin may use monomer components other than the resin affinity segment A and the cationic group segment B as necessary. For example, the cationic group segment B may be a copolymer of a hydrophilic monomer component such as 2-hydroxyethyl (meth) acrylate or polyethylene glycol methyl ether (meth) acrylate and a cationic monomer component.

  It is preferable to use at least one component selected from the group consisting of these cationizing agents as the cationizing agent. That is, these cationizing agents may be used alone or in combination of two or more.

The cationic group amount of the cationizing agent The degree of cationization of the cationizing agent can be calculated by the following method using a particle charge meter.

  After diluting the cationizing agent to 0.02% by mass with ion-exchanged water, 10 cc is sampled in a particle charge meter cell. Next, after adjusting to pH 3, titration is performed using a 1 / 1,000 N potassium polyvinyl sulfonate (PVSK) aqueous solution until the streaming potential becomes zero. Calculate the cationization degree (oxidation) of the cationizing agent from the titration of 1 / 1,000N PVSK aqueous solution and the following formula.

Cation degree (meq / g) = 1 / 1,000N Titration volume of PVSK aqueous solution (ml) / 2
The cationization degree of the cationizing agent is preferably about 0.80 to 2.00.

  By satisfying this range, the cationizing agent can be easily dissolved in water or dispersed in water, and the reaction between the cationizing agent and the non-fibrous anionized polysaccharide is uniform and easily proceeds uniformly.

(1-5) Other Embodiments The composition of the present invention can also be expressed as including a complex of a non-fibrous anionized polysaccharide and a cationizing agent and cellulose fibers. The composition of the present invention can also be expressed as a composition comprising an anionic cellulose fiber containing non-fibrous anionized polysaccharide and cellulose fiber, and a cationizing agent.

  The cellulose fiber may be CNF. The resin composition containing the said composition and resin is preferable. It is possible to prepare a molded body by molding this resin composition.

  The composite of the present invention can also be expressed as including a neutralized product of a non-fibrous anionized polysaccharide and a cationizing agent and cellulose fibers. The composite of the present invention can also be expressed as comprising a non-fibrous anionized polysaccharide, a cationizing agent, and cellulose fibers. The composite of the present invention can also be expressed as including an anionic cellulose fiber containing a non-fibrous anionized polysaccharide and a cellulose fiber, and a cationizing agent. In this case, the cellulose fiber treated with the non-fibrous anionized polysaccharide is called an anionic cellulose fiber.

  The composite of the present invention can also be expressed as non-fibrous anionized polysaccharide-modified cellulose fibers and a cationizing agent. The composite of the present invention can also be expressed as a cationizing agent adsorbed on anionic cellulose fibers containing non-fibrous anionized polysaccharide.

  The present invention can also be expressed as a modified cellulose fiber comprising a non-fibrous anionized polysaccharide and a cationizing agent. The present invention can also be expressed as a modified cellulose fiber containing a neutralized product of a non-fibrous anionized polysaccharide and a cationizing agent and a cellulose fiber. The present invention can also be expressed as an anionic cellulose fiber containing a non-fibrous anionized polysaccharide and a cellulose fiber, and a modified cellulose fiber containing a cationizing agent. In this case, the cellulose fiber treated with the non-fibrous anionized polysaccharide is referred to as an anionic cellulose fiber, and further includes a cationizing agent so as to be referred to as a modified cellulose fiber as a whole.

  The present invention can also be expressed as a modified cellulose fiber in which a neutralized product of a non-fibrous anionized polysaccharide and a cationizing agent is adsorbed on the cellulose fiber. The present invention can also be expressed as a modified cellulose fiber in which a cationizing agent is adsorbed on an anionic cellulose fiber containing a non-fibrous anionized polysaccharide. The present invention can also be expressed as a modified cellulose fiber obtained by treating a cellulose fiber treated with a non-fibrous anionized polysaccharide with a cationizing agent.

  The present invention can also be expressed as an anionic cellulose fiber containing non-fibrous anionized polysaccharide and cellulose fiber, and a neutralized product containing a cationizing agent.

  This invention is a resin composition containing the said composite and resin, and is a resin composition containing the said modified cellulose fiber and resin. This invention is a molded object formed by shape | molding the said resin composition.

(2) Composition and composite manufacturing method
(2-1) Composition and method for producing complex The composition or complex of the present invention comprises:
(1) a step of treating cellulose fibers with a non-fibrous anionized polysaccharide, and (2) a step of treating the cellulose fibers obtained in step 1 with a cationizing agent,
It can manufacture with the manufacturing method containing.

  In the resulting composite, it is preferable that a neutralized product of a non-fibrous anionized polysaccharide and a cationizing agent is adsorbed on cellulose fibers.

  In the present invention, a cellulose fiber obtained by treating a cellulose fiber with a non-fibrous anionized polysaccharide and then treating with a cationizing agent can also be referred to as a modified cellulose fiber.

Step 1: Step of treating cellulose fibers with non-fibrous anionized polysaccharide In step 1, the non-fibrous anionized polysaccharide can be added to and mixed with an aqueous dispersion in which cellulose fibers are dispersed. Since the non-fibrous anionized polysaccharide does not immediately dissolve in water, it is preferable to add a non-fibrous anionized polysaccharide previously dissolved in water. It is preferable to uniformly mix the cellulose fiber and the non-fibrous anionized polysaccharide using a stirring blade or the like. By mixing uniformly, the cellulose fibers are uniformly treated with the non-fibrous anionized polysaccharide.

Mixing ratio of cellulose fiber and non-fibrous anionized polysaccharide The mixing ratio of cellulose fiber and non-fibrous anionized polysaccharide is not particularly limited. The blending ratio (mass ratio) of cellulose fiber: non-fibrous anionized polysaccharide is preferably about 100: 1 to 100: 100, more preferably about 100: 5 to 100: 50, and about 100: 10 to 100: 40. Most preferred. By satisfying this range, the freeness of the cellulose fiber is good and the physical properties of the cellulose fiber are good.

Step 2: Step of treating the cellulose fiber obtained in Step 1 with a cationizing agent Step 2 is a step of applying a cationizing agent to the aqueous dispersion of cellulose fiber obtained by treating with the non-fibrous anionized polysaccharide obtained in Step 1. Can be added.

  The cationizing agent is preferably added dropwise to promote the reaction with the fibrous anionized polysaccharide.

  There is no particular limitation on the dropping time. The dropping time is preferably 10 minutes or longer. By applying for 10 minutes or more, the cationizing agent and the non-fibrous anionized polysaccharide gradually progress, so that water insolubilization is delayed and the reaction rate is improved. Further, it is preferable to uniformly mix the cellulose fiber treated with the non-fibrous anionized polysaccharide and the cationizing agent using a stirring blade or the like. By mixing uniformly, the reaction between the cationizing agent and the non-fibrous anionized polysaccharide proceeds uniformly and uniformly.

The mixing ratio of the non-fibrous anionized polysaccharide and the cationizing agent The mixing ratio of the non-fibrous anionized polysaccharide and the cationizing agent is not particularly limited. The blending ratio (mass ratio) of non-fibrous anionized polysaccharide: cationizing agent is preferably about 100: 1 to 100: 10,000, more preferably about 100: 5 to 100: 2,000, and about 100: 10 to 100: 500. Is most preferred. By satisfying this range, the neutralization reaction proceeds and the drainage increases.

Mixing ratio of cellulose fiber and modified part The mixing ratio of cellulose fiber and modified part (non-fibrous anionized polysaccharide + cationizing agent) is not particularly limited. The blending ratio (mass ratio) of cellulose fiber: modified part is preferably about 100: 1 to 100: 1,000, more preferably about 100: 10 to 100: 500, and most preferably about 100: 40 to 100: 200. . By satisfying this range, the freeness of the cellulose fiber is good and the physical properties of the cellulose fiber are good.

(2-2) Composition and composite production method (CNF 1)
When the cellulose fiber contained in the composition or composite of the present invention is CNF,
(1) a step of treating cellulose fibers with a non-fibrous anionized polysaccharide;
(2) It can be produced by a production method comprising a step of treating the cellulose fiber obtained in step 1 with a cationizing agent, and (3) a step of defibrating the modified cellulose fiber obtained in step 2.

Step 1: Step of treating cellulose fiber with non-fibrous anionized polysaccharide The same as Step 1 of the method for producing the modified cellulose fiber.

Step 2: A step of treating the cellulose fiber obtained in Step 1 with a cationizing agent The same as Step 2 of the method for producing the modified cellulose fiber.

Step 3: Step of defibrating the modified cellulose fiber obtained in Step 2 Step 3 can be defibrated by applying mechanical shear force to the modified cellulose fiber obtained in Step 2 in a solvent or resin. it can.

  This modified cellulose fiber is obtained by treating a cellulose fiber with a non-fibrous anionized polysaccharide and then with a cationizing agent. A composition comprising a fiber "," a composition comprising a neutralized product of a non-fibrous anionized polysaccharide and a cationizing agent and a cellulose fiber ", or" a non-fibrous anionized polysaccharide and a cationized cellulose fiber. A composite in which a neutralized product with an agent is adsorbed ”.

  The defibrating treatment is preferably performed in the resin from the viewpoint of easy mixing with the molding resin.

  As a means for giving a shearing force, a means such as a bead mill, an ultrasonic homogenizer, an extruder such as a single screw extruder or a twin screw extruder, a Banbury mixer, a grinder, a pressure kneader, a known kneader such as a two-roll machine, or the like is used. It is preferable.

(2-3) Composition and composite manufacturing method (CNF 2)
When the cellulose fiber contained in the composition or composite of the present invention is CNF,
(1) a step of treating CNF with a non-fibrous anionized polysaccharide, and (2) a step of treating CNF obtained in step 1 with a cationizing agent,
It can manufacture with the manufacturing method containing.

Step 1: Process of treating CNF with non-fibrous anionized polysaccharide In Step 1, raw material and CNF are used, and the non-fibrous anionized polysaccharide can be added to an aqueous dispersion in which CNF is dispersed and mixed. Since the non-fibrous anionized polysaccharide does not immediately dissolve in water, it is preferable to add a non-fibrous anionized polysaccharide previously dissolved in water. Further, it is desirable to uniformly mix CNF and non-fibrous anionized polysaccharide using a stirring blade or the like. By mixing uniformly, CNF is uniformly treated with non-fibrous anionized polysaccharide.

Ratio of CNF to non-fibrous anionized polysaccharide
The mixing ratio of CNF and non-fibrous anionized polysaccharide is not particularly limited. The blending ratio (mass ratio) of cellulose fiber: non-fibrous anionized polysaccharide is preferably about 100: 1 to 100: 100, more preferably about 100: 5 to 100: 50, and about 100: 10 to 100: 40. Most preferred. By satisfying this range, the freeness of the cellulose fiber is good and the physical properties of the cellulose fiber are good.

Step 2: Treating the CNF obtained in Step 1 with a cationizing agent The step of treating the CNF obtained in Step 1 with a cationizing agent is treated with the non-fibrous anionized polysaccharide obtained in Step 1. A cationizing agent may be added to an aqueous dispersion of CNF. The cationizing agent is preferably added dropwise to promote the reaction with the fibrous anionized polysaccharide. The dropping time is not particularly limited, but is preferably 10 minutes or longer. By applying for 10 minutes or more, the cationizing agent and the non-fibrous anionized polysaccharide gradually progress, so that water insolubilization is delayed and the reaction rate is improved.

  In addition, it is desirable to uniformly mix CNF treated with non-fibrous anionized polysaccharide and a cationizing agent using a stirring blade or the like. By mixing uniformly, the reaction between the cationizing agent and the non-fibrous anionized polysaccharide proceeds evenly.

Ratio of non-fibrous anionized polysaccharide and cationizing agent The mixing ratio of the non-fibrous anionized polysaccharide and cationizing agent is not particularly limited. The blending ratio (mass ratio) of non-fibrous anionized polysaccharide: cationizing agent is preferably about 100: 1 to 100: 10,000, more preferably about 100: 5 to 100: 2,000, and about 100: 10 to 100: 500. Is most preferred. By satisfying this range, the neutralization reaction proceeds and the drainage increases.

Ratio of CNF and modified part (non-fibrous anionized polysaccharide + cationizing agent)
The mixing ratio of CNF and the modified part (non-fibrous anionized polysaccharide + cationizing agent) is not particularly limited. The blending ratio (mass ratio) of cellulose fiber: modified part is preferably about 100: 1 to 100: 1,000, more preferably about 100: 10 to 100: 500, and most preferably about 100: 40 to 100: 200. . By satisfying this range, the freeness of the cellulose fiber is good and the physical properties of the cellulose fiber are good.

(3) Recovery of cellulose fiber and CNF As a method of recovering cellulose fiber or CNF, a method of separating solids in an aqueous medium is preferable. Methods such as filter filtration, filter press, and centrifugation are preferred.

  The recovered cellulose fiber or CNF can be further dried with a drier, and can be prepared in a powder form with a crusher or the like. The recovered cellulose fiber or CNF can also be dried to prepare a sheet.

  In the present invention, the state before recovering cellulose fibers or CNF or the state after recovering cellulose fibers or CNF can be referred to as a composition or a composite.

(4) Resin composition
(4-1) Blending of cellulose fibers and CNF into resin Cellulose fibers or CNF recovered by filtering from an aqueous medium (composition or composite) can be suitably blended into a molding resin. In the present invention, it is also possible to blend the composition or composite into a molding resin.

  As the molding resin, a thermosetting resin, a radical curable resin, a thermoplastic resin, or the like is preferable.

Thermosetting resin A well- known thermosetting resin can be used. Preference is given to thermosetting resins such as phenol resins, urea resins, melamine resins, unsaturated polyester resins, epoxy resins, diallyl phthalate resins, polyurethane resins, silicon resins, polyimide resins and the like.

  These components are preferably at least one component.

Radical curable resin The radical curable resin does not particularly require heat, and is preferably a resin that radically cures when exposed to light, radiation, or at room temperature. An acrylic resin or the like is preferable.

The thermoplastic resin is not basically limited, and a known thermoplastic resin can be used.

  Polyolefin resins such as polyethylene and polypropylene are preferred. Polyester resins such as polyethylene terephthalate and polybutylene terephthalate are preferred. Acrylic resin fats such as polymethyl methacrylate and polyethyl methacrylate are preferred. Styrene resins such as polystyrene, acrylonitrile-butadiene-styrene resin, acrylonitrile-acrylic rubber-styrene resin, acrylonitrile-ethylene rubber-styrene resin, (meth) acrylic ester-styrene resin, styrene-butadiene-styrene resin are preferable. Polyamide resins such as ionomer resins, polyacrylonitrile, and nylon are preferred. Chlorine resins such as ethylene-vinyl acetate resin, ethylene-acrylic acid resin, ethylene-ethyl acrylate resin, ethylene-vinyl alcohol resin, polyvinyl chloride, and polyvinylidene chloride are preferable. Fluorine resins such as polyvinyl fluoride and polyvinylidene fluoride are preferred. Thermoplastic resins such as polycarbonate resin, modified polyphenylene ether resin, methylpentene resin, and cellulose resin are preferred. Preferred are thermoplastic elastomers such as olefin elastomers, vinyl chloride elastomers, styrene elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, and the like. A mixture of seeds or more can be mentioned.

  These components are preferably at least one component.

Blending Cellulose Fiber and CNF into Molding Resin It is preferable to use at least one component selected from the group consisting of the above resins. That is, these resins may be used alone or in combination of two or more.

  The method for blending cellulose fibers or CNF into the molding resin is not particularly limited. Cellulose fibers or CNF sheets or aggregates can be impregnated with a molding resin. Cellulose fiber or CNF can be dried and ground and mixed with the molding resin. In the case of a molding resin kneaded at a high temperature, wet cellulose fibers or CNF and the molding resin may be mixed to remove moisture from the kneading.

Cellulose Fiber or CNF Content The cellulose fiber or CNF content of the resin composition is preferably about 0.1 to 30% by mass of CNF excluding the modified portion. When the content of CNF satisfies this range, the reinforcing effect by CNF can be exhibited well, and the resin composition can be molded well.

(4-2) Additives to resin composition The resin composition may contain various additives as long as the effects of the invention are not impaired. For example, organic or inorganic fillers, pigments, thickeners, thickeners, plasticizers, light resistant additives (ultraviolet absorbers, stabilizers, etc.), antioxidants, antiozonants, activators, antistatic agents Addition of lubricants, anti-friction agents, surface conditioners (leveling agents, antifoaming agents, anti-blocking agents, etc.), anti-fungal agents, antibacterial agents, dispersants, flame retardants and wake accelerators and auxiliaries An agent can be blended.

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

(5) Resin molding
Manufacture of a molded product The resin composition can be manufactured by a known and commonly used molding resin composition molding method. It is preferable to use a molding method such as compression molding, injection molding, extrusion molding, or foam molding. The molding conditions can be adapted by appropriately adjusting the molding conditions of the resin as necessary.

Use of molded product The modified CNF-containing resin molded product obtained is lightweight and has high strength.

  The modified CNF-containing resin molded product can be used in a field where mechanical strength is required. For example, it is preferably used for interior materials, exterior materials, structural materials, and the like of transportation equipment such as automobiles, trains, ships, and airplanes. It is preferable to use it for housings, structural materials, internal parts, etc. of electrical appliances such as personal computers, televisions and telephones. It is preferably used for a housing of office equipment such as building materials, stationery, and OA equipment. It is preferably used for sports / leisure goods and structural materials.

(1) Preparation of cellulose fiber and cationizing agent
Production Example 1: Pulp 1 (cellulose fiber)
Refiner treatment was repeated with a single disc refiner (manufactured by Kumagai Riki Kogyo Co., Ltd.) until the Canadian standard freeness was 100 mL or less for the slurry of coniferous bleached kraft pulp (NBKP) (slurry concentration: 2 mass%). Dehydration was performed by pressure filtration to obtain Pulp 1.

  The moisture content of this pulp 1 was 81.2% by mass when measured under the condition of 110 ° C. using an infrared moisture meter FD-720 manufactured by Kett Science Laboratory.

  Hereinafter, the moisture content was measured under the condition of 110 ° C. using an infrared moisture meter FD-720 manufactured by Kett Science Laboratory.

Cationizing agent 1: Acrylic resin A water-dispersible resin having a cationic group and a (meth) acrylic skeleton, and having a resin affinity segment A and a cationic group segment B.

Monomer component of resin affinity segment A: lauryl methacrylate Monomer component of cationic group segment B: acrylamide While charging 600 parts of isopropyl alcohol in a four-necked flask equipped with a thermometer, stirrer, nitrogen introduction tube, and cooling tube, stirring The reaction vessel was purged with nitrogen. The temperature inside the reaction vessel was raised to 80 ° C. while maintaining a nitrogen atmosphere, and then 100 parts of synthetic lauryl methacrylate (“Blenmer (registered trademark) SLMA” manufactured by NOF Corporation), 300 parts of acrylamide, t-butyl per A mixed solution of 27 parts of oxy (2-ethylhexanoate) (“Perbutyl (registered trademark)” O manufactured by NOF Corporation) was dropped over 2 hours and 30 minutes.

  After completion of the dropwise addition, the reaction was further continued for 11 hours at the same temperature. Two hours later, t-butyl peroxy (2-ethylhexanoate) (“Perbutyl (registered trademark) O” manufactured by NOF CORPORATION) was added in two portions 3 hours and 6 hours after the completion of the dropping. After completion of the reaction, 1,000 g of water was added to room temperature.

  Isopropylpyr alcohol (IPA) was distilled off under reduced pressure, and water was further added to obtain a 4% by mass acrylic resin aqueous solution.

Cationizing agent 2: Block dispersant 1
This is a 4% by mass solution of a water-dispersible resin having a cationic group and a (meth) acryl skeleton and having a resin affinity segment A having a block copolymer structure and a cationic group segment B having a block copolymer structure.

Monomer component of polymer block A (resin affinity segment):
Dimethyldiglycol (DMDG): 106 parts Dicyclopentenyloxyethyl methacrylate (DCPOEMA): 62 parts Iodine: 1.0 part Diphenylmethane (DPM): 0.2 part
Monomer component of polymer block B (cationic group segment):
2- (dimethylamino) ethyl methacrylate (DMAEMA): 38 parts

Cationizing agent 3: Block dispersant 2
This is a 4% by mass solution of a water-dispersible resin having a cationic group and a (meth) acryl skeleton and having a resin affinity segment A having a block copolymer structure and a cationic group segment B having a block copolymer structure.

Monomer component of polymer block A (resin affinity segment):
DMDG: 106 copies
DCPOEMA: 85 parts Iodine: 1.0 part
DPM: 0.2 parts
Monomer component of polymer block B (cationic group segment)
DMAEMA: 15 copies

Cationizing agent 4: Commercial product (4% by mass)
Dioleyldimethylammonium chloride made by NOF Corporation Nissan Cation (registered trademark) 2-OLR

Method for calculating degree of cationization The degree of cationization was determined using a particle charge meter PCD-02 manufactured by Spectris Co., Ltd.

  The measurement method is shown below.

  After diluting the cationizing agent to 0.02% by mass with ion-exchanged water, 10 cc was sampled in a PCD-02 cell. Subsequently, after adjusting to pH 3, it titrated using 1 / 1,000N potassium polyvinyl sulfonate (PVSK) aqueous solution until a streaming potential became zero. The cationization degree (acid value) of the cationizing agent was calculated from the titration of 1 / 1,000N PVSK aqueous solution and the following formula.

      Cation degree (meq / g) = 1 / 1,000N Titration volume of PVSK aqueous solution (ml) / 2

(2) Preparation of composition or composite (containing cellulose fiber or CNF)
Example
Example 1: Production of Cellulose Fiber 1 Cellogen (registered trademark) 5A (Carboxymethylcellulose manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (hereinafter abbreviated as CMC)) 40 g was dissolved in 960 g of water to prepare a 4% by mass CMC aqueous solution. (Non-fibrous anionized polysaccharide).

  Into a 10 L stainless steel container, 532 g of pulp 1 (cellulose fiber) produced in Production Example 1 (solid content: 100 g), 750 g of 4% by weight CMC aqueous solution (solid content: 30 g), and 2,718 g of water were charged, and a stirring blade was used. The mixture was stirred at 150 rpm for 2 hours.

  While stirring at a rotational speed of 150 rpm, 2,350 g (94 g solid content) of a 4% by mass acrylic resin aqueous solution (cationizing agent 1) was dropped into the solution over 10 minutes. After completion of dropping, the mixture was further stirred for 1 hour.

  Thereafter, pressure filtration was performed at 0.3 MPa. Filtration was performed until the filtrate did not come out for 1 minute or longer, and cellulose fiber 1 was obtained.

  The moisture content of the cellulose fiber 1 was less than 30%. Cellulose fiber 1 was dried with a dryer at 110 ° C. for 16 hours, and then pulverized with a pulverizer (sanitary crusher manufactured by Sansho Industry Co., Ltd.) to obtain powdered cellulose fiber 1. The moisture content of the powdered cellulose fiber 1 was 2.0% by mass. Further, the adsorption amount of the non-fibrous anionized polysaccharide and the cationizing agent calculated from the dry weight was 99% or more.

Evaluation of drainage The moisture content of cellulose fiber 1 after pressure filtration was measured.

Freeness x: When the water content is 70% or more Freeness △: When the water content is 30% or more and less than 70% Freeness ○: When the water content is less than 30%

  Hereinafter, the same determination was made for Examples 2 to 9 and Comparative Examples 1 to 5.

Production of Cellulose Fiber (CNF) -Containing Composition 1 (PE Composite 1) Suntech (registered trademark) J320 (High Density Polyethylene (PE) manufactured by Asahi Kasei Chemicals Corporation) was pulverized using a 1.3 mm screen. 155.7 g of pulverized PE (J320) and 45.7 g (solid content 44.8 g) of the cellulose fiber 1 were mixed, and a twin-screw kneader (KZW manufactured by Technobel Co., Ltd., screw diameter: 1) mm, L / D: 45, screw rotation speed: 200 rpm) at 140 ° C. for one pass. Cellulose nanofiber composite PE1 (CNF composite PE1) was obtained by pelletizing the obtained melt-kneaded product using a pelletizer (manufactured by Technobel Co., Ltd.).

  Aggregates were not observed by visual confirmation of the film. Even in the observation with a polarizing microscope, CNF was clearly dispersed.

Confirmation of dispersibility by visual observation and dispersibility by polarizing microscope 0.5 g of the pelletized CNF composite PE1 is sandwiched between polyester films (Lumirror (registered trademark) T60 # 188 manufactured by Toray Industries, Inc.), and the outside is 3 mm thick. Sandwiched between metal plates. It was set in a 160 ° C hot press. Pressing was performed at 3,000 kg / cm ² and 160 ° C. for 3 minutes.

  After cooling to room temperature, cellulose nanofiber composite PE film 1 (CNF composite PE film 1) was obtained.

  The CNF composite PE film 1 was visually checked for the presence of aggregates.

Visual dispersibility ×: with aggregates Visual dispersibility ○: without aggregates

  Next, the CNF composite PE film 1 was observed with a polarizing microscope at 80 times.

Polarizing microscope dispersibility x: Cellulose lump confirmed Polarizing microscope dispersibility ○: Cellulose lump not confirmed

  Hereinafter, the same determination was made for Examples 2 to 9 and Comparative Examples 1 to 5.

Evaluation of moldability A tensile test was conducted according to ASTM D638 using the pelletized CNF composite PE1. The test size was TYPE IV. An injection molding machine (iM18 manufactured by Sumitomo Heavy Industries, Ltd.) was used as the injection molding machine, and molding was performed under the conditions of an injection temperature of 160 ° C. and a mold temperature of 40 ° C. A universal testing machine (Instron 3365 type testing machine manufactured by Instron Japan Ltd.) was used as the testing machine.

Determination of the refined state of cellulose fibers From the test piece obtained by the above molding, a section was cut out with a microtome, and the cellulose fibers were observed with a transmission microscope (TEM). Ten photos were taken at 10,000 times magnification.

Fine state ○: When the ratio of the number of cellulose fibers of 500 nm or less is 50% or more Fine state Δ: When the ratio of the number of the cellulose fibers of 500 nm or less is 10% or more and less than 50% Fine state x: When the ratio of the number of cellulose fibers of 500 nm or less is less than 10%

  Hereinafter, the same determination was made for Examples 2 to 9 and Comparative Examples 1 to 5.

Example 2 Production of Cellulose Fiber 2 Serogen (registered trademark) 5A (CMC made by Daiichi Kogyo Seiyaku Co., Ltd.) 20 g was dissolved in 480 g of water to prepare a 4% by mass CMC aqueous solution (non-fibrous anionized polysaccharide). did.

  Into a 10-liter stainless steel container, 532 g of pulp 1 (cellulose fiber) produced in Production Example 1 (solid content 100 g), 375 g of 4% by weight CMC aqueous solution (solid content 15 g), and 3,093 g of water were charged, and a stirring blade was used. The mixture was stirred at 150 rpm for 2 hours.

  While stirring at a rotational speed of 150 rpm, 1,175 g (47 g solid content) of a 4% by mass acrylic resin aqueous solution (cationizing agent 1) was dropped into the solution over 10 minutes. After completion of dropping, the mixture was further stirred for 1 hour.

  Thereafter, pressure filtration was performed at 0.3 MPa. Filtration was performed until the filtrate did not come out for 1 minute or longer, and cellulose fiber 2 was obtained.

  The moisture content of the cellulose fiber 2 was less than 30%. Cellulose fiber 2 was dried with a dryer at 110 ° C. for 16 hours, and then pulverized with a pulverizer (Sanitary Crusher manufactured by Sansho Industry Co., Ltd.) to obtain powdered cellulose fiber 2. The moisture content of the powdered cellulose fiber 2 was 1.9% by mass. Further, the adsorption amount of the non-fibrous anionized polysaccharide and the cationizing agent calculated from the dry weight was 99% or more.

Manufacture of cellulose fiber (CNF) -containing composition 2 (CNF composite PE2) 33.0 g (32.4 g solid content) of cellulose fiber 2 and 167.6 g of PE (J320) pulverized in Example 1 were mixed, and a twin-screw kneader (KZW manufactured by Technobel Co., Ltd., screw diameter: 15 mm, L / D: 45, screw rotation speed: 200 rpm), and one pass at 140 ° C. Cellulose nanofiber composite PE2 (CNF composite PE2) was obtained by pelletizing the obtained melt-kneaded product using a pelletizer (manufactured by Technobel Co., Ltd.).

  As a result of TEM observation, nanofibers were confirmed. In addition, no aggregates were observed in the visual confirmation of the film. Even in the observation with a polarizing microscope, CNF was clearly dispersed.

Evaluation of moldability A tensile test was conducted according to ASTM D638 using the pelletized CNF composite PE2. The test size was TYPE IV. An injection molding machine (iM18 manufactured by Sumitomo Heavy Industries, Ltd.) was used as the injection molding machine, and molding was performed under the conditions of an injection temperature of 160 ° C. and a mold temperature of 40 ° C. A universal testing machine (Instron 3365 type testing machine manufactured by Instron Japan Company Limited) was used as a testing machine.

Example 3 Production of Cellulose Nanofiber Composite PE3 (CNF Composite PE3) 99.1 g (solid content 97.2 g) of cellulose fiber 2 of Example 2 and 102.8 g of PE (J320) pulverized in Example 1 were mixed. One pass was carried out at 140 ° C. with a shaft kneader (KZW manufactured by Technobel Co., Ltd., screw diameter: 15 mm, L / D: 45, screw rotation speed: 200 rpm). Cellulose nanofiber composite PE3 (CNF composite PE3) obtained by pelletizing the obtained melt-kneaded product using a pelletizer (manufactured by Technobel Co., Ltd.) was obtained.

  As a result of TEM observation, nanofibers were confirmed. In addition, no aggregates were observed in the visual confirmation of the film. Even in the observation with a polarizing microscope, CNF was clearly dispersed.

Evaluation of moldability A tensile test was conducted according to ASTM D638 using the pelletized CNF composite PE3. The test size was TYPE IV. An injection molding machine (iM18 manufactured by Sumitomo Heavy Industries, Ltd.) was used as the injection molding machine, and molding was performed under the conditions of an injection temperature of 160 ° C. and a mold temperature of 40 ° C. A universal testing machine (Instron 3365 type testing machine manufactured by Instron Japan Company Limited) was used as a testing machine.

Example 4: Production of cellulose fiber 3
40 g of CMC Daicel (registered trademark) 1330 (CMC manufactured by Daicel Finechem Co., Ltd.) was dissolved in 960 g of water to prepare a 4% by mass CMC aqueous solution (non-fibrous anionized polysaccharide).

  In a 10L stainless steel container, 532 g of pulp 1 (cellulose fiber) produced in Production Example 1 (solid content 100 g), 925 g of 4% by weight CMC aqueous solution (solid content 37 g), and 2,543 g of water were charged, and a stirring blade was used. The mixture was stirred at 150 rpm for 2 hours.

  While stirring at a rotational speed of 150 rpm, 1,575 g (solid content 63 g) of a 4% by mass acrylic resin aqueous solution (cationizing agent 1) was dropped into the solution over 10 minutes. After completion of dropping, the mixture was further stirred for 1 hour. Thereafter, pressure filtration was performed at 0.3 MPa. Filtration was performed until the filtrate did not come out for 1 minute or longer, and cellulose fiber 3 was obtained.

  The moisture content of the cellulose fiber 3 was less than 30%. Cellulose fiber 3 was dried for 16 hours with a dryer at 110 ° C., and then pulverized with a pulverizer (Sanitary Crusher manufactured by Sansho Industry Co., Ltd.) to obtain powdered cellulose fiber 3. The moisture content of the powdered cellulose fiber 3 was 2.4% by mass. Further, the adsorption amount of the non-fibrous anionized polysaccharide and the cationizing agent calculated from the dry weight was 99% or more.

Manufacture of cellulose fiber (CNF) -containing composition 4 (CNF composite PE4) 41.0 g (solid content 40.0 g) of cellulose fiber 3 and 160.0 g of PE (J320) pulverized in Example 1 were mixed, and a twin-screw kneader (KZW manufactured by Technobel Co., Ltd., screw diameter: 15 mm, L / D: 45, screw rotation speed: 200 rpm), and one pass at 140 ° C. Cellulose nanofiber composite PE4 (CNF composite PE4) was obtained by pelletizing the obtained melt-kneaded product using a pelletizer (manufactured by Technobel Co., Ltd.).

  As a result of TEM observation, nanofibers were confirmed. In addition, no aggregates were observed in the visual confirmation of the film. Even in the observation with a polarizing microscope, CNF was clearly dispersed.

Evaluation of Formability A tensile test was performed according to ASTM D638 using the pelletized CNF composite PE4. The test size was TYPE IV. An injection molding machine (iM18 manufactured by Sumitomo Heavy Industries, Ltd.) was used as the injection molding machine, and molding was performed under the conditions of an injection temperature of 160 ° C. and a mold temperature of 40 ° C. A universal testing machine (Instron 3365 type testing machine manufactured by Instron Japan Company Limited) was used as a testing machine.

Example 5: Production of Cellulose Fiber 4 40 g of Celogen (registered trademark) 5A (CMC manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was dissolved in 960 g of water to prepare a 4% by mass CMC aqueous solution (non-fibrous anionized polysaccharide). did.

  Cellulose nanofiber (CNF) (Selish (registered trademark) KY-100G manufactured by Daicel FineChem, Inc., solid content concentration: 10% by mass)) 250 g (solid content 25.0 g (cellulose fiber)), 4 A mass% LC-100 aqueous solution (187.5 g, solid content: 7.5 g) and water (4,562.5 g) were charged, and the mixture was stirred with a stirring blade at 150 rpm for 2 hours.

  While stirring at a rotational speed of 150 rpm, 587.5 g (solid content 23.5 g) of a 4% by mass acrylic resin aqueous solution (cationizing agent 1) was dropped into the solution over 10 minutes. After completion of dropping, the mixture was further stirred for 1 hour. Thereafter, pressure filtration was performed at 0.3 MPa. Filtration was performed until the filtrate did not come out for 1 minute or more to obtain CNF4.

  The moisture content of this CNF4 was less than 30%. CNF4 was dried with a dryer at 110 ° C. for 16 hours and then pulverized with a pulverizer (sanitary crusher manufactured by Sansho Industry Co., Ltd.) to obtain powdered CNF4. The moisture content of powdered CNF4 was 2.1%. Further, the adsorption amount of the non-fibrous anionized polysaccharide and the cationizing agent calculated from the dry weight was 99% or more.

Production of cellulose nanofiber (CNF) -containing composition 5 (CNF composite PE5) 45.8 g (solid content 44.8 g) of CNF4 and 155.2 g of PE (J320) pulverized in Example 1 were mixed, and a twin-screw kneader ( One pass was performed at 140 ° C. with KZW manufactured by Technobel, screw diameter: 15 mm, L / D: 45, screw rotation speed: 200 rpm. The obtained melt-kneaded product was pelletized using a pelletizer (manufactured by Technobel Co., Ltd.) to obtain CNF-containing composition 5 (CNF composite PE5).

  As a result of TEM observation, nanofibers were confirmed. In addition, no aggregates were observed in the visual confirmation of the film. Even in the observation with a polarizing microscope, CNF was clearly dispersed.

Evaluation of moldability A tensile test was conducted according to ASTM D638 using the pelletized CNF composite PE5. The test size was TYPE IV. An injection molding machine (iM18 manufactured by Sumitomo Heavy Industries, Ltd.) was used as the injection molding machine, and molding was performed under the conditions of an injection temperature of 160 ° C. and a mold temperature of 40 ° C. A universal testing machine (Instron 3365 type testing machine manufactured by Instron Japan Company Limited) was used as a testing machine.

Example 6: Production of cellulose fiber 5 Cellogen (registered trademark) 5A (CMC manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 40 g was dissolved in 960 g of water to prepare a 4% by mass CMC aqueous solution (non-fibrous anionized polysaccharide). did.

  Nissan Cation (registered trademark) 2-OLR (Dioleyldimethylammonium chloride manufactured by NOF Corporation) was diluted with water to obtain a 4% by mass solution of the cationizing agent 4.

  Into a 10L stainless steel container, 532 g of pulp 1 (cellulose fiber) produced in Production Example 1 (solid content: 100 g), 850 g of 4% by weight CMC aqueous solution (solid content: 34 g) and 2,618 g of water were charged, and a stirring blade was used. The mixture was stirred at 150 rpm for 2 hours.

  While stirring at 150 rpm, 1,650 g (66 g solid content) of the cationizing agent 4 solution was dropped into the solution over 10 minutes. After completion of dropping, the mixture was further stirred for 1 hour. Thereafter, pressure filtration was performed at 0.3 MPa. Filtration was performed until the filtrate did not come out for 1 minute or longer, and cellulose fiber 5 was obtained.

  The moisture content of the cellulose fiber 5 was less than 30%. Cellulose fiber 5 was dried with a dryer at 110 ° C. for 16 hours and then pulverized with a pulverizer (sanitary crusher manufactured by Sansho Industry Co., Ltd.) to obtain powdered cellulose fiber 5. The moisture content of the powdered cellulose fiber 5 was 2.5%. Further, the adsorption amount of the non-fibrous anionized polysaccharide and the cationizing agent calculated from the dry weight was 99% or more.

Manufacture of cellulose fiber (CNF) -containing composition 6 (CNF composite PE6) 41.0 g (solid content 40.0 g) of cellulose fiber 5 and 160.0 g of PE (J320) pulverized in Example 1 were mixed, and a twin-screw kneader (KZW manufactured by Technobel Co., Ltd., screw diameter: 15 mm, L / D: 45, screw rotation speed: 200 rpm), and one pass at 140 ° C. The obtained melt-kneaded product was pelletized using a pelletizer (manufactured by Technobel Co., Ltd.) to obtain a CNF-containing composition 6 (CNF composite PE6).

  As a result of TEM observation, nanofibers were confirmed. In addition, no aggregates were observed in the visual confirmation of the film. Even in the observation with a polarizing microscope, CNF was clearly dispersed.

Evaluation of moldability A tensile test was conducted according to ASTM D638 using the pelletized CNF composite PE6. The test size was TYPE IV. An injection molding machine (iM18 manufactured by Sumitomo Heavy Industries, Ltd.) was used as the injection molding machine, and molding was performed under the conditions of an injection temperature of 160 ° C. and a mold temperature of 40 ° C. A universal testing machine (Instron 3365 type testing machine manufactured by Instron Japan Company Limited) was used as a testing machine.

Example 7: Production of cellulose fiber 6
20 g of CMC Daicel (registered trademark) 1330 (CMC manufactured by Daicel FineChem Co., Ltd.) was dissolved in 480 g of water to prepare a 4 mass% CMC aqueous solution (non-fibrous anionized polysaccharide).

  Nissan Cation (registered trademark) 2-OLR (Dioleyldimethylammonium chloride manufactured by NOF Corporation) was diluted with water to obtain a 4% by mass solution of the cationizing agent 4.

  Into a 10 L stainless steel container, 532 g of pulp 1 (cellulose fiber) produced in Production Example 1 (solid content 100 g), 425 g of 4% by weight CMC aqueous solution (solid content 17 g) and 3,043 g of water were charged, and a stirring blade was used. The mixture was stirred at 150 rpm for 2 hours.

  While stirring at 150 rpm, 825 g (33 g solid content) of the cationizing agent 4 solution was dropped into the solution over 10 minutes. After completion of dropping, the mixture was further stirred for 1 hour. Thereafter, pressure filtration was performed at 0.3 MPa. Filtration was performed until the filtrate did not come out for 1 minute or longer, and cellulose fiber 6 was obtained.

  The moisture content of the cellulose fiber 6 was less than 30%. Cellulose fibers 6 were dried for 16 hours with a dryer at 110 ° C. and then pulverized with a pulverizer (sanitary crusher manufactured by Sansho Industry Co., Ltd.) to obtain powdered cellulose fibers 6. The moisture content of the powdered cellulose fiber 6 was 1.9%. Further, the adsorption amount of the non-fibrous anionized polysaccharide and the cationizing agent calculated from the dry weight was 99% or more.

Production of cellulose fiber (CNF) -containing composition 7 (CNF composite PE7) 30.6 g (solid content 30.0 g ) of cellulose fiber 6 and 170.0 g of PE (J320) pulverized in Example 1 were mixed, and a twin-screw kneader (KZW manufactured by Technobel Co., Ltd., screw diameter: 15 mm, L / D: 45, screw rotation speed: 200 rpm), and one pass at 140 ° C. Cellulose nanofiber composite PE7 (CNF composite PE7) was obtained by pelletizing the obtained melt-kneaded product using a pelletizer (manufactured by Technobel Co., Ltd.).

  As a result of TEM observation, nanofibers were confirmed. In addition, no aggregates were observed in the visual confirmation of the film. Even in the observation with a polarizing microscope, CNF was clearly dispersed.

Evaluation of moldability A tensile test was conducted according to ASTM D638 using the pelletized CNF composite PE7. The test size was TYPE IV. An injection molding machine (iM18 manufactured by Sumitomo Heavy Industries, Ltd.) was used as the injection molding machine, and molding was performed under the conditions of an injection temperature of 160 ° C. and a mold temperature of 40 ° C. A universal testing machine (Instron 3365 type testing machine manufactured by Instron Japan Company Limited) was used as a testing machine.

Example 8: Production of cellulose fiber 7 Cellogen (registered trademark) 5A (CMC manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 40 g was dissolved in 960 g of water to prepare a 4% by mass CMC aqueous solution (non-fibrous anionized polysaccharide). did.

  Into a 10 L stainless steel container, 532 g of pulp 1 (cellulose fiber) produced in Production Example 1 (solid content: 100 g), 750 g of 4% by weight CMC aqueous solution (solid content: 30 g), and 2,718 g of water were charged, and a stirring blade was used. The mixture was stirred at 150 rpm for 2 hours.

  While stirring at 150 rpm, 1,300 g (52 g solid content) of a 4 mass% block dispersant 1 solution (cationizing agent 2) was added dropwise over 10 minutes. After completion of dropping, the mixture was further stirred for 1 hour. Thereafter, pressure filtration was performed at 0.3 MPa. Filtration was performed until the filtrate did not come out for 1 minute or longer, and cellulose fiber 7 was obtained.

  The moisture content of the cellulose fiber 7 was less than 30%. Cellulose fibers 7 were dried with a dryer at 110 ° C. for 16 hours, and then pulverized with a pulverizer (sanitary crusher manufactured by Sansho Industry Co., Ltd.) to obtain powdered cellulose fibers 7. The moisture content of the powdered cellulose fiber 7 was 1.8%. Further, the adsorption amount of the non-fibrous anionized polysaccharide and the cationizing agent calculated from the dry weight was 99% or more.

Production of cellulose fiber (CNF) -containing composition 8 (CNF composite PE8) 37.1 g of cellulose fiber 7 (solid content 36.4 g) and 163.6 g of PE (J320) pulverized in Example 1 were mixed, and a twin-screw kneader (KZW manufactured by Technobel Co., Ltd., screw diameter: 15 mm, L / D: 45, screw rotation speed: 200 rpm), and one pass at 140 ° C. Cellulose nanofiber composite PE8 (CNF composite PE8) was obtained by pelletizing the obtained melt-kneaded product using a pelletizer (manufactured by Technobel Co., Ltd.).

  As a result of TEM observation, nanofibers were confirmed. In addition, no aggregates were observed in the visual confirmation of the film. Even in the observation with a polarizing microscope, CNF was clearly dispersed.

Evaluation of moldability A tensile test was conducted according to ASTM D638 using the pelletized CNF composite PE8. The test size was TYPE IV. An injection molding machine (iM18 manufactured by Sumitomo Heavy Industries, Ltd.) was used as the injection molding machine, and molding was performed under the conditions of an injection temperature of 160 ° C. and a mold temperature of 40 ° C. A universal testing machine (Instron 3365 type testing machine manufactured by Instron Japan Company Limited) was used as a testing machine.

Example 9: Production of cellulose fiber 8 Cellogen (registered trademark) 5A (CMC manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 40 g was dissolved in 960 g of water to prepare a 4 mass% CMC aqueous solution (non-fibrous anionized polysaccharide). did.

  Into a 10 L stainless steel container, 532 g of pulp 1 (cellulose fiber) produced in Production Example 1 (solid content: 100 g), 750 g of 4% by weight CMC aqueous solution (solid content: 30 g), and 2,718 g of water were charged, and a stirring blade was used. The mixture was stirred at 150 rpm for 2 hours.

  While stirring at 150 rpm, 2,300 g (92 g solid content) of a 4 mass% block dispersant 2 solution (cationizing agent 3) was dropped into the solution over 10 minutes. After completion of dropping, the mixture was further stirred for 1 hour. Thereafter, pressure filtration was performed at 0.3 MPa. Filtration was performed until the filtrate did not come out for 1 minute or longer, and cellulose fiber 8 was obtained.

  The moisture content of the cellulose fiber 8 was less than 30%. Cellulose fiber 8 was dried for 16 hours with a dryer at 110 ° C., and then pulverized with a pulverizer (sanitary crusher manufactured by Sansho Industry Co., Ltd.) to obtain powdered cellulose fiber 8. The moisture content of the powdered cellulose fiber 8 was 2.3%. Further, the adsorption amount of the non-fibrous anionized polysaccharide and the cationizing agent calculated from the dry weight was 99% or more.

Manufacture of cellulose fiber (CNF) -containing composition 9 (CNF composite PE9) 45.6 g of the cellulose fiber 8 (solid content 44.4 g) and 155.6 g of PE (J320) pulverized in Example 1 were mixed, and a twin-screw kneader (KZW manufactured by Technobel Co., Ltd., screw diameter: 15 mm, L / D: 45, screw rotation speed: 200 rpm), and one pass at 140 ° C. Cellulose nanofiber composite PE9 (CNF composite PE9) was obtained by pelletizing the obtained melt-kneaded product using a pelletizer (manufactured by Technobel Co., Ltd.).

  As a result of TEM observation, nanofibers were confirmed. In addition, no aggregates were observed in the visual confirmation of the film. Even in the observation with a polarizing microscope, CNF was clearly dispersed.

Evaluation of moldability A tensile test was conducted according to ASTM D638 using the pelletized CNF composite PE9. The test size was TYPE IV. An injection molding machine (iM18 manufactured by Sumitomo Heavy Industries, Ltd.) was used as the injection molding machine, and molding was performed under the conditions of an injection temperature of 160 ° C. and a mold temperature of 40 ° C. A universal testing machine (Instron 3365 type testing machine manufactured by Instron Japan Company Limited) was used as a testing machine.

Comparative example
Comparative Example 1
Evaluation of Formability A tensile test was performed according to ASTM D638 using Suntech (registered trademark) J320 (high density polyethylene manufactured by Asahi Kasei Chemicals Corporation). The test size was TYPE IV. An injection molding machine (iM18 manufactured by Sumitomo Heavy Industries, Ltd.) was used as the injection molding machine, and molding was performed under the conditions of an injection temperature of 160 ° C. and a mold temperature of 40 ° C. A universal testing machine (Instron 3365 type testing machine manufactured by Instron Japan Company Limited) was used as a testing machine.

Comparative Example 2
106 g of pulp 1 produced in Production Example 1 (solid content 20.0 g) and 180.0 g of PE (J320) pulverized in Example 1 were mixed, and a twin-screw kneader (KZW manufactured by Technobel Co., Ltd., screw diameter: 15 mm, L / D: 45, screw rotation speed: 200 rpm), and one pass at 140 ° C. Cellulose fiber composite PE10 obtained by pelletizing the obtained melt-kneaded product using a pelletizer (manufactured by Technobel Co., Ltd.) was obtained.

  When miniaturization was confirmed by TEM observation, nanofibers were hardly confirmed. Moreover, many aggregates were observed by visual confirmation of the film. Even in observation with a polarizing microscope, the cellulose was not neatly dispersed.

Evaluation of moldability A tensile test was conducted according to ASTM D638 using the pelletized cellulose fiber composite PE10. The test size was TYPE IV. An injection molding machine (iM18 manufactured by Sumitomo Heavy Industries, Ltd.) was used as the injection molding machine, and molding was performed under the conditions of an injection temperature of 160 ° C. and a mold temperature of 40 ° C.

  Tensile tests were not performed because large agglomerates were present and could not be molded cleanly.

Comparative Example 3
Serogen (registered trademark) 5A (CMC manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 40 g was dissolved in 960 g of water to prepare a 4% by mass CMC aqueous solution.

  In a 10 L stainless steel container, 532 g of pulp 1 produced in Production Example 1 (solid content: 100 g), 750 g of 4% by weight CMC aqueous solution (solid content: 30 g), and 2,718 g of water were charged and stirred at 150 rpm. The mixture was stirred for 2 hours at the rotation speed.

  Thereafter, dehydration was performed by pressure filtration, but filtration was hardly possible. The residue on the filter paper could not be removed in the state of dispersion.

Comparative Example 4
In a 10 L stainless steel container, 532 g of pulp 1 produced in Production Example 1 (solid content: 100 g) and 3,468 g of water were charged and stirred for 2 hours at a rotation speed of 150 rpm using a stirring blade.

  While stirring at a rotational speed of 150 rpm, 2,350 g (94 g solid content) of a 4% by mass acrylic resin aqueous solution (cationizing agent 1) was dropped into the solution over 10 minutes. After completion of dropping, the mixture was further stirred for 1 hour. Thereafter, pressure filtration was performed at 0.3 MPa. Filtration was performed until the filtrate did not come out for 1 minute or longer, and cellulose fiber 9 was obtained.

  The moisture content of the cellulose fiber 9 was 70% or more. Cellulose fiber 9 was dried with a dryer at 110 ° C. for 16 hours, and then pulverized with a pulverizer (sanitary crusher manufactured by Sansho Industry Co., Ltd.) to obtain powdered cellulose fiber 9. The adsorption amount of the cationizing agent calculated from the dry weight was less than 1% and could not be modified with acrylic resin 1 alone.

Comparative Example 5
Nissan Cation (registered trademark) 2-OLR (Dioleyldimethylammonium chloride manufactured by NOF Corporation) was diluted with water to prepare a 4% by mass cationizing agent solution 1.

  In a 10 L stainless steel container, 532 g of pulp 1 produced in Production Example 1 (solid content: 100 g) and 3,468 g of water were charged and stirred for 2 hours at a rotation speed of 150 rpm using a stirring blade.

  While stirring at a rotation speed of 150 rpm, 1,650 g (66 g solid content) of a 4 mass% cationizing agent solution 1 was dropped into the liquid over 10 minutes. After completion of dropping, the mixture was further stirred for 1 hour. Thereafter, pressure filtration was performed at 0.3 MPa. Filtration was performed until the filtrate did not come out for 1 minute or longer, and cellulose fiber 10 was obtained.

  The moisture content of the cellulose fiber 10 was 70% or more. Cellulose fiber 10 was dried for 16 hours with a dryer at 110 ° C., and then pulverized with a pulverizer (sanitary crusher manufactured by Sansho Industry Co., Ltd.) to obtain powdered modified cellulose fiber 10. The adsorption amount of the cationizing agent calculated from the dry weight was less than 1% and could not be modified only with Nissan Cation (registered trademark) 2-OLR (cationic surfactant manufactured by NOF Corporation).

Industrial Applicability Compositions and composites containing the cellulose fibers and CNF of the present invention can be suitably used as a reinforcing agent for molding resins.

  The CNF-containing molding resin composition and molded product of the present invention have high mechanical strength, for example, in addition to the fields where conventional CNF molded products have been used, higher mechanical strength (such as bending strength) is required. Can also be used in other fields.

  The CNF-containing molding resin composition and molded article of the present invention are, for example, interior materials, exterior materials, structural materials, etc. for transportation equipment such as automobiles, trains, ships, airplanes, etc., electrical appliances such as personal computers, televisions, telephones, etc. It can be effectively used as housings, structural materials, internal parts, building materials, stationery, office equipment such as office equipment, sports / leisure goods, and structural materials.

Claims (11)

  A composition comprising a non-fibrous anionized polysaccharide, a cationizing agent, and cellulose fibers.   A composition comprising a neutralized product of a non-fibrous anionized polysaccharide and a cationizing agent, and cellulose fibers.   The composition according to claim 1 or 2, wherein the non-fibrous anionized polysaccharide is carboxymethylcellulose.   The cationizing agent is a dispersion of an alkyl ketene dimer with a cationic dispersant, a cationic polystyrene resin, a cationic fatty acid derivative, a cationic poly (meth) acrylic resin, a cationic polyester resin, a cationic polyolefin resin, a cationic poly The composition according to any one of claims 1 to 3, which is at least one component selected from the group consisting of an ether resin, a cationic polyurethane resin, and a quaternary ammonium compound.   The composition of Claims 1-4 whose said cellulose fiber is a cellulose nanofiber.   The resin composition containing the composition of Claims 1-5, and resin.   The molded object formed by shape | molding the resin composition of Claim 6. It is a manufacturing method of the composition of Claims 1-5,
(1) treating cellulose fibers with non-fibrous anionized polysaccharide, and
(2) a step of treating the cellulose fiber obtained in step 1 with a cationizing agent,
Manufacturing method.   A complex in which a neutralized product of a non-fibrous anionized polysaccharide and a cationizing agent is adsorbed on cellulose fibers. A method for producing a composite, comprising:
(1) treating cellulose fibers with non-fibrous anionized polysaccharide, and
(2) a step of treating the cellulose fiber obtained in step 1 with a cationizing agent,
Manufacturing method.   The manufacturing method according to claim 10, wherein the complex is a complex in which a neutralized product of a non-fibrous anionized polysaccharide and a cationizing agent is adsorbed on cellulose fibers.