JP6886649B2 - Modified cellulose and resin composition using it - Google Patents

Description

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

Cellulose fibers that make up wood pulp and the like have long been used as naturally-derived renewable raw materials for paper, clothing, packaging materials, and the like. Cellulose fibers are polysaccharides and usually do not exist as molecules, but have a multi-layered structure such as cellulose microfibrils (MFCs) in which the cellulose molecules are aggregated, microfibril bundles in which the MFCs are aggregated, and aggregates thereof. There is.

Further, a technique has been developed in which cellulose fibers are mechanically and / or chemically treated to obtain cellulose nanofibers (CNF) defibrated to nano size. 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 resins having a low specific density and high strength. CNF is usually obtained by mechanically treating cellulose fibers in an aqueous medium.

Cellulose fibers are lightweight, strong, and have low linear thermal swelling. Therefore, a technique has been developed in which cellulose fibers are blended in a matrix of a resin or the like to increase the mechanical strength of the resin composition. However, since the cellulose fiber has a hydroxyl group and is highly hydrophilic, it has an aspect of being inferior in compatibility with the hydrophobic resin.

In addition, CNF obtained after defibrating 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, when dehydrating the CNF aqueous dispersion (slurry) by filtration or the like, it takes a long time to drain the water. In addition, once the CNF after drainage was dried, it aggregated due to hydrogen bonds between the CNFs, and it was difficult to uniformly redisperse the CNFs. Therefore, it has been difficult to combine highly hydrophilic CNF in the resin.

Therefore, it has been attempted to improve the compatibility between the cellulose fiber or CNF and the resin by introducing a functional group into cellulose or CNF by chemical treatment (Patent Documents 1 and 2).

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

The above-mentioned conventional technique is a technique using a hydrophobicized cellulose fiber or CNF obtained by directly introducing a hydrophobic group into the hydrophilic group of the cellulose fiber or CNF.

Japanese Unexamined Patent Publication No. 2010-106251 Japanese Unexamined Patent Publication No. 2011-047084 Patent No. 5150792

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

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

An object of the present invention is to provide a resin molded product containing a composition containing cellulose fibers or a composite containing cellulose fibers and exhibiting high strength.

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

By first surface-treating the cellulose fibers with a non-fibrous anionic polysaccharide and then neutralizing them with a cationizing agent, the present inventors shorten the drainage time when recovering the cellulose fibers from the aqueous medium. I found that. The present inventors have stated that the cellulose fibers or the cellulose nanofibers (CNF) obtained by further defibrating the cellulose fibers are uniformly dispersed in the resin, and the resin composition containing these cellulose fibers and CNF. It was found that the resin molded product prepared from the product had increased strength.

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

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

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

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

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

Item 4.
The cationizing agent is a dispersion of an alkylketen 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, or a cationic poly. Item 2. 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 2. The composition according to Item 1 to 4, wherein the cellulose fiber is CNF.

Item 6.
Items 1 to 5 and a resin composition containing a resin.

Item 7.
A molded product obtained by molding the resin composition according to Item 6.

Item 8.
The method for producing a composition according to Items 1 to 5, wherein the composition is produced.
(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,
Manufacturing method including.

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

Item 10.
A method for manufacturing a complex
(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,
Manufacturing method including.

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

According to the present invention, it is possible to obtain a composition containing cellulose fibers (or CNF) and a composite containing cellulose fibers (or CNF), which can significantly shorten the drainage time at the time of recovery of cellulose fibers (or CNF). That is, these compositions and complexes contain cellulose fibers (or CNF) having a reduced time required for dehydration treatment, drying treatment, etc. of cellulose fibers (or CNF) and having high drainage.

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

The resin molded product prepared by using the resin composition containing the cellulose fiber (or CNF) has improved strength as compared with the case of using the untreated cellulose fiber or CNF.

It is a figure which shows the aspect of this invention. It is a figure which shows the aspect of this invention.

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

In the following, cellulose nanofibers will also be referred to as CNF.

(1) Composition and Composite The composition of the present invention contains a non-fibrous anionic polysaccharide, a cationizing agent and a cellulose fiber. The composition of the present invention is a composition containing a neutralized product of a non-fibrous anionic polysaccharide and a cationizing agent, and cellulose fibers. The composition can be prepared by treating the cellulose fibers with a non-fibrous anionic polysaccharide and then with a cationizing agent.

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

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

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

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

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

Cellulose fibers or CNFs (complexes) treated with non-fibrous anionized polysaccharides 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 anionic polysaccharide appearing on the surface of the cellulose fiber or CNF and the anionic functional group of the cationizing agent are intermolecular such as ionic interaction. They interact by force. That is, the anionic functional group of the non-fibrous anionic polysaccharide and the anionic functional group of the cationizing agent are familiar.

Due to this action, in the cellulose fibers or CNF contained in the composition or composite, first (i) on the surface of the cellulose fibers or CNF, the anions of the non-fibrous anionized polysaccharides are mediated by the polysaccharides of the non-fibrous anionized polysaccharides. Sexual functional groups appear. This is a cellulosic fiber or CNF (complex) treated with a non-fibrous anionic polysaccharide. Then, (ii) in the anionic functional group of the non-fibrous anionic polysaccharide present on the surface of the complex, the resin portion (or monomer portion) of the cationizing agent is passed through the cationic functional group of the cationizing agent. ) Appears. Cellulose fiber or CNF, non-fibrous anionic polysaccharide polysaccharide, non-fibrous anionic polysaccharide anionic functional group, cationizing agent cationic functional group, cationizing agent resin moiety (or monomer moiety) in that order 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 anionic polysaccharide and a cationizing agent, and cellulose fibers.

Further, the complex of the present invention can be expressed as having a neutralized product of a non-fibrous anionic polysaccharide and a cationizing agent adsorbed on the cellulose fiber.

The cellulose fibers or CNF contained in the composition or complex of the present invention are neutralized as a whole. As a result, the cellulose fibers or CNF contained in the composition or complex has a low solubility in an aqueous solution and a high drainage. As a result, the cellulose fibers and / or CNF contained in the composition or complex can be significantly reduced in drainage time during recovery from the aqueous solution.

Cellulose fiber has high drainage, so it is a suitable material for subsequent defibration treatment.

The resin composition contains cellulose fibers or CNF, as well as a resin. The resin composition can be molded to produce a molded product.

The resin portion (or monomer portion) of the cationizing agent appears on the surface of the cellulose fiber or CNF as a whole. The resin portion (or monomer portion) of the cationizing agent appearing on the surface of the cellulose fiber or CNF and the resin (matrix material) have hydrophobic interactions, hydrogen bonds, dipole interactions, van der Waals forces, etc. They interact with each other due to intermolecular forces. That is, the resin portion (or monomer portion) of the cationizing agent and the resin (matrix material) are familiar.

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

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

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

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

(1-1) Cellulose fiber Fiber is generally an elongated thread-like substance (solid), which is a component whose width is so thin that it cannot be directly measured by the naked eye and whose length is infinitely long compared to the width. Fibers are generally made of chain polymer material. Fibers generally have a large intermolecular force, a high glass transition point, and good crystallinity. Fibers generally have a large surface area and the molecules are oriented in the fiber direction.

The raw material of the cellulose fiber is not particularly limited. The cellulose fiber is a plant fiber, and a cellulose fiber produced from pulp as a raw material is preferable. Cellulose, which is a polysaccharide, does not usually exist as a molecule, and has a multi-layered structure such as a cellulose microfibril (MFC) in which the cellulose molecules are aggregated, a microfibril bundle in which the MFC is aggregated, and an aggregate thereof.

The pulp is preferably a plant fiber produced by using plant raw materials such as wood, bamboo, hemp, jute, kenaf, cotton, beet, agricultural waste, and cloth as raw materials. As the wood used as a raw material for pulp, sitka spruce, sugi, cypress, eucalyptus, acacia and the like are preferable. Pulp is obtained by chemically and / or mechanically pulping plant raw materials. 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.

As the cellulose fiber, regenerated cellulose fiber such as rayon or cellophane is preferable. As the cellulose fiber, a commercially available product can be used, and for example, KC Flock (Nippon Paper Chemicals 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 nano-size level. CNF is a nanofiller derived from a natural raw material and is a composite material for resins having low specific density and high strength.

CNF is generally a cellulose fiber-containing material (water) using a refiner, a high-pressure homogenizer, a medium stirring mill (bead mill, etc.), a stone mill, a grinder, a uniaxial or multiaxial kneader (preferably a biaxial kneader), or the like. Suspension or slurry) is mechanically ground and / or beaten to defibrate or refine it.

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), etc.).

As CNF, a commercially available product can be used, and for example, Serish (Daicel Chemical Industry Co., Ltd.) or the like can be used.

The CNF may be treated with an alkaline solution (for example, an aqueous alkali metal hydroxide solution, aqueous ammonia, etc.).

CNF first forms a cellulose fiber-containing material into a shape (for example, powder, fibrous, sheet, etc.) that can be efficiently treated with an alkaline solution using a refiner, ball mill, cutter mill, etc., if necessary, and then treats this with an alkaline solution. Then, the processed product is obtained by grinding and / or beating with a known defibration or micronization technique used for producing CNF, generally a high-pressure homogenizer, a medium stirring mill, a stone mill, a grinder, or the like. Can be done.

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

CNF is a fiber whose fiber length is very long with respect to the fiber diameter. The average value of the fiber length of CNF is preferably about 5 times or more, more preferably about 10 times or more, and further preferably about 20 times or more. The average value of the 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 becomes large when it is combined with the resin to form a composition. Thereby, the 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 small thermal deformation (low thermal expansion).

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

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

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

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 anion groups of the non-fibrous anionized polysaccharide is preferably about 0.5 to 1.5 per anhydrous glucose.

(1-4) Cationic agent The 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, and a cationic polyolefin resin. Examples thereof include cationic polyether resins, cationic polyurethane resins, and quaternary ammonium compounds. Among them, 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 an 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 preferable. 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.

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

The gradient copolymer structure is, for example, a copolymer composed of repeating units derived from two types of monomers A and B having different properties (for example, polarity), from one end of a polymer chain rich in A units to B units. The structure has a distribution gradient of repeating units such that the proportion of A units decreases and the proportion of B units increases toward the other end, which is rich in polymer. A gradient copolymer structure can be obtained by using a known living polymerization.

As the monomer component of the resin affinity segment A, methyl (meth) acrylate, ethyl (meth) acrylate, 2-methoxyethyl methacrylate, propyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, and hexyl ( Meta) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tetradecyl (meth) acrylate, octadecyl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobolonyl (meth) ) Acrylate, trimethylcyclohexyl (meth) acrylate, cyclodecyl (meth) acrylate, cyclodecylmethyl (meth) acrylate, tricyclodecyl (meth) acrylate, dicyclopentenyloxyethyl (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 type of the above-mentioned monomer, or may be composed of two or more types.

A cationic unsaturated monomer can be mentioned as a monomer component of the cationic group segment B.

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

Examples of the cationic unsaturated monomer include compounds having an unsaturated bond and a 1st to tertiary amino group in one molecule and salts thereof, a compound having a quaternary ammonium salt, and a compound having a primary amide group. Be done.

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

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

As monomers having a tertiary amino group, 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 dialkylaminoalkyl (meth) acrylamides such as N, N-dimethylaminopropyl (meth) acrylamide, Examples thereof include 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 1-vinylimidazole and the like.

Salts of these unsaturated monomers having a primary to tertiary amino group can also be used. Examples of salts include inorganic salts such as hydrochlorides and sulfates, and organic acid salts such as formates and acetates.

In addition, for monomers having a tertiary amino group,
The unsaturated monomer having a secondary amino group and
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, A monomer obtained as a tertiary amine acid salt by reaction with any of glycidyl group-containing compounds such as epichlorohydrin and glycidyltrialkylammonium chloride, 3-chloro-2-hydroxypropyltrimethylammonium chloride, and monochloroacetate is also available. Can be mentioned.

Examples of the unsaturated monomer which is a quaternary ammonium salt include diallyldimethylammonium chloride, dimetharyldimethylammonium chloride, diallyldiethylammonium chloride, diethyldimethallylammonium chloride and the like.

Further, examples of the unsaturated monomer which is a quaternary ammonium salt include an unsaturated monomer obtained by reacting the unsaturated monomer having a tertiary amino group with a quaternary agent. .. Examples of the quaternary agent 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 thereof include glycidyl group-containing compounds such as alkylene oxide, styrene oxide, epichlorohydrin, and glycidyl trialkylammonium chloride, 3-chloro-2-hydroxypropyltrimethylammonium chloride, sodium monochloroacetate and the like.

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 ₆ ^-, BF ₄ ^- may be to convert the counter anion such.

Examples of the unsaturated monomer which is a quaternary ammonium salt synthesized by using these quaternary agents include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, and (meth). ) Acryloyloxypropyldimethylbenzylammonium chloride, 2-hydroxy-3- (meth) acryloyloxypropyltrimethylammonium chloride and the like.
Further, the reaction with the quaternary agent may be carried out after polymerizing the unsaturated monomer having a tertiary amino group.

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

As the cationic (meth) acrylic resin, a monomer component other than the resin affinity segment A and the cationic group segment B may be used, if necessary. For example, as the cationic group segment B, 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 may be used.

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

Cationic group amount of 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 with ion-exchanged water to 0.02% by mass, 10 cc of it is sampled in the cell of the particle charge meter. Then, after adjusting to pH 3, titration is performed using a 1/1000 N aqueous solution of potassium polyvinyl sulfonate (PVSK) until the flow potential becomes zero. The degree of cationization (oxidation) of the cationizing agent is calculated from the titration amount of 1 / 1,000N PVSK aqueous solution and the following formula.

Degree of cationization (meq / g) = 1/1000 N PVSK aqueous solution titration (ml) / 2
The degree of cationization of the cationizing agent is preferably about 0.80 to 2.00.

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

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

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

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

The complex of the present invention can also be expressed as a non-fibrous anionized polysaccharide-modified cellulose fiber and a cationizing agent. The complex of the present invention can also be expressed as an anionic cellulose fiber containing a non-fibrous anionic polysaccharide in which a cationizing agent is adsorbed.

The present invention can also be described as a modified cellulose fiber containing a non-fibrous anionic 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 anionic 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 anionic 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 anionic polysaccharide is called an anionic cellulose fiber, and by further containing a cationizing agent, it is called a modified cellulose fiber as a whole.

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

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

The present invention is a resin composition containing the complex and the resin, and the resin composition containing the modified cellulose fiber and the resin. The present invention is a molded product obtained by molding the resin composition.

(2) Method for producing composition and complex
(2-1) Method for Producing Composition or Complex The composition or complex of the present invention is:
(1) A step of treating the cellulose fiber with a non-fibrous anionized polysaccharide, and (2) a step of treating the cellulose fiber obtained in the step 1 with a cationizing agent.
It can be manufactured by a manufacturing method including.

The obtained complex preferably has a cellulose fiber adsorbed with a neutralized product of a non-fibrous anionic polysaccharide and a cationizing agent.

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

Step 1: 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 the non-fibrous anionized polysaccharide previously dissolved in water. It is preferable to uniformly mix the cellulose fibers and the non-fibrous anionized polysaccharide using a stirring blade or the like. By uniformly mixing, the cellulose fibers are evenly and uniformly treated with the non-fibrous anionized polysaccharide.

Blending ratio of cellulose fiber and non-fibrous anionized polysaccharide The blending 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 water-filtering property of the cellulose fiber is good, and the physical properties of the cellulose fiber are good.

Step 2: Treat the cellulose fibers obtained in Step 1 with a cationizing agent In Step 2, the cationizing agent is applied to the aqueous dispersion of the cellulose fibers obtained in Step 1 treated with the non-fibrous anionized polysaccharide. Can be added.

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

The dropping time is not particularly limited. The dropping time is preferably 10 minutes or more. By taking 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 uniformly mixing, the reaction between the cationizing agent and the non-fibrous anionized polysaccharide proceeds uniformly and uniformly.

Blending ratio of non-fibrous anionic polysaccharide and cationizing agent The blending ratio of non-fibrous anionic polysaccharide and cationizing agent is not particularly limited. The blending ratio (mass ratio) of the non-fibrous anionic 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 the most preferable. By satisfying this range, the neutralization reaction proceeds and the drainage becomes high.

Blending ratio of cellulose fiber and modified portion The blending ratio of cellulose fiber and modified portion (non-fibrous anionized polysaccharide + cationizing agent) is not particularly limited. The blending ratio (mass ratio) of the cellulose fiber: modified portion 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 water-filtering property of the cellulose fiber is good, and the physical properties of the cellulose fiber are good.

(2-2) Method for producing composition and complex (1 in the case of CNF)
When the cellulose fiber contained in the composition or complex of the present invention is CNF
(1) Step of treating cellulose fibers with non-fibrous anionized polysaccharides,
It can be produced by a production method including (2) 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: A step of treating the cellulose fiber with a non-fibrous anionized polysaccharide The same as the 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 a modified cellulose fiber.

Step 3: Defibering the modified cellulose fiber obtained in Step 2. In Step 3, the modified cellulose fiber obtained in Step 2 can be defibrated by applying a mechanical shearing force in a solvent or a resin. it can.

The modified cellulose fiber is obtained by treating the cellulose fiber with a non-fibrous anionic polysaccharide and then with a cationizing agent, and is obtained by treating the cellulose fiber with a non-fibrous anionic polysaccharide and then a cationizing agent. "Composition containing fibers", "Composition containing a neutralized product of a non-fibrous anionized polysaccharide and a cationizing agent, and cellulose fibers", or "Cationulose fibers with a non-fibrous anionized polysaccharide and cationization" A complex in which a neutralized product with an agent is adsorbed. "

In the defibration treatment, it is preferable to perform the defibration treatment in the resin from the viewpoint of ease of mixing with the molding resin.

As the means for applying the shearing force, means such as a bead mill, an ultrasonic homogenizer, an extruder such as a single-screw extruder and a twin-screw extruder, a Banbury mixer, a grinder, a pressure kneader, and a known kneader such as a double roll are used. Is preferable.

(2-3) Method for producing composition and complex (2 for CNF)
When the cellulose fiber contained in the composition or complex of the present invention is CNF
(1) A step of treating CNF with a non-fibrous anionized polysaccharide, and (2) a step of treating the CNF obtained in Step 1 with a cationizing agent,
It can be manufactured by a manufacturing method including.

Step 1: Treating CNF with non-fibrous anionized polysaccharide In step 1, the raw material and CNF can be 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 the non-fibrous anionized polysaccharide previously dissolved in water. In addition, it is desirable to uniformly mix CNF and non-fibrous anionized polysaccharide using a stirring blade or the like. By uniformly mixing, the CNF is evenly treated with the non-fibrous anionized polysaccharide.

Ratio of CNF to non-fibrous anionized polysaccharide
The blending ratio of CNF and the 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 water-filtering property of the cellulose fiber is good, and the physical properties of the cellulose fiber are good.

Step 2: Treat 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 the aqueous dispersion of CNF. The cationizing agent is preferably added dropwise to promote the reaction with the fibrous anionic polysaccharide. The dropping time is not particularly limited, but 10 minutes or more is preferable. By taking 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 desirable to uniformly mix the CNF treated with the non-fibrous anionized polysaccharide and the cationizing agent using a stirring blade or the like. By uniformly mixing, 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 anionizing polysaccharide and the cationizing agent is not particularly limited. The blending ratio (mass ratio) of the non-fibrous anionic 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 the most preferable. By satisfying this range, the neutralization reaction proceeds and the drainage becomes high.

Ratio of CNF and modified part (non-fibrous anionized polysaccharide + cationizing agent)
The blending ratio of CNF and the modified portion (non-fibrous anionized polysaccharide + cationizing agent) is not particularly limited. The blending ratio (mass ratio) of the cellulose fiber: modified portion 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 water-filtering property 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 for recovering cellulose fiber or CNF, a method of separating solid matter 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 in a dryer, and can be prepared in powder form by a pulverizer or the like. The recovered cellulose fiber or CNF can also be dried and prepared in the form of a sheet.

In the present invention, the state before the recovery of the cellulose fiber or CNF or the state after the recovery of the cellulose fiber or CNF can be referred to as a composition or a complex.

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

As the molding resin, a thermosetting resin, a radical curable resin, a thermoplastic resin and the like are preferable.

Thermosetting resin A known thermosetting resin can be used. Thermosetting resins such as phenol resin, urea resin, melamine resin, unsaturated polyester resin, epoxy resin, diallyl phthalate resin, polyurethane resin, silicon resin, and polyimide resin are preferable.

It is preferable to use at least one of these components.

Radical-curable resin The radical-curable resin is preferably a resin that does not require heat and is radical-cured by light or radiation, or by being left at room temperature. Acrylic resin or the like is preferable.

Thermoplastic resin Basically, a known thermoplastic resin can be used without limitation.

Polyolefin resins such as polyethylene and polypropylene are preferable. Polyester resins such as polyethylene terephthalate and polybutylene terephthalate are preferable. Acrylic tree-based fats such as polymethylmethacrylate and polyethylmethacrylate are preferable. Styrene resins such as polystyrene, acrylonitrile-butadiene-styrene resin, acrylonitrile-acrylic rubber-styrene resin, acrylonitrile-ethylene rubber-styrene resin, (meth) acrylic acid ester-styrene resin, and styrene-butadiene-styrene resin are preferable. Polyamide resins such as ionomer resin, polyacrylic nitrile, and nylon are preferable. 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. Fluororesin such as polyvinyl fluoride and polyvinylidene fluoride is preferable. Thermoplastic resins such as polycarbonate resin, modified polyphenylene ether resin, methylpentene resin, and cellulose resin are preferable. Thermoplastic elastomers such as olefin-based elastomers, vinyl chloride-based elastomers, styrene-based elastomers, urethane-based elastomers, polyester-based elastomers, and polyamide-based elastomers are preferable. Mixtures of seeds and above can be mentioned.

It is preferable to use at least one of these components.

Formulation of Cellulose Fiber and CNF in 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 of blending the cellulose fiber or CNF into the molding resin is not particularly limited. Cellulose fibers or CNF sheets or aggregates can be impregnated with molding resin. Cellulose fibers or CNF can be dried and pulverized and mixed with a molding resin. In the case of a molding resin that is kneaded at a high temperature, wet cellulose fibers or CNF may be mixed with the molding resin to remove water from the kneading.

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

(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, anti-ozone agents, activators, anti-static agents. , Lubricants, anti-friction agents, surface conditioners (leveling agents, antifoaming agents, anti-blocking agents, etc.), antifungal agents, antibacterial agents, dispersants, flame retardants, addition accelerators, addition of addition accelerators, etc. The agent can be blended.

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

(5) Resin molded product
Production of Molded Body The resin composition can be produced by a known and conventional molding method of a resin composition for molding. 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 needed.

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

The modified CNF-containing resin molded product can be used in fields 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 preferably used for housings, structural materials, internal parts, etc. of electric appliances such as personal computers, televisions, and telephones. It is preferable to use it for the housing of office equipment such as building materials, stationery, and OA equipment. It is preferably used for sports / leisure goods, structural materials, etc.

(1) Preparation of cellulose fiber and cationizing agent
Production example 1: Pulp 1 (cellulose fiber)
A slurry of softwood bleached kraft pulp (NBKP) (slurry concentration: 2% by mass) was repeatedly treated with a single disc refiner (manufactured by Kumagai Riki Kogyo Co., Ltd.) until the Canadian standard freeness became 100 mL or less. Dehydration was carried out by pressure filtration to obtain pulp 1.

The moisture content of this pulp 1 was measured at 110 ° C. using an infrared moisture meter FD-720 manufactured by Kett Scientific Research Institute, Inc. and found to be 81.2% by mass.

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

Cationic 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 600 parts of isopropyl alcohol is charged into a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube, and while stirring. The inside of the reaction vessel was replaced with nitrogen. After raising the temperature inside the reaction vessel to 80 ° C while maintaining a nitrogen atmosphere, 100 parts of synthetic lauryl methacrylate (“Blemmer (registered trademark) SLMA” manufactured by NOF CORPORATION), 300 parts of acrylamide, and t-butylper from a dropping device. A mixed solution of 27 parts of oxy (2-ethylhexanoate) (“Perbutyl (registered trademark)” O manufactured by NOF CORPORATION) was added dropwise over 2 hours and 30 minutes.

After completion of the dropping, the reaction was continued for 11 hours at the same temperature. Two parts each of t-butylperoxy (2-ethylhexanoate) ("Perbutyl (registered trademark) O" manufactured by NOF CORPORATION) was added 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.

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

Cationic agent 2: Block dispersant 1
It is a 4% by mass solution of an aqueous dispersible resin having a cationic group and a (meth) acrylic 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 parts Diphenylmethane (DPM): 0.2 parts
Monomer component of polymer block B (cationic group segment):
2- (Dimethylamino) ethyl methacrylate (DMAEMA): 38 parts

Cationic agent 3: Block dispersant 2
It is a 4% by mass solution of an aqueous dispersible resin having a cationic group and a (meth) acrylic 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 parts
DPM: 0.2 copies
Monomer component of polymer block B (cationic group segment)
DMAEMA: 15 copies

Cationic agent 4: Commercial product (4% by mass)
Georail Dimethylammonium Chloride Nissan Cation (registered trademark) 2-OLR manufactured by NOF CORPORATION

Calculation method of cationization degree The cationization degree 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 with ion-exchanged water to 0.02% by mass, 10 cc of it was sampled in the cell of PCD-02. Then, after adjusting to pH 3, titration was performed using a 1/1000 N aqueous solution of potassium polyvinyl sulfonate (PVSK) until the flow potential became zero. The degree of cationization (acid value) of the cationizing agent was calculated from the titration amount of 1 / 1,000N PVSK aqueous solution and the following formula.

Degree of cationization (meq / g) = 1/1000 N PVSK aqueous solution titration (ml) / 2

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

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

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

Then, pressure filtration was performed at 0.3 MPa. Cellulose fiber 1 was obtained by filtering until the filtrate did not come out for 1 minute or more.

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

Evaluation of Filtration Water content The water content of cellulose fiber 1 after pressure filtration was measured.

Water drainage ×: When the water content is 70% or more Water flow △: When the water content is 30% or more and less than 70% Water flow ○: 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 Co., Ltd.) was pulverized using a 1.3 mm screen. 45.7 g (solid content 44.8 g) of the cellulose fiber 1 and 155.2 g of crushed PE (J320) 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), 1 pass at 140 ° C. The obtained melt-kneaded product was pelletized using a pelletizer (manufactured by Technobel Co., Ltd.) to obtain a cellulose nanofiber composite PE1 (CNF composite PE1).

No agglomerates were observed by visual confirmation of the film. CNF was well dispersed even when observed with a polarizing microscope.

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

The mixture was cooled to room temperature to obtain a cellulose nanofiber composite PE film 1 (CNF composite PE film 1).

The presence or absence of agglomerates was visually confirmed on the CNF composite PE film 1.

Visual dispersibility ×: With agglomerates Visual dispersibility ○: No agglomerates

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

Polarizing microscope dispersibility ×: Cellulose lumps confirmed Polarizing microscope dispersibility ○: Cellulose lumps 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 performed using the pelletized CNF composite PE1 according to ASTM D638. The test size used 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 the testing machine.

Determining the Finer State of Cellulose Fibers A section was cut out from the test piece obtained by the above molding with a microtome, and the cellulose fiber was observed with a transmission microscope (TEM). I took 10 pictures of 10,000 times.

Miniaturized state ○: When the ratio of the number of cellulose fibers of 500 nm or less is 50% or more Miniaturized state Δ: When the ratio of the number of cellulose fibers of 500 nm or less is 10% or more and less than 50% Miniaturized state ×: 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 20 g of cellogen (registered trademark) 5A (CMC manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) is dissolved in 480 g of water to prepare a 4 mass% CMC aqueous solution (non-fibrous anionized polysaccharide). did.

In a 10 L stainless steel container, 532 g (solid content 100 g) of pulp 1 (cellulose fiber) produced in Production Example 1, 375 g (solid content 15 g) of 4 mass% CMC aqueous solution and 3,093 g of water were charged, and a stirring blade was used. Then, the mixture was stirred at a rotation speed of 150 rpm for 2 hours.

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

Then, pressure filtration was performed at 0.3 MPa. Cellulose fiber 2 was obtained by filtering until the filtrate did not come out for 1 minute or more.

The water content of this cellulose fiber 2 was less than 30%. Cellulose fiber 2 was dried in a dryer at 110 ° C. for 16 hours and then pulverized with a crusher (sanitary crusher manufactured by Sansho Industry Co., Ltd.) to obtain powdered cellulose fiber 2. The water content of the powdered cellulose fiber 2 was 1.9% by mass. 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 2 (CNF Composite PE2) 33.0 g (solid content 32.4 g) of the cellulose fiber 2 and 167.6 g of PE (J320) crushed in Example 1 were mixed, and a twin-screw kneader was used. (KZW manufactured by Technobel Co., Ltd., screw diameter: 15 mm, L / D: 45, screw rotation speed: 200 rpm) was used for one pass at 140 ° C. The obtained melt-kneaded product was pelletized using a pelletizer (manufactured by Technobel Co., Ltd.) to obtain a cellulose nanofiber composite PE2 (CNF composite PE2).

When the miniaturization was confirmed by TEM observation, nanofibers could be confirmed. In addition, no agglomerates were observed by visual confirmation of the film. CNF was well dispersed even when observed with a polarizing microscope.

Evaluation of Moldability A tensile test was performed using the pelletized CNF composite PE2 according to ASTM D638. The test size used 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 the 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) crushed in Example 1 are mixed and mixed. One pass was performed 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). The obtained melt-kneaded product was pelletized using a pelletizer (manufactured by Technobel Co., Ltd.) to obtain a cellulose nanofiber composite PE3 (CNF composite PE3).

When the miniaturization was confirmed by TEM observation, nanofibers could be confirmed. In addition, no agglomerates were observed by visual confirmation of the film. CNF was well dispersed even when observed with a polarizing microscope.

Evaluation of Moldability A tensile test was performed using the pelletized CNF composite PE3 according to ASTM D638. The test size used 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 the 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 mass% CMC aqueous solution (non-fibrous anionized polysaccharide).

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

While stirring at a rotation speed of 150 rpm, 1,575 g (solid content 63 g) of a 4 mass% acrylic resin aqueous solution (cationizing agent 1) was added dropwise into the liquid over 10 minutes. After completion of the dropping, the mixture was further stirred for 1 hour. Then, pressure filtration was performed at 0.3 MPa. Cellulose fiber 3 was obtained by filtering until the filtrate did not come out for 1 minute or more.

The water content of this cellulose fiber 3 was less than 30%. Cellulose fiber 3 was dried in a dryer at 110 ° C. for 16 hours and then pulverized with a crusher (sanitary crusher manufactured by Sansho Industry Co., Ltd.) to obtain powdered cellulose fiber 3. The water content of the powdered cellulose fiber 3 was 2.4% by mass. 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 4 (CNF Composite PE4) 41.0 g (solid content 40.0 g) of the cellulose fiber 3 and 160.0 g of PE (J320) crushed in Example 1 were mixed, and a twin-screw kneader was used. (KZW manufactured by Technobel Co., Ltd., screw diameter: 15 mm, L / D: 45, screw rotation speed: 200 rpm) was used for one pass at 140 ° C. The obtained melt-kneaded product was pelletized using a pelletizer (manufactured by Technobel Co., Ltd.) to obtain a cellulose nanofiber composite PE4 (CNF composite PE4).

When the miniaturization was confirmed by TEM observation, nanofibers could be confirmed. In addition, no agglomerates were observed by visual confirmation of the film. CNF was well dispersed even when observed with a polarizing microscope.

Evaluation of Moldability A tensile test was performed using the pelletized CNF composite PE4 according to ASTM D638. The test size used 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 the testing machine.

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

Cellulose nanofibers (CNF) (Selish (registered trademark) KY-100G manufactured by Daicel FineChem Co., Ltd., solid content concentration: 10% by mass)) 250 g (solid content 25.0 g (cellulose fiber)), 4 in a 10 L stainless steel container. 187.5 g (7.5 g of solid content) of a mass% LC-100 aqueous solution and 4,562.5 g of water were charged, and the mixture was stirred at a rotation speed of 150 rpm for 2 hours using a stirring blade.

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

The water content of this CNF4 was less than 30%. CNF4 was dried in a dryer at 110 ° C. for 16 hours and then crushed with a crusher (sanitary crusher manufactured by Sansho Industry Co., Ltd.) to obtain powdered CNF4. The water content of powdered CNF4 was 2.1%. 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 the above CNF4 and 155.2 g of PE (J320) crushed 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) was used for 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 5 (CNF composite PE5).

When the miniaturization was confirmed by TEM observation, nanofibers could be confirmed. In addition, no agglomerates were observed by visual confirmation of the film. CNF was well dispersed even when observed with a polarizing microscope.

Evaluation of Moldability A tensile test was performed using the pelletized CNF composite PE5 according to ASTM D638. The test size used 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 the testing machine.

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

Nissan cation (registered trademark) 2-OLR (diorail dimethylammonium chloride manufactured by NOF CORPORATION) was diluted with water to prepare a solution of 4% by mass of cationizing agent 4.

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

A solution of the cationizing agent 4 was added dropwise in a solution of 1,650 g (solid content 66 g) over 10 minutes while stirring at a rotation speed of 150 rpm. After completion of the dropping, the mixture was further stirred for 1 hour. Then, pressure filtration was performed at 0.3 MPa. Cellulose fiber 5 was obtained by filtering until the filtrate did not come out for 1 minute or more.

The water content of this cellulose fiber 5 was less than 30%. Cellulose fiber 5 was dried in a dryer at 110 ° C. for 16 hours and then pulverized with a crusher (sanitary crusher manufactured by Sansho Industry Co., Ltd.) to obtain powdered cellulose fiber 5. The water content of the powdered cellulose fiber 5 was 2.5%. 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 6 (CNF Composite PE6) 41.0 g (solid content 40.0 g) of the cellulose fiber 5 and 160.0 g of PE (J320) crushed in Example 1 were mixed, and a twin-screw kneader was used. (KZW manufactured by Technobel Co., Ltd., screw diameter: 15 mm, L / D: 45, screw rotation speed: 200 rpm) was used for 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).

When the miniaturization was confirmed by TEM observation, nanofibers could be confirmed. In addition, no agglomerates were observed by visual confirmation of the film. CNF was well dispersed even when observed with a polarizing microscope.

Evaluation of Moldability A tensile test was performed using the pelletized CNF composite PE6 according to ASTM D638. The test size used 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 the 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 (diorail dimethylammonium chloride manufactured by NOF CORPORATION) was diluted with water to prepare a solution of 4% by mass of cationizing agent 4.

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

A solution of the cationizing agent 4 was added dropwise in a solution of 825 g (solid content 33 g) over 10 minutes while stirring at a rotation speed of 150 rpm. After completion of the dropping, the mixture was further stirred for 1 hour. Then, pressure filtration was performed at 0.3 MPa. Cellulose fiber 6 was obtained by filtering until the filtrate did not come out for 1 minute or more.

The water content of this cellulose fiber 6 was less than 30%. Cellulose fiber 6 was dried in a dryer at 110 ° C. for 16 hours and then pulverized with a crusher (sanitary crusher manufactured by Sansho Industry Co., Ltd.) to obtain powdered cellulose fiber 6. The water content of the powdered cellulose fiber 6 was 1.9%. 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 the cellulose fiber 6 and 170.0 g of PE (J320) crushed 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) was used for one pass at 140 ° C. The obtained melt-kneaded product was pelletized using a pelletizer (manufactured by Technobel Co., Ltd.) to obtain a cellulose nanofiber composite PE7 (CNF composite PE7).

When the miniaturization was confirmed by TEM observation, nanofibers could be confirmed. In addition, no agglomerates were observed by visual confirmation of the film. CNF was well dispersed even when observed with a polarizing microscope.

Evaluation of Moldability A tensile test was performed using the pelletized CNF composite PE7 according to ASTM D638. The test size used 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 the testing machine.

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

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

A solution of 4% by mass of the block dispersant 1 (cationizing agent 2) was added dropwise to the liquid over 10 minutes while stirring at a rotation speed of 150 rpm (solid content 52 g). After completion of the dropping, the mixture was further stirred for 1 hour. Then, pressure filtration was performed at 0.3 MPa. Cellulose fiber 7 was obtained by filtering until the filtrate did not come out for 1 minute or more.

The water content of this cellulose fiber 7 was less than 30%. Cellulose fiber 7 was dried in a dryer at 110 ° C. for 16 hours and then pulverized with a crusher (sanitary crusher manufactured by Sansho Industry Co., Ltd.) to obtain powdered cellulose fiber 7. The water content of the powdered cellulose fiber 7 was 1.8%. 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 (solid content 36.4 g) of the cellulose fiber 7 and 163.6 g of PE (J320) crushed in Example 1 were mixed, and a twin-screw kneader was used. (KZW manufactured by Technobel Co., Ltd., screw diameter: 15 mm, L / D: 45, screw rotation speed: 200 rpm) was used for one pass at 140 ° C. The obtained melt-kneaded product was pelletized using a pelletizer (manufactured by Technobel Co., Ltd.) to obtain a cellulose nanofiber composite PE8 (CNF composite PE8).

When the miniaturization was confirmed by TEM observation, nanofibers could be confirmed. In addition, no agglomerates were observed by visual confirmation of the film. CNF was well dispersed even when observed with a polarizing microscope.

Evaluation of Moldability A tensile test was performed using the pelletized CNF composite PE8 according to ASTM D638. The test size used 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 the testing machine.

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

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

A solution of 4% by mass of the block dispersant 2 (cationizing agent 3) was added dropwise to the liquid over 10 minutes while stirring at a rotation speed of 150 rpm (solid content 92 g). After completion of the dropping, the mixture was further stirred for 1 hour. Then, pressure filtration was performed at 0.3 MPa. Cellulose fiber 8 was obtained by filtering until the filtrate did not come out for 1 minute or more.

The water content of this cellulose fiber 8 was less than 30%. Cellulose fiber 8 was dried in a dryer at 110 ° C. for 16 hours and then pulverized with a crusher (sanitary crusher manufactured by Sansho Industry Co., Ltd.) to obtain powdered cellulose fiber 8. The water content of the powdered cellulose fiber 8 was 2.3%. 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 9 (CNF Composite PE9) 45.4 g (solid content 44.4 g) of the cellulose fiber 8 and 155.6 g of PE (J320) crushed in Example 1 were mixed, and a twin-screw kneader was used. (KZW manufactured by Technobel Co., Ltd., screw diameter: 15 mm, L / D: 45, screw rotation speed: 200 rpm) was used for one pass at 140 ° C. The obtained melt-kneaded product was pelletized using a pelletizer (manufactured by Technobel Co., Ltd.) to obtain a cellulose nanofiber composite PE9 (CNF composite PE9).

When the miniaturization was confirmed by TEM observation, nanofibers could be confirmed. In addition, no agglomerates were observed by visual confirmation of the film. CNF was well dispersed even when observed with a polarizing microscope.

Evaluation of Moldability A tensile test was performed using the pelletized CNF composite PE9 according to ASTM D638. The test size used 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 the testing machine.

Comparative example
Comparative example 1
Evaluation of Moldability A tensile test was conducted using Suntech (registered trademark) J320 (high-density polyethylene manufactured by Asahi Kasei Chemicals Co., Ltd.) according to ASTM D638. The test size used 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 the testing machine.

Comparative example 2
106 g (solid content 20.0 g) of pulp 1 produced in Production Example 1 and 180.0 g of PE (J320) crushed in Example 1 were mixed, and a twin-screw kneader (KZW manufactured by Technobel Co., Ltd.), screw diameter: One pass was performed at 140 ° C. at 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 a cellulose fiber composite PE10.

When miniaturization was confirmed by TEM observation, almost no nanofibers could be confirmed. In addition, a large number of agglomerates were observed by visual confirmation of the film. Cellulose was not well dispersed even when observed with a polarizing microscope.

Evaluation of Moldability A tensile test was performed using the pelletized cellulose fiber composite PE10 according to ASTM D638. The test size used 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.

No tensile test was performed due to the presence of large agglomerates and the inability to form cleanly.

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

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

After that, dehydration was performed by pressure filtration, but almost no filtration was possible. The residue on the filter paper could not be taken out in the state of the dispersion liquid.

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

While stirring at a rotation speed of 150 rpm, 2,350 g (solid content 94 g) of a 4 mass% acrylic resin aqueous solution (cationizing agent 1) was added dropwise into the liquid over 10 minutes. After completion of the dropping, the mixture was further stirred for 1 hour. Then, pressure filtration was performed at 0.3 MPa. Cellulose fiber 9 was obtained by filtering until the filtrate did not come out for 1 minute or more.

The water content of the cellulose fiber 9 was 70% or more. Cellulose fiber 9 was dried in a dryer at 110 ° C. for 16 hours and then pulverized with a crusher (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 the acrylic resin 1 alone.

Comparative example 5
Nissan cation (registered trademark) 2-OLR (diorail dimethylammonium 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 (solid content 100 g) of pulp 1 produced in Production Example 1 and 3,468 g of water were charged, and the mixture was stirred at a rotation speed of 150 rpm for 2 hours using a stirring blade.

While stirring at a rotation speed of 150 rpm, 1,650 g (solid content 66 g) of 4% by mass cationizing agent solution 1 was added dropwise to the liquid over 10 minutes. After completion of the dropping, the mixture was further stirred for 1 hour. Then, pressure filtration was performed at 0.3 MPa. Cellulose fiber 10 was obtained by filtering until the filtrate did not come out for 1 minute or more.

The water content of the cellulose fiber 10 was 70% or more. Cellulose fiber 10 was dried in a dryer at 110 ° C. for 16 hours and then pulverized with a crusher (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 by Nissan cation (registered trademark) 2-OLR (cationic surfactant manufactured by NOF CORPORATION).

Industrial Applicability The compositions and complexes containing the cellulose fibers and CNFs 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 in which conventional CNF molded products have been used, higher mechanical strength (bending strength, etc.) is required. It can also be used in fields where it is used.

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

Claims (6)

A resin composition containing a composite in which a neutralized product of a non-fibrous anionic polysaccharide and a cationizing agent is adsorbed on cellulose nanofibers, and a resin. The resin composition according to claim 1, wherein the non-fibrous anionic polysaccharide is carboxymethyl cellulose. 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, or a cationic poly. The resin composition according to claim 1 or 2 , which is at least one component selected from the group consisting of an ether resin, a cationic polyurethane resin, and a quaternary ammonium compound. A molded product obtained by molding the resin composition according to any one of claims 1 to 3. The method for producing a resin composition according to any one of claims 1 to 3.
(1) Step of treating cellulose fibers with non-fibrous anionic polysaccharides,
(2) Step (1) obtained in cellulose fiber is treated with a cationic agent Ru obtain a modified cellulose fiber process,
(3) A step of defibrating the modified cellulose fiber obtained in step (2) to obtain a composite in which a neutralized product of a non-fibrous anionic polysaccharide and a cationizing agent is adsorbed on the cellulose nanofiber. as well as
(4) A step of blending the complex obtained in step (3) with a resin to obtain a resin composition.
Manufacturing method including. The method for producing a resin composition according to any one of claims 1 to 3.
(1) A step of treating cellulose nanofibers with a non-fibrous anionized polysaccharide,
(2) The cellulose nanofibers obtained in step (1) are treated with a cationizing agent to form a complex in which a neutralized product of a non-fibrous anionized polysaccharide and a cationizing agent is adsorbed on the cellulose nanofibers. Obtaining process and
(3) A step of blending the complex obtained in step (2) with a resin to obtain a resin composition.
Manufacturing method including.

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