JP2020063408A - Dispersion and cellulose-containing composition - Google Patents

Abstract

To provide a dispersion for cellulose nanofibers that can disperse cellulose nanofibers without flocculation in a system having water as the main medium by a convenient method; a cellulose nanofiber hydrous dispersion that can be easily redispersed in water after drying and gives excellent dispersibility of cellulose nanofibers into resin; and a cellulose nanofiber dry body that, when dispersed in resin, gives a resin composition sufficient mechanical properties and heat properties, while giving excellent coatability and wear resistance in practical use.SOLUTION: A dispersion has (A) a surface treatment agent that is a water-soluble polymer having a hydrophilic segment and a hydrophobic segment with a number average molecular weight of 200-30000, and (B) a mixture of polyurethane and water.SELECTED DRAWING: None

Description

  The present invention relates to dispersions and cellulose-containing compositions.

  Since thermoplastic resins are light and have excellent processing characteristics, they are widely used in various fields such as automobile parts, electric / electronic parts, office equipment housings, and precision parts. However, the resin alone often has insufficient mechanical properties, slidability, thermal stability, paintability, dimensional stability, etc., and composites of resin and various inorganic materials are generally used. .

  A resin composition in which a thermoplastic resin is reinforced with a reinforcing material that is an inorganic filler such as glass fiber, carbon fiber, talc, and clay has a problem that the weight of a resin molded product obtained is large because of its high specific gravity. Further, the glass fiber reinforced thermoplastic resin flows through the production line at a high temperature when the surface of the vehicle body is painted, and the paint containing the organic solvent is sprayed. In this process, VOC (volatile organic compound) reduction request at the time of drying, request for improvement in durability due to glass fiber being raised on the surface and obstructing adhesion due to high temperature, request for improvement in appearance defect of resin surface after drying are required. There are challenges.

  Therefore, in recent years, cellulose, which has a low environmental impact, has come to be used as a new reinforcing material for resins.

Cellulose is known to have a high elastic modulus comparable to that of aramid fiber and a linear expansion coefficient lower than that of glass fiber as its simple substance. Further, the true density is as low as 1.56 g / cm ^3, and glass (density 2.4 to 2.6 g / cm ³ ) and talc (density 2.7 g / used as a reinforcing material for general thermoplastic resins are used. It is an overwhelmingly light material compared to cm ³ ).

  Cellulose is not only made from trees, but also from hemp, cotton, kenaf, cassava, etc. Furthermore, bacterial cellulose represented by Nata de Coco is also known. A large amount of these natural resources, which are raw materials, exist on the earth, and the technique of utilizing cellulose in the resin as a filler has attracted attention for its effective use.

  CNF (cellulose nanofiber) is obtained by using pulp or the like as a raw material, hydrolyzing the hemicellulose portion to weaken it, and then defibrating it by a pulverizing method such as a high pressure homogenizer, a microfluidizer, a ball mill or a disc mill. It is known that it forms a highly dispersed state or network at a level called fine nanodispersion in water.

  However, in order to mix CNF into the resin, it is necessary to dry and powder the CNF, but CNF becomes a strong agglomerate in the process of separating from water and becomes a strong aggregate, which makes it difficult to redisperse. is there. This cohesive force is expressed by hydrogen bonds due to the hydroxyl groups of cellulose, and is said to be extremely strong.

  Therefore, in order to exhibit sufficient performance, it is necessary to alleviate hydrogen bonds due to the hydroxyl groups of cellulose. Even if the relaxation of hydrogen bonds can be sufficiently realized, it is difficult to maintain the defibrated state (nanometer size (that is, less than 1 μm)) in the resin. That is, in order to miniaturize cellulose having a low environmental load into CNF and highly disperse it in a resin as a nanofiller, there is a social demand for a technique of suppressing aggregation by an easy operation when drying CNF. .

  A technique for suppressing aggregation of these CNFs during drying and a technique for a composition in which CNF is used as a filler and composited with various resins have been proposed. For example, Patent Documents 1 and 2 describe a technique of forming a composite of cellulose and a resin by using a dispersant.

International Publication No. 2015/152189 International Publication No. 2017/006997 International Publication No. 2018/012643 International Publication No. 2014/133019 JP, 2005-143337, A

  In Patent Document 1, by using a special methacrylate-based polymer dispersant, a surfactant, and a large amount of an organic solvent, uniform dispersion in an aqueous system is achieved. Further, in Patent Document 1, uniform dispersion in a resin is achieved by using a special methacrylate-based polymer dispersant and cellulose in an equivalent amount of 1: 1. However, Patent Document 1 also describes that a large amount of a special polymer dispersant based on methacrylate is required and that the effect of improving the mechanical properties of the composition is very small. Further, the technique described in Patent Document 1 still has problems such as slidability, paintability, and thermal characteristics which are practical characteristics.

  In Patent Document 2, a resin-reinforcing mixture using a blocked isocyanate compound is prepared and uniformly dispersed in a resin. However, also in Patent Document 2, a production example describes a composition using a large amount of a blocked isocyanate compound and further a surfactant. The technique described in Patent Document 2 still has problems such as slidability, paintability, and thermal characteristics.

  Patent Document 3 describes a resin composition containing cellulose nanofibers and a resin, describes a water-soluble resin, a water-dispersible resin, a water-soluble urethane resin, a modified nylon resin, and the like as a resin, and also relates to a dispersant with a resin affinity. The polymerized segment, the cellulose affinity segment, the molecular weight, etc. are described, and the molding of a film-shaped or film-shaped molded product is also mentioned. The dispersant exhibits dispersibility due to the effect of electrostatic repulsion with cellulose, but the effect of improving mechanical properties and thermal properties is very small. It still has problems such as mobility, paintability, and thermal characteristics.

  Further, in Patent Document 4, water / NMP is added to hydrous CNF, a special dispersant in an emulsion state is used, and the CNF is uniformly dispersed in a resin by substituting with ethanol or another organic solvent. However, a large amount of organic solvent such as NMP is necessary to make a special dispersant into an emulsion state. The technique described in Patent Document 4 still has problems such as slidability, paintability, and thermal characteristics of the thermoplastic resin.

  Further, Patent Document 5 describes a technique of bonding a special dispersant, which is an EO (ethylene oxide) / PO (propylene oxide) copolymer compound and has an amine at the terminal, to a carboxy group on the surface of TEMPO-oxidized CNF. However, this reaction requires multiple reactions and therefore applies only to some special CNFs. The technique described in Patent Document 5 still has problems such as slidability of thermoplastic resin and coatability.

  Therefore, the techniques described in Patent Documents 1 to 5 face a problem that they are not suitable for actual use. That is, at the present time, a sufficient amount of cellulose to express the desired mechanical properties of the resin molded product is finely dispersed in the resin composition to obtain high mechanical properties and thermal properties (particularly reduced thermal expansion). In order to obtain a cellulose nanofiber-containing resin molded product having excellent coating properties and abrasion resistance (especially abrasion resistance during sliding), a dispersion liquid for cellulose nanofibers, a water dispersion liquid containing cellulose nanofibers, A dried cellulose nanofiber is not obtained.

  The present invention solves the above problems, a dispersion for cellulose nanofibers that can be dispersed without aggregating cellulose nanofibers in a system using water as a main medium in a simple method, and easily redispersed in water after drying. Cellulose nanofiber hydrous dispersion capable of providing excellent dispersibility of cellulose nanofibers in the resin, and when dispersed in the resin, while giving the resin composition sufficient mechanical properties and thermal properties, It is an object of the present invention to provide a dried cellulose nanofiber which gives excellent paintability and abrasion resistance in practical use.

  In order to solve the above-mentioned problems, the present inventors have conducted extensive studies, and as a result, the above-mentioned problems by combining a dispersion liquid containing a specific water-soluble surface treatment agent, polyurethane, and water with cellulose nanofibers. The inventors have found that the above can be solved and have completed the present invention.

That is, the present invention includes the following aspects.
[1] (A) A surface treatment agent which is a water-soluble polymer having a hydrophilic segment and a hydrophobic segment and having a number average molecular weight of 200 to 30,000,
(B) polyurethane and water,
A dispersion liquid containing.
[2] The dispersion liquid according to Aspect 1, further comprising (C) a water-soluble organic solvent.
[3] (A) A surface treatment agent which is a water-soluble polymer having a hydrophilic segment and a hydrophobic segment and having a number average molecular weight of 200 to 30,000,
(B) polyurethane,
(D) Cellulose nanofibers having an average fiber diameter of 1000 nm or less, and water,
A water-containing dispersion of cellulose nanofibers.
[4] 0.1 to 100 parts by mass of (A) surface treatment agent,
(B) 0.1 to 100 parts by mass of polyurethane,
(D) The water-containing dispersion of cellulose nanofibers according to the above aspect 3, containing 100 parts by mass of cellulose nanofibers and water.
[5] The aqueous cellulose nanofiber dispersion according to Aspect 3 or 4, wherein the HLB value of the surface treating agent (A) is 0.1 or more and less than 8.0.
[6] The aqueous dispersion of cellulose nanofibers according to any one of the above aspects 3 to 5, wherein the surface treatment agent (A) has a cloud point of 10 ° C or higher.
[7] The aqueous dispersion of cellulose nanofibers according to any one of the above aspects 3 to 6, wherein the hydrophilic segment contains a polyoxyethylene block and the hydrophobic segment contains a polyoxypropylene block.
[8] The cellulose according to any one of the above aspects 3 to 7, wherein the molecular structure of the surface treating agent (A) is one selected from an ABA type triblock structure, a three-branched structure, and a four-branched structure. Nanofiber hydrous dispersion.
[9] The aqueous dispersion of cellulose nanofibers according to the above aspect 8, wherein the molecular structure of the surface treatment agent (A) is a triblock structure of hydrophilic segment-hydrophobic segment-hydrophilic segment.
[10] The cellulose nano according to any one of the above aspects 3 to 9, wherein the hydrophilic segment and the hydrophobic segment have a molecular weight ratio (hydrophobic segment molecular weight / hydrophilic segment molecular weight) of 0.1 to 3. Fiber-containing water dispersion.
[11] The aqueous dispersion of cellulose nanofibers according to any one of the above aspects 3 to 10, wherein the surface treatment agent (A) is a nonionic surfactant.
[12] The aqueous dispersion of cellulose nanofibers according to the above aspect 11, wherein the surface treatment agent (A) is an ether type nonionic surfactant.
[13] The water-containing cellulose nanofiber dispersion according to any one of aspects 3 to 12, wherein the polyurethane (B) has a soft segment and a hard segment.
[14] The aqueous dispersion of cellulose nanofibers according to any one of the above aspects 3 to 13, wherein the (B) polyurethane is a modified polyurethane having a blocked isocyanate group.
[15] The aqueous dispersion of cellulose nanofibers according to any one of the above aspects 3 to 14, further comprising (C) a water-soluble organic solvent.
[16] The aqueous dispersion of cellulose nanofibers according to any one of the above aspects 3 to 15, further comprising (E) a binder component.
[17] A dried cellulose nanofiber, which is a dried product of the aqueous dispersion of cellulose nanofiber according to any one of the above aspects 3 to 16.
[18] The aqueous dispersion of cellulose nanofibers according to any one of the above aspects 3 to 16 or the dried cellulose nanofiber according to the above aspect 17, and (F) a thermoplastic resin,
A cellulose nanofiber composition comprising:
[19] (A) 0.1 to 50% by mass of a surface treatment agent which is a water-soluble polymer having a hydrophilic segment and a hydrophobic segment and a number average molecular weight of 200 to 30,000,
(B) 0.1 to 50% by mass of polyurethane,
(D) 1 to 50% by mass of cellulose nanofibers having an average fiber diameter of 1000 nm or less, and (F) 1 to 98.8% by mass of a thermoplastic resin,
A cellulose nanofiber resin composition containing the same.
[20] The cellulose nanofiber resin composition according to Aspect 18 or 19, wherein the (A) surface treatment agent has an HLB value of 0.1 or more and less than 8.0.
[21] The cellulose nanofiber resin composition according to any of Aspects 18 to 20, wherein the clouding point of the surface treating agent (A) is 10 ° C. or higher.
[22] The cellulose nanofiber resin composition according to any one of Aspects 18 to 21, wherein the hydrophilic segment contains a polyoxyethylene block and the hydrophobic segment contains a polyoxypropylene block.
[23] The cellulose according to any one of Aspects 18 to 22, wherein the molecular structure of the surface treating agent (A) is one selected from an ABA type triblock structure, a three-branched structure, and a four-branched structure. Nanofiber resin composition.
[24] The cellulose nanofiber resin composition according to Aspect 23, wherein the molecular structure of the surface treatment agent (A) is a triblock structure of hydrophilic segment-hydrophobic segment-hydrophilic segment.
[25] The cellulose nanoparticle according to any one of the above aspects 18 to 24, wherein a molecular weight ratio between the hydrophilic segment and the hydrophobic segment (hydrophobic segment molecular weight / hydrophilic segment molecular weight) is 0.1 to 3. Fiber resin composition.
[26] The cellulose nanofiber resin composition according to any of Aspects 18 to 25, wherein the surface treating agent (A) is a nonionic surfactant.
[27] The cellulose nanofiber resin composition according to the above aspect 26, wherein the surface treatment agent (A) is an ether type nonionic surfactant.
[28] (B) The polyurethane has a soft segment and a hard segment,
The cellulose nanofiber resin composition according to any one of the above aspects 18 to 27, wherein (B) polyurethane is bonded to (D) cellulose nanofiber and / or (F) thermoplastic resin.
[29] (F) 0.1 to 200 parts by mass of the surface treatment agent and (D) 1 to 200 parts by mass of cellulose nanofiber, relative to 100 parts by mass of the thermoplastic resin,
(A) The cellulose nanofiber resin composition according to any of Aspects 18 to 28, wherein the number average molecular weight of the surface treatment agent is 200 to 25,000.
[30] The cellulose nanofiber resin composition according to any one of aspects 18 to 29, which further contains water and is in the form of a water-containing dispersion.
[31] The cellulose nanofiber resin composition according to the above aspect 30, further comprising (C) a water-soluble organic solvent.
[32] The cellulose nanofiber resin composition according to any one of the aspects 18 to 29, which is in the form of a dried product.
[33] The cellulose nanofiber resin composition according to any one of Aspects 18 to 32, further including (E) a binder component.
[34] A total of 0.1 to 100 parts by mass of the (A) surface treatment agent, and (B) polyurethane and (E) binder components based on 100 parts by mass of (D) cellulose nanofibers. The cellulose nanofiber resin composition according to any of Aspects 18 to 33, which comprises a mass part.
[35] The cellulose nanofiber resin composition according to the above aspect 33 or 34, wherein the binder component (E) is bound or adsorbed to the cellulose nanofiber (D).
[36] The cellulose nanofiber resin composition according to any one of the above aspects 33 to 35, wherein the binder component (E) is bound or adsorbed to the thermoplastic resin (F).
[37] (F) The thermoplastic resin is a polyolefin resin, a polyamide resin, a polyester resin, a polyacetal resin, a polyacrylic resin, a polyphenylene ether resin, a polyphenylene sulfide resin, or any two or more of them. The cellulose nanofiber resin composition according to any one of the above aspects 18 to 36, which is selected from the group consisting of a mixture.
[38] From the mass content a of (D) cellulose nanofibers in the cellulose nanofiber resin composition, the tensile yield strength b of the resin composition, and the tensile yield strength c of the (F) thermoplastic resin, Formula (1):
Tensile yield strength improvement rate = (b / c-1) / a (1)
38. The cellulose nanofiber resin composition according to any one of the aspects 18 to 37, wherein the tensile yield strength improvement rate obtained according to the above is greater than 1.0.
[39] From the mass content a of the (D) cellulose nanofibers in the cellulose nanofiber resin composition, the bending elastic modulus d of the resin composition, and the bending elastic modulus e of the (F) thermoplastic resin, Formula (2):
Flexural modulus improvement rate = (d / e-1) / a
The cellulose nanofiber resin composition according to any one of the above aspects 18 to 38, wherein the flexural modulus improvement rate obtained according to the above is greater than 3.0.
[40] A resin molded product formed from the cellulose nanofiber resin composition according to any of Aspects 18 to 39.
[41] A method for producing the cellulose nanofiber resin composition according to any one of the above aspects 18 to 39,
At least (A) a surface treating agent which is a water-soluble polymer having a hydrophilic segment and a hydrophobic segment and a number average molecular weight of 200 to 30,000, (B) polyurethane, (D) cellulose nanofiber, and (F) ) A method comprising kneading with a thermoplastic resin.
[42] A method for producing a cellulose nanofiber resin composition according to any one of Aspects 18 to 39,
Preparing the cellulose nanofiber-containing water-containing aqueous dispersion according to any one of the above aspects 3 to 16 or the cellulose nanofiber dry-body according to the above aspect 17, and the cellulose nanofiber-containing water-containing dispersion or the cellulose nanofiber dried body. And kneading at least (F) a thermoplastic resin,
Including the method.

  According to the present invention, a dispersion liquid for cellulose nanofibers which can be dispersed in a system having water as a main medium in a simple method without agglomerating the cellulose nanofibers, which can be easily redispersed in water after drying, and into a resin. Cellulose nanofiber water-containing dispersion that gives excellent dispersibility of the above-mentioned cellulose nanofiber, and an excellent coating in practical use while giving sufficient mechanical properties and thermal properties to the resin composition when dispersed in a resin. Provided is a dried cellulose nanofiber that imparts resistance and abrasion resistance.

  Illustrative aspects of the invention are specifically described below, but the invention is not limited to these aspects.

  One aspect of the present invention is a surface treatment agent which is a water-soluble polymer having (A) a hydrophilic segment and a hydrophobic segment and having a number average molecular weight of 200 to 30,000 (in the present disclosure, “(A) surface treatment agent”). Also referred to as a), (B) polyurethane, and water.

  One aspect of the present invention includes (A) a surface treatment agent, (B) polyurethane, and (D) a cellulose nanofiber having an average fiber diameter of 1000 nm or less (also referred to as “(D) cellulose nanofiber” in the present disclosure). And a water-containing dispersion of cellulose nanofibers, and a dried cellulose nanofiber which is a dried product of the water-containing dispersion of cellulose nanofibers.

In one aspect, the aqueous dispersion of cellulose nanofibers,
(A) 0.1 to 100 parts by mass of the surface treatment agent,
(B) 0.1 to 100 parts by mass of polyurethane,
(D) 100 parts by mass of cellulose nanofibers and water.

  One aspect of the present invention is a resin composition containing (A) a surface treatment agent, (B) polyurethane, (D) cellulose nanofibers and (F) a thermoplastic resin, and a resin molded body formed from the resin composition. I will provide a. In one aspect, the resin composition further comprises water and is in the form of a hydrous dispersion. In one aspect, the resin composition is in the form of a dry body.

  In one embodiment, the cellulose nanofiber composition comprises the cellulose nanofiber aqueous dispersion of the present disclosure or the dried cellulose nanofiber of the present disclosure, and (F) a thermoplastic resin.

In one aspect, the cellulose nanofiber resin composition is
(A) 0.1 to 50% by mass of a surface treatment agent which is a water-soluble polymer having a hydrophilic segment and a hydrophobic segment and a number average molecular weight of 200 to 30,000;
(B) 0.1 to 50% by mass of polyurethane,
(D) 1 to 50% by mass of cellulose nanofibers having an average fiber diameter of 1000 nm or less, and (F) 1 to 98.8% by mass of a thermoplastic resin,
Including.

  In one embodiment, the cellulose nanofiber resin composition has 1 to 200 parts by mass of the (A) surface treatment agent and 1 to 100 parts by mass of the (D) cellulose nanofiber with respect to 100 parts by mass of the thermoplastic resin (F). 200 parts by mass are included, and the number average molecular weight of the surface treating agent (A) is 200 to 25,000.

  In one embodiment, the cellulose nanofiber resin composition has 0.1 to 100 parts by mass of the (A) surface treatment agent, and (B) polyurethane and (E) binder with respect to 100 parts by mass of (D) cellulose nanofibers. The components are contained in a total amount of 0.1 to 100 parts by mass.

≪ (A) Surface treatment agent≫
The surface treatment agent (A) of the present disclosure is a water-soluble polymer, has a hydrophilic segment and a hydrophobic segment, and has a number average molecular weight of 200 to 30,000. In the present disclosure, "water-soluble" means that 0.1 g or more is dissolved in 100 g of water at 23 ° C. The (A) surface treatment agent is a component different from the (B) polyurethane, (E) binder component and (F) thermoplastic resin described below. For example, the (A) surface treatment agent is a modified product (for example, an acid modified product or a copolymer) of the same kind of polymer as the (B) polyurethane, (E) binder component or (F) thermoplastic resin of the present disclosure, (B). ) It is different from (B) polyurethane, (E) binder component and (F) thermoplastic resin because it is a polymer different from polyurethane, (E) binder component or (F) thermoplastic resin. For example, the thermoplastic resin (F) does not have water solubility, and the surface treatment agent (A) has water solubility. The surface-treating agent (A) may be mixed with the polyurethane (B) in the form of, for example, an aqueous dispersion containing the surface-treating agent (A) at a high concentration or an aqueous solution. The surface treating agent (A) may be a commercially available reagent or product.

  The hydrophilic segment of the surface treating agent (A) has good affinity with the surface of cellulose. The hydrophobic segment can suppress aggregation of celluloses through the hydrophilic segment. Therefore, in the surface treatment agent (A), the hydrophilic segment and the hydrophobic segment must be present in the same molecule.

  In a typical embodiment, the hydrophilic segment contains a hydrophilic structure (for example, one or more hydrophilic groups selected from a hydroxyl group, a carboxy group, a carbonyl group, an amino group, an ammonium group, an amide group, a sulfo group, etc.). Is a portion showing a good affinity with (D) cellulose nanofibers. As the hydrophilic segment, a segment of polyethylene glycol (that is, a segment of plural oxyethylene units) (PEG block), a segment containing a repeating unit containing a quaternary ammonium salt structure, a segment of polyvinyl alcohol, a segment of polyvinylpyrrolidone, poly Acrylic acid segment, carboxyvinyl polymer segment, cationized guar gum segment, hydroxyethyl cellulose segment, methyl cellulose segment, carboxymethyl cellulose segment, polyurethane soft segment (soft segment) (specifically diol segment), etc. It can be illustrated. In a preferred embodiment, the hydrophilic segment comprises oxyethylene units.

Examples of the hydrophobic segment include a segment having an alkylene oxide unit having 3 or more carbon atoms (for example, PPG block), a segment including the following polymer structure, and the like:
Acrylic polymer, styrene resin, vinyl chloride resin, vinylidene chloride resin, polyolefin resin, polyhexamethylene adipamide (6,6 nylon), polyhexamethylene azeramide (6,9 nylon), polyhexamethylene Organic dicarboxylic acids having 4 to 12 carbon atoms and 2 to 13 carbon atoms, such as sebacamide (6,10 nylon), polyhexamethylene dodecanoamide (6,12 nylon), polybis (4-aminocyclohexyl) methandodecane, etc. Polycondensate with an organic diamine, a polycondensate of ω-amino acid (for example, ω-aminoundecanoic acid) (for example, polyundecane amide (11 nylon), etc.), and a polycapramide which is a ring-opening polymer of ε-aminocaprolactam ( 6 Nylon), polylauric lacquer which is a ring-opening polymer of ε-aminolaurolactam Amino acid lactam containing ring-opening polymer of lactam, such as vinyl (12 nylon), polymer composed of diamine and dicarboxylic acid, polyacetal resin, polycarbonate resin, polyester resin, polyphenylene sulfide resin, polysulfone resin , Polyetherketone resin, polyimide resin, fluorine resin, hydrophobic silicone resin, melamine resin, epoxy resin, phenol resin.

Further examples of structures that the hydrophobic segment contains include the following:
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) Acrylic containing one or more repeating units among acrylate, cyclohexylmethyl (meth) acrylate, (meth) acrylic acid, adamantyl (meth) acrylate, norbonyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, etc. Polymer
Contains one or more repeating units of styrene, α-methylstyrene, o-, m-, and p-methylstyrene, ethylstyrene, propylstyrene, butylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene, etc. Styrene resin;
Polyvinyl chloride, or comonomers copolymerizable with vinyl chloride and the vinyl chloride (for example, acrylic acid esters such as methyl acrylate, ethyl acrylate and butyl acrylate, methacrylic acid esters such as methyl methacrylate and ethyl methacrylate, dibutyl maleate) , Maleic acid esters such as diethyl maleate, vinyl ethers such as vinyl butyl ether and vinyl butyl ether, α-olefins such as ethylene, propylene and styrene, vinylidene halides such as vinylidene chloride or vinyl halides) Vinyl chloride resin containing polymer;

Polyvinylidene chloride or comonomers copolymerizable with vinylidene chloride (for example, acrylic acid esters such as methyl acrylate, ethyl acrylate and butyl acrylate, methacrylic acid esters such as methyl methacrylate and ethyl methacrylate, dibutyl maleate, diethyl maleate) Vinylidene chloride resin containing a copolymer of maleic acid ester, vinyl butyl ether, vinyl butyl ether and other vinyl ethers, ethylene, propylene, styrene and other α-olefins, vinyl chloride) and vinylidene chloride;
Polyolefin resins such as polyethylene, polypropylene and polybutene;
Polyhexamethylene adipamide (6,6 nylon), polyhexamethylene azeramide (6,9 nylon), polyhexamethylene sebacamide (6,10 nylon), polyhexamethylene dodecanoamide (6,12 nylon) A polycondensation product of an organic dicarboxylic acid having 4 to 12 carbon atoms and an organic diamine having 2 to 13 carbon atoms, such as polybis (4-aminocyclohexyl) methandodecane;
polycondensation product of ω-amino acid (for example, ω-aminoundecanoic acid) (for example, polyundecane amide (11 nylon));
Amino acid lactams containing ring-opening polymers of lactams, such as polycapramide (6 nylon), which is a ring-opening polymer of ε-aminocaprolactam, and polylauric lactam (12 nylon), which is a ring-opening polymer of ε-aminolaurolactam. ;
Polymers composed of diamines and dicarboxylic acids;
A polyacetal resin containing a homopolymer of formaldehyde or a copolymer of formaldehyde and other components;

  2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, bis (4 -Hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (4- Hydroxy-3-t-butylphenyl) propane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis 4-hydroxy-3-methylphenyl) fluorene, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4 Aromatic bisphenols such as -bis {2- (4-hydroxyphenyl) propyl} benzene, 2,2-bis (4-hydroxyphenyl) -1,1,1-3,3,3-hexafluoropropane, 2, A polycondensation product of a dihydroxy compound such as an aliphatic diol such as 2-dimethyl-1,3-propanediol, spiroglycol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol with phosgene or diphenyl carbonate. A polycarbonate resin;

Polyester-based resin containing polyester or a copolymer of a polyester-derived component and another polymer-derived component;
A polyphenylene sulfide-based resin containing polyphenylene sulfide or a copolymer of a component derived from polyphenylene sulfide and a component derived from another polymer;
A polysulfone homopolymer having an aromatic ring group and a sulfone group as a bonding group in the main chain, or a polysulfone resin containing a copolymer of a component derived from the polysulfone homopolymer and a component derived from another polymer;
A polyetherketone-based resin containing a polyetherketone polymer or a copolymer of a component derived from a polyetherketone and a component derived from another polymer;
Aromatic diamines such as p-phenylenediamine, m-phenylenediamine, 1,4-diaminonaphthalene, and 1,5-diaminonaphthalene, and pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic acid Dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 2,3,4,5-thiophenetetracarboxylic dianhydride A polyimide resin which is a reaction product of an acid anhydride such as a compound;
A homopolymer or copolymer of a monomer selected from tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether, vinylidene fluoride and vinyl fluoride, or a copolymer of the above monomer and ethylene, etc. Fluorine-based resin;
Hydrophobic silicone resin such as alkylpolysiloxane, perfluoroalkylsilane, fluorinated olefin telomer, organosilane;
Urea such as urea, thiourea and ethylene urea, guanamines such as benzoguanamine, acetoguanamine, formguanamine, phenylacetoguanamine and CTU guanamine, other amino compounds such as guanidine, dicyandiamide and paratoluenesulfonamide, phenol, cresol, Melamine resin, which is a cocondensation product of phenols such as xylenol, ethylphenol, butylphenol, and bisphenol A;

  Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin or other bisphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin or other novolac type epoxy resin, trisphenol Aromatic epoxy resins such as methanetriglycidyl ether, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, and hydrogenated or brominated products thereof, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-Epoxy-2-methylcyclohexylmethyl-3,4-epoxy-2-methylcyclohexanecarboxylate, bis (3,4-epoxycyclohexyl) adipate, bis ( , 4-Epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexanone-meta Of alicyclic epoxy resins such as dioxane, bis (2,3-epoxycyclopentyl) ether, trade name “EHPE-3150” (softening temperature 71 ° C., manufactured by Daicel Chemical Industries), 1,4-butanediol Diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, carbon number 2-9 (preferably Is 2-4) Aliphatic epoxy resin such as polyglycidyl ether of long chain polyol containing polyoxyalkylene glycol containing groups and polytetramethylene ether glycol, diglycidyl phthalate, diglycidyl tetrahydrophthalate, dihydrohexaphthalate Glycidyl ester type epoxy resin such as glycidyl ester, diglycidyl-p-oxybenzoic acid, glycidyl ether-glycidyl ester of salicylic acid, glycidyl dimer acid, triglycidyl isocyanurate, N, N'-diglycidyl derivative of cyclic alkylene urea, Glycidylamine type epoxy resins such as N, N, O-triglycidyl derivatives of p-aminophenol and N, N, O-triglycidyl derivatives of m-aminophenol, glycidyl (meth) Copolymers of acrylates with radically polymerizable monomers such as ethylene, vinyl acetate, (meth) acrylic acid ester, etc., polymers mainly composed of conjugated diene compounds such as epoxidized polybutadiene, etc. or partially hydrogenated products thereof. Polymer block mainly composed of vinyl aromatic compounds such as epoxidized unsaturated carbon double bond, epoxidized SBS, etc., and polymer block mainly composed of conjugated diene compound or partial hydrogenation thereof A block copolymer having a polymer block in the same molecule as the conjugated diene compound in which the unsaturated carbon double bond is epoxidized, and the various epoxy group-containing compounds described above include NBR, CTBN, polybutadiene, and acrylic rubber Epoxy resin such as rubber-modified epoxy resin containing a rubber component such as;

  Unsubstituted phenols such as phenol, resorcinol, hydroquinone, monosubstituted phenols such as cresol, ethylphenol, n-propylphenol, octylphenol, nonylphenol, phenylphenol, xylenol, methylpropylphenol, dipropylphenol, dibutylphenol, guaiacol , Disubstituted phenols such as guetol, trisubstituted phenols such as trimethylphenol, naphthols such as naphthol and methylnaphthol, and bisphenols such as bisphenol, bisphenol A, and bisphenol F as monomers, and at least the aromatic ring. A phenolic resin such as a novolac type phenolic resin or a resol type phenolic resin which is a compound having one phenolic hydroxyl group.

  The surface treatment agent (A) may have a graft copolymer structure and / or a block copolymer structure. These may be used alone or in combination of two or more. When two or more kinds are used together, they may be used as a polymer alloy. Further, it may be a partially modified product or a terminal modified product (for example, an acid modified product) of these copolymers.

  The structure of the surface-treating agent (A) is not particularly limited, but when the hydrophilic segment is A and the hydrophobic segment is B, an AB type block copolymer, an ABA type block (that is, triblock) copolymer, BAB type block copolymer, ABAB type block copolymer, ABABA type block copolymer, BABAB type copolymer, three-branch type copolymer containing A and B, four-branched type copolymer containing A and B , A star-shaped copolymer containing A and B, a monocyclic copolymer containing A and B, a polycyclic copolymer containing A and B, a cage copolymer containing A and B, and the like.

  The structure of the surface-treating agent (A) is preferably an AB type block copolymer, an ABA type block copolymer, a three-branched copolymer containing A and B, or a four-branched copolymer containing A and B. And more preferably an ABA type block copolymer, a three-branched copolymer containing A and B, or a four-branched copolymer containing A and B. In order to ensure good affinity with (D) cellulose nanofibers, the structure of (A) surface treatment agent is preferably the above structure.

  Preferred examples of the surface-treating agent (A) include compounds that give hydrophilic segments (for example, polyethylene glycol), compounds that give hydrophobic segments (for example, polypropylene glycol, poly (tetramethylene ether) glycol (PTMEG), and polybutadiene diol. Etc.) (for example, a block copolymer of propylene oxide and ethylene oxide, a block copolymer of tetrahydrofuran and ethylene oxide) and the like. The surface treatment agents may be used alone or in combination of two or more. When two or more kinds are used together, they may be used as a polymer alloy. Further, it is also possible to use a modified product of the above-mentioned copolymer (for example, a product modified with at least one compound selected from unsaturated carboxylic acids, acid anhydrides or derivatives thereof).

  Among these, a copolymer of polyethylene glycol and polypropylene glycol, a copolymer of polyethylene glycol and poly (tetramethylene ether) glycol (PTMEG), and a mixture thereof are preferable from the viewpoint of heat resistance, paintability and mechanical properties. Among them, a copolymer of polyethylene glycol and polypropylene glycol is more preferable from the viewpoint of handleability and cost.

  In an exemplary embodiment, (A) the surface treatment agent has a functional group (that is, a group of the present disclosure) capable of chemically or physically binding or interacting with (D) cellulose nanofibers and / or (F) a thermoplastic resin. It has one or more reactive functional groups). In one aspect, the reactive functional group contained in the surface treating agent (A) is a group that exhibits binding or adsorptivity with at least a hydroxyl group. As the reactive functional group, a hydroxyl group, a carboxyl group, a formyl group, an acyl group, an amino group, an azo group, an adi group, an imino group, a carbonyl group, a thiocarbonyl group, a diimide group, a thiol group, an epoxy group, an isocyanate group, Isothiocyanate group, sulfone group, cyano group, nitro group, isonitrile group, vinyl group, allyl group, alkoxy group, acid anhydride group, carbon-carbon double bond, ester bond, thioester bond, ether bond, thioether bond, disulfide A bond, an amide bond, an imide bond, a urethane bond, etc. are mentioned. One or more of these reactive functional groups can be present in the molecule.

  Among these, a hydroxyl group, a carboxyl group, a formyl group, an amino group, a carbonyl group, and an isocyanate group can be preferably used from the viewpoint of reactivity with (D) cellulose nanofibers and / or (F) thermoplastic resin. .

  In one embodiment, the surface treatment agent (A) is a nonionic surfactant, preferably an ether type nonionic surfactant.

  In a typical embodiment, the surface treatment agent (A) has a cloud point. When the temperature of an aqueous solution of a nonionic surfactant having a polyether chain such as a polyoxyethylene chain as a hydrophilic portion is increased, a certain temperature of a transparent or translucent aqueous solution is reached (this temperature is called a cloud point. ), There is a phenomenon that it becomes cloudy. That is, when an aqueous solution that is transparent or translucent at low temperature is heated, the solubility of the nonionic surfactant decreases sharply at a certain temperature, and the previously dissolved surfactants aggregate and become cloudy. And separate from water. It is considered that this is because the nonionic surfactant loses its hydration power at high temperatures (hydrogen bond between the polyether chain and water is broken and the solubility in water sharply decreases). The cloud point tends to be lower as the polyether chain is longer. If the temperature is below the cloud point, it will dissolve in water at an arbitrary ratio, so the cloud point is a measure of hydrophilicity in the surface treatment agent (A).

  The cloud point of the surface-treating agent (A) can be measured by the following method. Using a tuning fork type vibration viscometer (for example, SV-10A manufactured by A & D Co., Ltd.), the aqueous solution of (A) the surface treatment agent was changed to 0.5% by mass, 1.0% by mass and 5% by mass. It adjusts and measures in the temperature range of 0-100 degreeC. At this time, a portion showing an inflection point (change in increase in viscosity or a point where the aqueous solution becomes cloudy) at each concentration is defined as a cloud point.

  The lower limit of the cloud point of the surface-treating agent (A) is preferably 10 ° C, more preferably 20 ° C, and most preferably 30 ° C from the viewpoint of handleability. The upper limit of the cloud point is not particularly limited, but is preferably 120 ° C, more preferably 110 ° C, further preferably 100 ° C, and most preferably 60 ° C. In order to ensure good affinity with (D) cellulose nanofibers having an average fiber diameter of 1000 nm or less, the cloud point of (A) the surface treating agent is preferably within the above range.

  The lower limit of the melting point of the surface treatment agent (A) is preferably −50 ° C., more preferably −30 ° C., most preferably −10 ° C., from the viewpoint of not plasticizing the resin composition, and the upper limit. From the viewpoint of operability, the value is preferably 70 ° C, more preferably 60 ° C, and most preferably 55 ° C.

  The lower limit of the mass ratio (hydrophobic segment molecular weight / hydrophilic segment molecular weight) of the hydrophilic segment and the hydrophobic segment of the surface treating agent (A) is not particularly limited, but is preferably 0.1, and more preferably 0. 0.2, and most preferably 0.3. The upper limit of the mass ratio of the hydrophilic segment and the hydrophobic segment (hydrophobic segment molecular weight / hydrophilic segment molecular weight) is preferably 15, more preferably 10, and even more preferably from the viewpoint of solubility in water. 5, most preferably 3. In order to secure good affinity with (D) cellulose nanofibers having an average fiber diameter of 1000 nm or less, the above ratio of the (A) surface treatment agent is preferably within the above range. When the HLB value of the surface treatment agent (A) is set to 0.1 or more and less than 8.0 as described below, the above mass ratio (hydrophobic segment molecular weight / hydrophilic segment molecular weight) has a predetermined HLB value. From the standpoint of easy adjustment, it is preferably 1.5, more preferably 1.55, most preferably 1.6, and the point that the HLB value can be easily adjusted to a predetermined value or more, and water. The solubility is preferably 199, more preferably 100, more preferably 50, and most preferably 20.

  The lower limit of the number average molecular weight of the (A) surface treatment agent is 200, preferably 250, and more preferably 300, from the viewpoint of favorably improving the dispersibility of the cellulose nanofibers in the resin. It is more preferably 400, and most preferably 500. In addition, the upper limit of the number average molecular weight is 30,000, preferably 25,000, more preferably 23,000, further preferably 20,000, further preferably 10,000, further preferably 5,000, further preferably less than 5,000 from the viewpoint of handleability. , And more preferably 4000. (D) From the viewpoint of ensuring good affinity with cellulose nanofibers having an average fiber diameter of 1000 nm or less, and in one embodiment, (A) a surface treatment agent, (B) polyurethane and an optional (E) binder. The number average molecular weight of the (A) surface treatment agent is as described above from the viewpoint of improving the binding or adsorption of the combination with the components and the (D) cellulose nanofibers and / or (F) thermoplastic resin in the resin composition. It is desirable to be within the range.

  The lower limit of the molecular weight of the hydrophilic segment of the surface treatment agent (A) is preferably 100, more preferably 150, more preferably 200, more preferably 300, and most preferably from the viewpoint of affinity with cellulose nanofibers. It is 500, and the upper limit value is preferably 30,000, more preferably 25,000, most preferably 20,000, more preferably 15,000, and most preferably 10,000 from the viewpoint of solubility in water.

  The lower limit of the molecular weight of the hydrophobic segment of the (A) surface treatment agent is preferably 100, more preferably 150, more preferably 200, more preferably 500, from the viewpoint of dispersibility of the cellulose nanofibers in the resin. The most preferable value is 1000, and the upper limit value is preferably 5000, more preferably 4000, and most preferably 3500 from the viewpoint of solubility in water.

In one aspect, the surface treating agent (A) has an HLB value of 0.1 or more and less than 8.0. The HLB value is a value showing the balance between the hydrophobicity and hydrophilicity of the surfactant, and takes a value from 1 to 20. The smaller the value, the stronger the hydrophobicity, and the larger the value, the stronger the hydrophilicity. Show. In the present disclosure, the HLB value is a value calculated by the following Griffin's method. In addition, in the following formula 1, "sum of formula weights of hydrophilic groups / molecular weight" is% by mass of hydrophilic groups.
Formula 1) Griffin method: HLB value = 20 × (sum of formula weights of hydrophilic groups / molecular weight)

  The lower limit of the HLB value of the (A) surface treatment agent of the present disclosure is preferably 0.1, more preferably 0.2, and most preferably 1.0 from the viewpoint of easy solubility in water. Is. Moreover, the upper limit of the HLB value is preferably less than 8.0, more preferably 7.5, and more preferably 7. From the viewpoint of redispersibility of the cellulose nanofibers in water or an organic solvent. It is 0. Excellent redispersibility in an organic solvent means excellent dispersibility in a resin.

  In the dispersion liquid of one aspect, the preferable amount of the surface treatment agent (A) is 0.1 to 60 mass% with respect to the entire dispersion liquid. The upper limit amount is more preferably 50 mass%, more preferably 40 mass%, more preferably 35 mass%, more preferably 30 mass%, more preferably 20 mass%, more preferably 10 mass%, more preferably 5 mass%. %, Particularly preferably 3% by weight. The lower limit is not particularly limited, but is preferably 0.1% by mass, more preferably 0.2% by mass, more preferably 0.5% by mass, and most preferably 1% by mass. By setting the upper limit of the amount of the surface-treating agent (A) to the above value, the viscosity of the dispersion liquid does not become excessively high, and a uniform cellulose nanofiber water-containing dispersion liquid can be easily prepared using the dispersion liquid. Further, by setting the lower limit amount of the (A) surface treatment agent to the above, redispersibility of the cellulose nanofibers (that is, the dried cellulose nanofibers prepared by using the aqueous dispersion of the cellulose nanofibers is dispersed in water). The dispersibility of the cellulose nanofibers) can be increased.

  In each of the resin composition and the resin molded body, the preferable amount of the (A) surface treatment agent is in the range of 0.1 to 50 mass% with respect to the entire resin composition or the resin molded body. The upper limit is more preferably 18% by mass, further preferably 15% by mass, even more preferably 10% by mass, particularly preferably 5% by mass. The lower limit is not particularly limited, but is preferably 0.1% by mass, more preferably 0.2% by mass, and most preferably 0.5% by mass. By setting the upper limit of the amount of the surface treatment agent (A) to the above range, plasticization of the resin composition can be suppressed and good strength can be maintained. Further, by setting the lower limit amount of the (A) surface treatment agent to the above, the dispersibility of the (D) cellulose nanofibers in the (F) thermoplastic resin can be enhanced.

  In each of the resin composition and the resin molded body, the lower limit of the amount of the (A) surface treatment agent is preferably 0.01 part by mass, more preferably 0 part by mass, relative to 100 parts by mass of the (F) thermoplastic resin. 0.05 parts by mass, more preferably 0.1 parts by mass, more preferably 0.5 parts by mass, more preferably 1 part by mass, further preferably 2 parts by mass, and the upper limit amount is preferably 200 parts by mass, It is preferably 150 parts by mass, more preferably 100 parts by mass, more preferably 50 parts by mass, more preferably 10 parts by mass, and further preferably 5 parts by mass. By setting the upper limit of the amount of the surface treating agent (A) to the above range, it is possible to suppress the plasticization of the thermoplastic resin (F) and keep the strength good. Further, by setting the lower limit amount of the (A) surface treatment agent to the above, the dispersibility of the (D) cellulose nanofibers in the (F) thermoplastic resin can be enhanced.

  In each of the aqueous dispersion of cellulose nanofibers, the dried cellulose nanofibers, the resin composition and the resin molded product, the preferable amount of the (A) surface treatment agent is (D) the cellulose nanofiber 100 having an average fiber diameter of 1,000 nm or less. It is within the range of 0.1 to 100 parts by mass with respect to parts by mass. The upper limit amount is more preferably 99 parts by mass, more preferably 90 parts by mass, more preferably 80 parts by mass, even more preferably 70 parts by mass, even more preferably 50 parts by mass, particularly preferably 40 parts by mass. The lower limit is not particularly limited, but is preferably 0.1 part by mass, more preferably 0.5 part by mass, and most preferably 1 part by mass. By setting the upper limit of the amount of the surface treatment agent (A) to the above range, it is possible to suppress plasticization in the resin composition and the resin molded article and maintain good strength. Further, by setting the lower limit amount of the (A) surface treatment agent to the above, the redispersibility of the (D) cellulose nanofibers can be enhanced.

The amount of the surface treatment agent (A) in the dispersion can be easily confirmed by a person skilled in the art by a general method. The confirmation method is not limited, but the following method can be exemplified. Salting out or centrifugation is performed using the dispersion liquid. This makes it possible to separate the sediment (polyurethane) and the dispersion liquid other than polyurethane, and by concentrating (drying, air drying, vacuum drying, etc.) the isolated dispersion liquid other than polyurethane (A) the amount of the surface treatment agent can be determined. It is possible. Regarding the (A) surface treatment agent after concentration, gel permeation chromatography, MALDI (matrix assisted laser desorption ionization method) / TOF-MS (time of flight mass spectrometry), pyrolysis GC-MS (gas chromatograph mass spectrometry) Method), ¹ H-NMR, or ¹³ C-NMR (nuclear magnetic resonance spectroscopy), qualitative analysis (ie, identification) of the molecular structure and measurement of the molecular weight can be performed.

  The amount of the surface-treating agent (A) in the aqueous dispersion of cellulose nanofibers and in the dried cellulose nanofibers can be easily confirmed by those skilled in the art by a general method. The confirmation method is not limited, but the following method can be exemplified. Water is added to the dried cellulose nanofibers to obtain a cellulose nanofiber aqueous dispersion. Centrifugation is performed on the aqueous dispersion of cellulose nanofibers. As a result, it is possible to separate the sediment (cellulose nanofiber and polyurethane) and the surface treatment agent dispersion liquid. By concentrating (drying, air drying, drying under reduced pressure, etc.) the surface treatment agent dispersion, (A) the surface treatment agent can be quantified. The concentrated (A) surface treatment agent can be identified and the molecular weight can be measured by the methods described above.

  In each of the resin composition and the resin molded product, the amount of the (A) surface treatment agent can be easily confirmed by a person skilled in the art by a general method. The confirmation method is not limited, but the following method can be exemplified. When a resin composition or a fragment of a resin molded product is used and the resin composition is dissolved in a solvent (F) in which the thermoplastic resin is dissolved, a soluble component 1 (resin and surface treatment agent) and an insoluble component 1 ( (Cellulose and polyurethane and surface treatment agent) are separated. The soluble component 1 is reprecipitated with a solvent that does not dissolve polyurethane but does dissolve the surface treating agent, and is separated into an insoluble component 2 (resin) and a soluble component 2 (surface treating agent). Insoluble matter 1 is dissolved in a polyurethane-soluble solvent to separate soluble matter 3 (polyurethane and surface treatment agent) and insoluble matter 3 (cellulose). The soluble component 3 is reprecipitated with a solvent that does not dissolve polyurethane but does dissolve the surface treating agent, and is separated into an insoluble component 4 (polyurethane) and a soluble component 4 (surface treating agent). By concentrating the surface treatment agents (soluble matter 2 and soluble matter 4) isolated by the above operation, it is possible to quantify the surface treatment agent (A). The concentrated (A) surface treatment agent can be identified and the molecular weight can be measured by the methods described above.

  The method for adding the (A) surface treatment agent in preparing the dispersion is not particularly limited, but the (A) surface treatment agent is dissolved in water, and (B) polyurethane is added to the obtained surface treatment agent aqueous solution. A method of obtaining a dispersion by adding and mixing, a method of dispersing (B) polyurethane in water, adding (A) a surface treatment agent to the obtained polyurethane dispersion, and mixing to obtain a dispersion. Is mentioned.

  In addition, the method for adding the (A) surface treatment agent when preparing the resin composition is not particularly limited, but (F) a thermoplastic resin, (D) a cellulose nanofiber having an average fiber diameter of 1000 nm or less, And (A) a method of previously mixing and melt-kneading the surface-treating agent, (F) after adding the (A) surface-treating agent to the thermoplastic resin in advance, and preliminarily kneading if necessary, (D) an average fiber diameter of 1000 nm or less (D) Cellulose nanofibers having an average fiber diameter of 1000 nm or less and (A) a surface treatment agent are mixed in advance, and then (F) a thermoplastic resin is melt-kneaded. Method (D), (A) a surface treatment agent is added to a dispersion liquid in which cellulose nanofibers having an average fiber diameter of 1000 nm or less are dispersed in water, and the mixture is dried. After producing a cellulose dried body, a method of adding the dry body (F) a thermoplastic resin, and the like are exemplified.

  For example, when the resin composition contains the (E) binder component, the method of adding the (A) surface treatment agent is not particularly limited, but includes (F) a thermoplastic resin, (D) cellulose nanofiber, and (E). A method in which a binder component and (A) a surface treatment agent are mixed in advance and melt-kneaded, and (F) a binder component and (A) a surface treatment agent are previously added to a thermoplastic resin, and after preliminary kneading if necessary, (D) Method of adding cellulose nanofibers and melt-kneading, (D) Cellulose nanofibers, (E) Binder component and (A) Surface treating agent are mixed in advance, and then (F) Thermoplastic resin and melt-kneading And the like. (D) Cellulose nanofibers are dispersed in water. (E) A binder component and (A) a surface treatment agent are added to the dispersion and dried to prepare a cellulose preparation, and then the preparation is heated (F). The method of adding to the plastic resin is also effective.

≪ (B) Polyurethane≫
Next, the (B) polyurethane that can be used in the present invention will be described in detail. (B) Polyurethane is a component different from (A) surface treatment agent, (D) cellulose nanofibers and (F) thermoplastic resin, and typically has a number average molecular weight of 500 or more, and more typically, It has a number average molecular weight of 1000 or more. The lower limit of the number average molecular weight of the polyurethane (B) is preferably 500, more preferably 1000, particularly preferably 2000, and the upper limit is preferably 100,000, more preferably 50,000, and particularly preferably 30,000. In one aspect, (B) polyurethane has a soft segment and a hard segment. In one aspect, each of the soft and hard segments may be composed of one or more monomers (diisocyanates) and polymers. The polyurethane (B) may be added, for example, by a method of kneading with the resin in the state of an aqueous dispersion or an aqueous solution. The (B) polyurethane may be a commercially available reagent or product.

  (B) Polyurethane is, for example, (F) a polymer having a urethane bond with a modified product (for example, an acid-modified product or a hydroxyl-modified product) of the same type of polymer as the thermoplastic resin, and (F) a polymer of the same type as the thermoplastic resin. In addition, it is different from the thermoplastic resin (F) because it is a polymer having a urethane bond with a polymer having a different molecular weight. The (B) polyurethane is different from the (D) cellulose nanofiber by being, for example, a polymer having a urethane bond with the (D) cellulose nanofiber. The (B) polyurethane is different from the (A) surface treatment agent because it is, for example, a polymer having a urethane bond with the (A) surface treatment agent. The (B) polyurethane may be (A) a surface treatment agent, (D) a cellulose nanofiber, and (F) a polymer having one or more urethane bonds with a thermoplastic resin.

  The number average molar mass of the soft segment (particularly the diol segment) of the polyurethane (B) is preferably 500 to 50,000 g / mol, more preferably 1,000 to 30,000 g from the viewpoint of obtaining a good affinity with the (D) cellulose nanofiber. / Mol. Examples of the diol segment include segments such as polyether diols, polyester diols, polyether ester diols, and polycarbonate diols.

  Examples of the polyether diols include poly (tetramethylene ether) glycol (PTMEG), poly (propylene oxide) glycol, polybutadiene diol or copolymers thereof (for example, copolymers of propylene oxide and ethylene oxide, tetrahydrofuran and ethylene oxide). Copolymers) and the like. In addition, these can be obtained, for example, by ring-opening polymerization of ethylene oxide, propylene oxide or tetrahydrofuran.

Polyester diols include the above-mentioned polyether diols or dialcohols (for example, ethylene glycol, propylene 1,3-glycol, propylene 1,2-glycol, 1,4-butane diol, 1,3-butane diol, 2 -Methylpropanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, nonanediol, 1,10-decanediol, etc.), Obtained by an esterification reaction with a dicarboxylic acid (eg, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, etc.) or by a corresponding transesterification reaction You can This type of polyester diols can also be obtained by ring-opening polymerization of lactones (eg, caprolactone, propiolactone, valerolactone, etc.).
Polycarbonates are the above-mentioned polyether diols or dialcohols (for example, ethylene glycol, propylene 1,3-glycol, propylene 1,2-glycol, 1,4-butanediol, 1,3-butanediol, 2- Methyl propane diol, 1,5-pentane diol, 3-methyl-1,5-pentane diol, 1,6-hexane diol, neopentyl glycol, nonane diol, 1,10-decane diol, etc.) Or a phosgene.

Examples of the hard segment of polyurethane include a segment containing the following polymer structure and the like:
4,4'-diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI) (for example, isomers such as 2,4-toluene diisocyanate and 2,6-toluene diisocyanate and mixtures thereof), m-xylylene diisocyanate, p -Xylylene diisocyanate, 1,5-naphthylene diisocyanate (NDI), 3,3'-dimethyl-4,4'-diphenylene diisocyanate (TODI), 2,2-diphenylpropane-4,4 "-diisocyanate, p -Phenylene diisocyanate, m-phenylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate (H12MDI), isophorone diisocyanate (IPDI), cyclopentylene-1,3-diisocyanate, 1,6-hexamene One or more diisocyanates selected from the group consisting of tolylene diisocyanate (HMDI) and 1,4-butylene diisocyanate, and the following chain extender (sometimes referred to as a cross-linking agent), that is, diols (for example, ethylene Glycol, propylene 1,3-glycol, propylene 1,2-glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-ethyl-2butyl-1,3-propanediol, 2-methyl-2,4-pentane Diol, 2,2,4-trimethyl-1,3-pentanediol, dihydroxy-cyclopentane, 1, -Cyclohexanedimethylol, thiodiglycol, diethylene glycol, dipropylene glycol, 2-methyl-1,3-propanediol, 2-methyl-2-ethyl-1,3-propanediol, dihydroxyethyl ether of hydroquinone, and hydrogenation One selected from the group consisting of bisphenol A), diamines (eg, ethylenediamine, hexamethylenediamine, xylylenediamine, and 4,4′-diaminodiphenylmethane), and triols (eg, trimethylolpropane, and glycerin). A rigid urethane segment (hard segment) of polyurethane, which is a reaction product with the above chain extender;

  Acrylic polymer, styrene resin, vinyl chloride resin, vinylidene chloride resin, polyolefin resin, polyhexamethylene adipamide (6,6 nylon), polyhexamethylene azeramide (6,9 nylon), polyhexamethylene Organic dicarboxylic acid having 4 to 12 carbon atoms and 2 to 13 carbon atoms, such as sebacamide (6,10 nylon), polyhexamethylene dodecanoamide (6,12 nylon), polybis (4-aminocyclohexyl) methandodecane, etc. Polycondensate with an organic diamine, ω-amino acid (for example, ω-aminoundecanoic acid) polycondensate (for example, polyundecane amide (11 nylon), etc.), and polycapramide which is a ring-opening polymer of ε-aminocaprolactam ( 6 Nylon), polylauric lac which is a ring-opening polymer of ε-aminolaurolactam Amino acid lactam containing ring-opening polymer of lactam such as vinyl (12 nylon), polymer composed of diamine and dicarboxylic acid, polyacetal resin, polycarbonate resin, polyester resin, polyphenylene sulfide resin, polysulfone resin , Polyetherketone-based resin, polyimide-based resin, fluorine-based resin, hydrophobic silicone-based resin, melamine-based resin, epoxy-based resin, phenol-based resin, a reaction product with one or more chain extenders selected from the group consisting of Is a rigid urethane segment (hard segment) of polyurethane.

  Among them, the polyurethane hard segment is preferably 4,4′-diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), m-xylylene diisocyanate, p-xylylene diisocyanate, 1,5-naphthyl, from the viewpoint of production. Diisocyanate (NDI), 3,3'-dimethyl-4,4'-diphenylene diisocyanate (TODI), 2,2-diphenylpropane-4,4 "-diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, 4 , 4'-dicyclohexylmethane diisocyanate (H12MDI), isophorone diisocyanate (IPDI), cyclopentylene-1,3-diisocyanate, 1,6-hexamethylene diisocyanate (HMDI), and It is composed of more than one selected from the group consisting of 1,4-butylene diisocyanate.

  The number average molar mass of the hard segment of the polyurethane (B) is preferably 300 to 10000 g / mol, more preferably 500 to 5000 g / mol, from the viewpoint of obtaining a good affinity with the thermoplastic resin (F).

  In a preferred embodiment, (B) polyurethane is a modified polyurethane. Suitable examples of the modified polyurethane include, but are not limited to, aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, araliphatic polyisocyanate, blocked isocyanate compound (that is, the blocking group is removed at a specific temperature). Examples thereof include isocyanate compounds that can be separated to regenerate an isocyanate group) and polyisocyanates. In a preferred embodiment, the modified polyurethane is a blocked isocyanate compound. Blocking groups include oxime-based blocking agents, phenol-based blocking agents, lactam-based blocking agents, alcohol-based blocking agents, active methylene-based blocking agents, amine-based blocking agents, pyrazole-based blocking agents, bisulfite-based blocking agents, or imidazole-based blocking agents. It may be derived from a blocking agent such as a blocking agent. The modified polyurethane may be a dimer or trimer of polyisocyanate, a modified polyurethane such as buretted isocyanate, or polymethylene polyphenyl polyisocyanate (polymeric MDI). The polyurethane (B) may be added, for example, by a method of kneading with the resin in the state of an aqueous dispersion or an aqueous solution. The (B) polyurethane may be a commercially available reagent or product.

  More specific examples of the modified polyurethane, for example, tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene Diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane), tolylene diisocyanate (TDI), 2,2'-diphe Rumethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate , 1,4-phenylene diisocyanate), dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, α, α, α, α-tetramethylxylylene diisocyanate, a blocking agent for the above isocyanate compound (for example, oxime blocking agent, phenol blocking agent) , Lactam type blocking agent, alcohol type blocking agent, active methylene type blocking agent, amine type blocking agent, pyrazole type blocking agent, bisulfite type Examples thereof include modified polyurethanes obtained by reacting a blocking agent or an imidazole-based blocking agent).

  Among these, TDI, MDI, hexamethylene diisocyanate, and modified polyurethane prepared from modified hexamethylene diisocyanate and hexamethylene diisocyanate as raw materials can be preferably used in terms of reactivity, stability, cost, and the like.

  The upper limit of the dissociation temperature of the blocking group of the blocked isocyanate compound is preferably 210 ° C, more preferably 190 ° C, and even more preferably 150 ° C from the viewpoint of reactivity and stability. Further, the lower limit value is preferably 70 ° C, more preferably 80 ° C, and further preferably 110 ° C. Examples of the blocking agent having a block group dissociation temperature within this range include methyl ethyl ketone oxime, ortho-secondary butylphenol, caprolactam, sodium bisulfite, 3,5-dimethylpyrazole, and 2-methylimidazole.

  In a preferred embodiment, (B) the polyurethane has a hydrophilic property in the soft segment and a hydrophobic property in the hard segment remarkably exhibited, and thereby (D) the affinity for the cellulose nanofibers and the aggregation preventing effect. Is a polyurethane having a soft segment as a hydrophilic segment and a hard segment as a hydrophobic segment.

  In a preferred embodiment, (B) polyurethane contained in the dispersion, the cellulose nanofiber aqueous dispersion, the cellulose nanofiber dried product, or the cellulose nanofiber resin composition is a blocked isocyanate compound.

  In a preferred embodiment, the (B) polyurethane contained in the cellulose nanofiber resin composition or the resin molded article comprises an isocyanate compound (preferably a blocked isocyanate compound) and (D) cellulose nanofibers and / or (F) a thermoplastic resin. It is a portion derived from an isocyanate compound in the reaction product. In this case, the (B) polyurethane is bonded to the (D) cellulose nanofiber and / or the (F) thermoplastic resin.

  In one embodiment of the dispersion liquid, the preferable amount of (B) polyurethane is within the range of 0.1 to 50 mass% with respect to the entire dispersion liquid. The upper limit is more preferably 45% by mass, even more preferably 40% by mass, even more preferably 35% by mass, particularly preferably 30% by mass. The lower limit is not particularly limited, but is preferably 0.1% by mass, more preferably 1% by mass, and most preferably 10% by mass. By setting the upper limit of the amount of the polyurethane (B) to the above value, it is possible to suppress the sedimentation of the dispersion liquid, and it is possible to maintain a uniform morphology in the aqueous dispersion of cellulose nanofibers and the dried cellulose nanofibers. Further, by setting the lower limit of the amount of polyurethane (B) to the above value, good mechanical properties can be obtained in the resin composition and the resin molded product of one aspect.

  In each of the aqueous dispersion of cellulose nanofibers, the dried cellulose nanofibers, the resin composition and the resin molded product according to one embodiment, the preferable amount of (B) polyurethane is (D) an average fiber diameter of 1000 nm or less. It is within the range of 0.1 to 100 parts by mass with respect to 100 parts by mass. The upper limit is more preferably 80 parts by mass, even more preferably 70 parts by mass, even more preferably 50 parts by mass, particularly preferably 40 parts by mass. The lower limit is not particularly limited, but is preferably 0.1 part by mass, more preferably 0.5 part by mass, and most preferably 1 part by mass. By setting the upper limit of the amount of the polyurethane (B) to the above value, the plasticization of the thermoplastic resin (F) can be suppressed and the strength can be kept good. Moreover, the redispersibility of the cellulose nanofibers can be improved by setting the lower limit of the amount of the polyurethane (B) to the above.

  In the resin composition and the resin molded product according to one aspect, the preferable amount of (B) polyurethane is within the range of 0.1 to 50 mass% with respect to the entire resin composition. The upper limit amount is more preferably 45% by mass, even more preferably 40% by mass, even more preferably 30% by mass, particularly preferably 20% by mass. The lower limit is not particularly limited, but is preferably 0.1% by mass, more preferably 0.5% by mass, and most preferably 1% by mass. By setting the upper limit of the amount of (B) polyurethane to the above range, plasticization of the entire resin composition can be suppressed and good strength can be maintained. Further, by setting the lower limit of the amount of (B) polyurethane to the above, it is possible to enhance the dispersibility of (D) the cellulose nanofibers having an average fiber diameter of 1000 nm or less in the thermoplastic resin and maintain strong adhesion. I can.

The amount of polyurethane (B) in the dispersion can be easily confirmed by a person skilled in the art by a general method. The confirmation method is not limited, but the following method can be exemplified. The dispersion is salted out or centrifuged. This makes it possible to separate the sediment (polyurethane) and the dispersion liquid other than polyurethane, and the content can be calculated by drying the isolated polyurethane. In addition, qualitative (that is, identification) of the molecular structure and measurement of the molecular weight can be performed by measuring the polyurethane by using thermal decomposition GC-MS, ¹ H-NMR, or ¹³ C-NMR.

  The amount of polyurethane (B) in the aqueous dispersion of cellulose nanofibers and in the dried cellulose nanofibers can be easily confirmed by those skilled in the art by a general method. The confirmation method is not limited, but the following method can be exemplified. Water is added to the dried cellulose nanofibers to obtain a cellulose nanofiber aqueous dispersion. Centrifugation is performed on the aqueous dispersion of cellulose nanofibers. As a result, it is possible to separate the sediment (cellulose nanofiber and polyurethane) and the surface treatment agent dispersion liquid. The precipitate is dissolved in a polyurethane-soluble solvent and separated into a soluble component 1 (polyurethane) and an insoluble component 1 (cellulose). Soluble 1 is reprecipitated with a solvent that does not dissolve polyurethane, and polyurethane is isolated. The isolated polyurethane can be qualitatively and quantitatively analyzed by the method described above.

  The amount of polyurethane (B) in the resin composition and the resin molded product can be easily confirmed by those skilled in the art by a general method. The confirmation method is not limited, but the following method can be exemplified. The resin composition is dissolved in a solvent that dissolves the resin using the resin composition and a fragment of the molded product, and the soluble content 1 (resin and surface treatment agent) and the insoluble content 1 (cellulose and polyurethane and surface treatment agent) To separate. After the separation, the insoluble matter 1 is dissolved in a polyurethane-soluble solvent to separate it into a soluble matter 2 (polyurethane and surface treatment agent) and an insoluble matter 2 (cellulose). The soluble component 2 is reprecipitated with a solvent that does not dissolve polyurethane but does dissolve the surface treatment agent, and the polyurethane is isolated. The isolated polyurethane can be qualitatively and quantitatively analyzed by the method described above.

<< (C) Water-soluble organic solvent >>
Next, the water-soluble organic solvent (C) that can be used in the present invention will be described in detail. In one aspect, the dispersion, the water-containing dispersion of cellulose nanofibers, and the cellulose nanofiber resin composition may each include (C) a water-soluble organic solvent. (C) Water-soluble organic solvent is a solvent having “water solubility” as defined in the present disclosure. The (C) water-soluble organic solvent dissolves the (A) surface treatment agent present on the surface of the (D) cellulose nanofiber, and uniformly coats the (A) surface treatment agent on the (D) cellulose nanofiber. This can provide the advantage of further improving the redispersion of the dried cellulose nanofibers in water. The water-soluble organic solvent (C) may be a protic organic solvent or an aprotic organic solvent.

  The protic organic solvent is an organic solvent that has a hydrogen atom having a relatively high acidity bonded to an oxygen atom and serves as a hydrogen bond donor. On the other hand, the aprotic organic solvent is an organic solvent having a high acidity and having no hydrogen atom. The water-soluble organic solvent (C) may be a commercially available reagent or product.

  Specific examples that can be suitably used as the water-soluble organic solvent (C) include aprotic organic solvents such as 1,4-dioxane, anisole, diethylene glycol dimethyl ether, cyclohexanone, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, hexamethylphosphorus triamide, triethyl phosphate, succinonitrile, benzonitrile, pyridine, nitromethane, morpholine, ethylenediamine, dimethylsulfoxide, sulfolane, propylene carbonate, diethylene glycol ethyl Methyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, diethylene glycol dibutyl ether Le, triethylene glycol butyl methyl ether, and the like. As a protic organic solvent, isobutyl alcohol, isopentyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, phenol, benzyl alcohol, diethylene glycol, triethylene glycol, glycerin, diethylene glycol monomethyl ether, tri Examples thereof include ethylene glycol monomethyl ether and polyethylene glycol monomethyl ether.

  Among these, diethylene glycol dimethyl ether, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and hexamethylphosphorus are used as the aprotic organic solvent from the viewpoints of heat resistance and availability. Preferred examples include suntriamide, dimethyl sulfoxide, sulfolane, and triethylene glycol dimethyl ether, and N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, and triethylene glycol dimethyl ether, It is more preferable from the viewpoint of handleability and cost.

  From the viewpoint of heat resistance and availability, as a protic organic solvent, isobutyl alcohol, isopentyl alcohol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol, triethylene glycol, glycerin, triethylene. Glycol monomethyl ether is preferred, and isobutyl alcohol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol, triethylene glycol, and triethylene glycol monomethyl ether are more preferred from the viewpoint of handleability and cost. ..

  In a typical embodiment, the lower limit of the molecular weight of (C) the water-soluble organic solvent is 50, preferably 100, more preferably 300, and most preferably 1000. The upper limit of the number average molecular weight is not particularly limited, but is preferably 2000 or less from the viewpoint of handleability. From the viewpoint of dissolving the surface treating agent (A) and improving the binding or adsorption with the (F) thermoplastic resin and / or (D) cellulose nanofibers having an average fiber diameter of 1000 nm or less in the resin composition, It is desirable to be within the above range.

  In a typical embodiment, the lower limit of the boiling point of (C) the water-soluble organic solvent is 100 ° C., preferably 110 ° C., more preferably 120 ° C., more preferably 150 ° C., most preferably Is 180 ° C. In a preferred embodiment, the upper limit of the boiling point is 300 ° C, more preferably 290 ° C, more preferably 280 ° C, more preferably 260 ° C, most preferably 240 ° C. It is estimated that the lower limit of the boiling point of (C) the water-soluble organic solvent is in the above range, but it is estimated that in the dried cellulose nanofiber, water is vaporized first, and (A) the surface treatment agent and (C) the water-soluble organic solvent. An environment is formed in which the solvent coexists. Such an environment is advantageous for dissolving the (A) surface treatment agent present on the surface of the (D) cellulose nanofiber and uniformly applying the (A) surface treatment agent to the (D) cellulose nanofiber. Yes, it contributes to good redispersion of the dried cellulose nanofibers in water, and good dispersion of the aqueous dispersion of cellulose nanofibers and the dried cellulose nanofibers in the resin composition. On the other hand, when the upper limit of the boiling point of the water-soluble organic solvent (C) is within the above range, the water-soluble organic solvent (C) can be sufficiently vaporized during the production of the resin composition. This tends to suppress plasticization of the resin composition by the water-soluble organic solvent (C) and maintain good strength.

  In a typical embodiment, the lower limit value of the relative dielectric constant of the water-soluble organic solvent (C) at 25 ° C. is 1, preferably 2, more preferably 3, and most preferably 5, It is preferably 7. The upper limit of the relative dielectric constant at 25 ° C. is preferably 80, more preferably 70, more preferably 60, and most preferably 50. If the relative permittivity of the water-soluble organic solvent (C) is in the above range, it is estimated that the surface treatment agent (A) can be uniformly dispersed in the dispersion liquid, and even during the drying process (A) It seems that precipitation can be suppressed even above the cloud point of the surface treatment agent.

  The content of the water-soluble organic solvent (C) in the dispersion of one aspect is more preferably 50% by mass, even more preferably 30% by mass, and even more preferably 100% by mass of the entire dispersion. Is 20% by mass, particularly preferably 10% by mass. The lower limit is not particularly limited, but is preferably 0.1% by mass, more preferably 0.5% by mass, and most preferably 1% by mass. By setting the upper limit of the amount of the water-soluble organic solvent (C) to the above, it is possible to prepare a dispersion having excellent economic efficiency. Further, by setting the lower limit of the amount of the water-soluble organic solvent (C) to the above value, the redispersibility of the dried cellulose nanofibers in water can be enhanced. Further, the dispersion of the water-containing dispersion of cellulose nanofibers and the dried cellulose nanofibers in the resin composition tends to be good.

  In the resin composition and the resin molded product according to one aspect, the preferable amount of the water-soluble organic solvent (C) is in the range of 0.1 to 2000 ppm based on the mass of the entire resin composition. The upper limit amount is more preferably 1800 ppm, even more preferably 1500 ppm, even more preferably 1200 ppm, particularly preferably 1000 ppm. The lower limit is not particularly limited, but is preferably 0.1 ppm, more preferably 1 ppm, and most preferably 10 ppm. By setting the upper limit of the amount of the water-soluble organic solvent (C) to the above range, the plasticization of the thermoplastic resin (F) can be suppressed and the strength can be kept good. Further, by setting the lower limit of the amount of the water-soluble organic solvent (C) to the above value, the dispersibility of the cellulose nanofiber (D) having an average fiber diameter of 1000 nm or less in the (F) thermoplastic resin can be enhanced.

  In each of the water-containing dispersion of cellulose nanofibers, the dried cellulose nanofibers, the resin composition and the resin molded product, the preferable amount of the (C) water-soluble organic solvent is (D) an average fiber diameter of 1000 nm or less. It is within the range of 0.1 to 100 parts by mass with respect to 100 parts by mass. The upper limit is more preferably 80 parts by mass, even more preferably 50 parts by mass, particularly preferably 20 parts by mass. The lower limit is not particularly limited, but is preferably 0.5 part by mass, more preferably 1 part by mass, and most preferably 5 parts by mass. By setting the upper limit amount of the (C) water-soluble organic solvent to the above, the surface treatment agent can be uniformly coated on the cellulose nanofibers, and by setting the lower limit amount of the (C) water-soluble organic solvent to the above, The redispersibility of the dried cellulose nanofibers in water can be enhanced. Further, the dispersion of the water-containing dispersion of cellulose nanofibers and the dried cellulose nanofibers in the resin composition tends to be good.

  The amount of the water-soluble organic solvent (C) in the dispersion can be easily confirmed by a person skilled in the art by a general method. The confirmation method is not limited, but the following method can be exemplified. The dispersion liquid is directly subjected to pyrolysis GCMS measurement, and the water-soluble organic solvent (C) can be qualitatively identified from the chromatogram and the mass spectrum. By using the water-soluble organic solvent (C) detected at this time and preparing a calibration curve under the same conditions, the content in the dispersion can be quantified.

  The amount of the water-soluble organic solvent (C) in the aqueous dispersion of cellulose nanofibers and in the dried cellulose nanofibers can be easily confirmed by a person skilled in the art by a general method. The confirmation method is not limited, but the following method can be exemplified. The aqueous dispersion of cellulose nanofibers or the dried cellulose nanofibers is directly subjected to pyrolysis GCMS measurement, and the water-soluble organic solvent (C) can be qualitatively identified from the chromatogram and the mass spectrum. By using the (C) water-soluble organic solvent detected at this time and preparing a calibration curve under the same conditions, the content in the aqueous dispersion of cellulose nanofibers and the dried cellulose nanofibers can be quantified. I can.

  The amount of the water-soluble organic solvent (C) in the resin composition and the resin molded product can be easily confirmed by those skilled in the art by a general method. The confirmation method is not limited, but the following method can be exemplified. The fragment of the resin composition or the resin molded product is subjected to pyrolysis GCMS measurement, and the water-soluble organic solvent (C) can be qualitatively identified from the chromatogram and the mass spectrum. By using the water-soluble organic solvent (C) detected at this time and preparing a calibration curve under the same conditions, the content in the resin composition and the resin molded product can be quantified.

<< (D) Cellulose nanofiber having an average fiber diameter of 1000 nm or less >>
Next, (D) cellulose nanofibers having an average fiber diameter of 1000 nm or less that can be used in the present invention will be described in detail.

  Suitable examples of (D) cellulose nanofibers having an average fiber diameter of 1000 nm or less are not particularly limited, but, for example, cellulose nanofibers made from cellulose pulp or one or more modified products of these celluloses can be used. Among these, one or more modified cellulose products can be preferably used from the viewpoints of stability and performance. The average fiber diameter of the (D) cellulose nanofibers is 1000 nm or less, preferably 500 nm or less, and more preferably 200 nm or less from the viewpoint of obtaining good mechanical strength (particularly tensile elastic modulus) of the resin molded product. The average fiber diameter is preferably small, but from the viewpoint of ease of processing, it can be preferably 10 nm or more, more preferably 20 nm or more, still more preferably 30 nm or more. The average fiber diameter is a value determined by a laser diffraction / scattering particle size distribution meter as a spherical equivalent diameter (volume average particle diameter) of particles when the cumulative volume becomes 50%.

The average fiber diameter can be measured by the following method. (D) Cellulose nanofibers at a solid content of 40% by mass in a planetary mixer (for example, manufactured by Shinagawa Kogyo Co., Ltd., 5DM-03-R, with stirring blades of hook type) at 126 rpm at room temperature and atmospheric pressure of 30. The mixture was kneaded for a minute, then made into a pure water suspension at a concentration of 0.5% by mass, and a high shear homogenizer (for example, Nippon Seiki Co., Ltd., trade name "Excel Auto Homogenizer ED-7" treatment conditions) was used to rotate Disperse at 15,000 rpm for 5 minutes, and use a centrifuge (for example, Kubota Shoji Co., Ltd., trade name "6800 type centrifuge", rotor type RA-400 type), processing condition: centrifugal force 39200 m ² / The supernatant obtained by centrifuging at s for 10 minutes is collected, and the supernatant is centrifuged at 116000 m2 / s for 45 minutes, and the supernatant after centrifugation is collected. Using this supernatant, a laser diffraction / scattering method particle size distribution meter (for example, manufactured by Horiba Ltd., trade name “LA-910” or trade name “LA-950”, ultrasonic treatment 1 minute, refractive index 1. 20) The cumulative 50% particle diameter in the volume frequency particle size distribution (that is, the spherical equivalent diameter of particles when the cumulative volume becomes 50% with respect to the volume of the entire particle) is defined as the volume average particle diameter. .

  In a typical embodiment, the (D) cellulose nanofiber having an average fiber diameter of 1000 nm or less has an L / D ratio of 20 or more. The L / D lower limit of the cellulose nanofibers is preferably 30, more preferably 40, more preferably 50, more preferably 80, more preferably 100, and particularly preferably 120. , And most preferably 150. The upper limit is not particularly limited, but is preferably 10,000 or less, or 1000 or less from the viewpoint of handleability. In order for the resin composition of the present disclosure to exhibit good mechanical properties with a small amount of cellulose nanofibers, the L / D ratio of the cellulose nanofibers is preferably within the above range.

  In the present disclosure, the length, diameter, and L / D ratio of cellulose nanofibers, cellulose pulp, or cellulose whiskers described below are obtained by using a high-shear homogenizer to obtain an aqueous dispersion of each of cellulose nanofibers, cellulose pulp, or cellulose whiskers described below. (For example, manufactured by Nippon Seiki Co., Ltd., trade name “Excel Auto Homogenizer ED-7”), and treatment conditions: 0.1 to 0.5 of an aqueous dispersion dispersed at a rotation speed of 15,000 rpm × 5 minutes. It is diluted with pure water to a mass%, cast on mica, and air-dried to obtain a measurement sample, which is measured by an optical microscope, a high-resolution scanning microscope (SEM), or an atomic force microscope (AFM). Specifically, at least 100 cellulose nanofibers, cellulose pulp, or 100 randomly selected cellulose nanofibers or cellulose pulp in an observation field of view whose magnification is adjusted so that cellulose whiskers described below are observed. Alternatively, the length (L) and the diameter (D) of the cellulose whiskers described later are measured and the ratio (L / D) is calculated. The length and diameter of the cellulose nanofibers, cellulose pulp or cellulose whiskers described later of the present disclosure are the number average values of the above 100 celluloses.

  The length, diameter, and L / D ratio of each of the cellulose nanofibers, the cellulose pulp, or the cellulose whiskers described below in the resin composition and the resin molded product are determined by an organic or inorganic solvent capable of dissolving the resin component of the composition. After dissolving the resin component in the composition, separating the cellulose and thoroughly washing with the solvent, an aqueous dispersion liquid in which the solvent was replaced with pure water or a dispersible organic solvent was prepared. It can be confirmed by diluting with pure water to 1 to 0.5% by mass, casting on mica, and air-drying the sample to be measured by the above-mentioned measuring method. At this time, 100 or more randomly selected celluloses to be measured are measured.

  (D) Cellulose nanofibers are produced by treating pulp or the like with hot water at 100 ° C. or higher to hydrolyze and weaken the hemicellulose portion, and then pulverize with a high-pressure homogenizer, microfluidizer, ball mill, disc mill, or the like. It may be cellulose defibrated by the method. In one embodiment, the (D) cellulose nanofibers may have an L / D ratio of 30 or more and are not classified into cellulose pulp (that is, an L / D ratio of 40 or more and a fiber diameter of more than 1000 nm). .

  The (D) cellulose nanofiber in the present disclosure may be an unmodified product or a modified product. Examples of the modified product include those modified with one or more modifying agents selected from esterifying agents, silylating agents, isocyanate compounds, halogenated alkylating agents, alkylene oxides and / or glycidyl compounds. In a preferred embodiment, the (D) cellulose nanofiber is an unmodified product or an oxo acid-modified group (that is, a site in which the hydroxyl group of cellulose is converted with an oxo acid (eg, carboxylic acid) or a salt thereof (eg, carboxylic acid salt)). It is a non-containing modified product, and an example of this preferable modified product is a modified product with the modifying agents listed above.

  The esterifying agent as a modifier includes (D) an organic compound having at least one functional group capable of reacting with a hydroxyl group on the surface of the cellulose nanofiber to esterify the hydroxyl group. Esterification can be carried out by the method described in paragraph [0108] of WO 2017/159823. The esterifying agent may be a commercially available reagent or product.

  Suitable examples of the esterifying agent are not particularly limited, but include, for example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobaric acid. Aliphatic monocarboxylic acid such as butyric acid; alicyclic monocarboxylic acid such as cyclohexanecarboxylic acid; aromatic such as benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenylacetic acid Monocarboxylic acid; and a plurality of mixtures arbitrarily selected from these, and symmetrical anhydrides (acetic anhydride, maleic anhydride, cyclohexane-carboxylic acid anhydride, benzene-sulfonic acid anhydride) arbitrarily selected from these Mixed acid anhydrides (butyric acid-valeric acid anhydride), cyclic anhydrides (succinic anhydride, phthalic anhydride) Acid, naphthalene-1,8: 4,5-tetracarboxylic acid dianhydride, cyclohexane-1,2,3,4-tetracarboxylic acid 3,4-anhydride, ester acid anhydride (acetic acid 3- (ethoxy) Carbonyl) propanoic anhydride, benzoylethyl carbonate) and the like.

  Among these, from the viewpoint of reactivity, stability, price, etc., acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, benzoic acid, Acetic anhydride, maleic anhydride, succinic anhydride, and phthalic anhydride can be preferably used.

  The silylating agent as a modifier includes a Si-containing compound having at least one reactive group capable of reacting with a hydroxyl group on the surface of cellulose or a group after hydrolysis thereof. The silylating agent may be a commercially available reagent or product.

  Suitable examples of the silylating agent include, but are not limited to, chlorodimethylisopropylsilane, chlorodimethylbutylsilane, chlorodimethyloctylsilane, chlorodimethyldodecylsilane, chlorodimethyloctadecylsilane, chlorodimethylphenylsilane, and chloro (1-hexenyl). Dimethylsilane, dichlorohexylmethylsilane, dichloroheptylmethylsilane, trichlorooctylsilane, hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,3-divinyl-1,3 -Diphenyl-1,3-dimethyl-disilazane, 1,3-N-dioctyltetramethyl-disilazane, diisobutyltetramethyldisilazane, diethyltetramethyldisilazane, N-dipropyltetramethyldisilazane, N Dibutyltetramethyldisilazane or 1,3-di (para-t-butylphenethyl) tetramethyldisilazane, N-trimethylsilylacetamide, N-methyldiphenylsilylacetamide, N-triethylsilylacetamide, t-butyldiphenylmethoxysilane, octadecyl Examples thereof include dimethylmethoxysilane, dimethyloctylmethoxysilane, octylmethyldimethoxysilane, octyltrimethoxysilane, trimethylethoxysilane and octyltriethoxysilane.

  Among these, hexamethyldisilazane, octadecyldimethylmethoxysilane, dimethyloctylmethoxysilane, and trimethylethoxysilane can be preferably used in terms of reactivity, stability, cost, and the like.

  The halogenated alkylating agent as a modifier includes an organic compound having at least one functional group capable of reacting with a hydroxyl group on the surface of cellulose to halogenate and alkylate it. The halogenated alkylating agent may be a commercially available reagent or product.

  Suitable examples of the halogenated alkylating agent are not particularly limited, but chloropropane, chlorobutane, bromopropane, bromohexane, bromoheptane, iodomethane, iodoethane, iodooctane, iodooctadecane, iodobenzene and the like can be used. Among these, bromohexane and iodooctane can be preferably used from the viewpoints of reactivity, stability, cost and the like.

  The isocyanate compound as a modifier includes (D) an organic compound having at least one isocyanate group capable of reacting with the hydroxyl group on the surface of the cellulose nanofiber. Further, the isocyanate compound may be a blocked isocyanate compound capable of desorbing a blocking group at a specific temperature to regenerate the isocyanate group, and may also be a diisomer or trimer of polyisocyanate or a buretted isocyanate. It may be a modified product such as polymethylene polyphenyl polyisocyanate (polymeric MDI). These may be commercially available reagents or products.

  Suitable examples of the isocyanate compound include, but are not limited to, aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, araliphatic polyisocyanates, blocked isocyanate compounds, and polyisocyanates. For example, tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis (isocyanatomethyl) Cyclohexane), tolylene diisocyanate (TDI), 2,2'-diphenylmethane diisocyanate, 2,4'-dif Nylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate) , Dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, α, α, α, α-tetramethylxylylene diisocyanate, oxime-based blocking agents, phenol-based blocking agents, lactam-based blocking agents, alcohol-based blocking agents, active methylene to the above isocyanate compounds Block agent, amine block agent, pyrazole block agent, bisulfite block agent, or block block obtained by reacting an imidazole block agent Examples thereof include a cyanate compound.

  Among these, TDI, MDI, hexamethylene diisocyanate, and blocked isocyanates obtained by using a modified hexamethylene diisocyanate and hexamethylene diisocyanate as raw materials can be preferably used from the viewpoints of reactivity, stability, cost, and the like.

  From the viewpoint of reactivity and stability, the upper limit of the dissociation temperature of the block group of the blocked isocyanate compound is preferably 210 ° C, more preferably 190 ° C, and further preferably 150 ° C. Further, the lower limit value is preferably 70 ° C, more preferably 80 ° C, and further preferably 110 ° C. Examples of the blocking agent having a block group dissociation temperature within this range include methyl ethyl ketone oxime, ortho-secondary butylphenol, caprolactam, sodium bisulfite, 3,5-dimethylpyrazole, and 2-methylimidazole.

  The alkylene oxide and / or glycidyl compound as a modifier includes an organic compound having at least one alkylene oxide group, glycidyl group and / or epoxy group capable of reacting with the hydroxyl group on the surface of cellulose. The alkylene oxide and / or glycidyl compound may be a commercially available reagent or product.

  Suitable examples of the alkylene oxide and / or glycidyl compound are not particularly limited, but include, for example, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, 2-methyloctyl glycidyl ether, phenyl glycidyl ether, p. -Tertiary butyl phenyl glycidyl ether, sec-butyl phenyl glycidyl ether, n-butyl phenyl glycidyl ether, phenyl phenol glycidyl ether, cresyl glycidyl ether, dibromo cresyl glycidyl ether and other glycidyl ethers; glycidyl acetate, glycidyl stearate, etc. Glycidyl ester; ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether 1,4-butanediol diglycidyl ether, hexamethylene glycol diglycidyl ether, resorcinol diglycidyl ether, bisphenol A diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polybutylene glycol diglycidyl ether, glycerol Examples thereof include polyhydric alcohol glycidyl ethers such as triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, polyglycerol polyglycidyl ether, and diglycerol polyglycidyl ether.

  Among these, 2-methyloctyl glycidyl ether, hexamethylene glycol diglycidyl ether, and pentaerythritol tetraglycidyl ether can be preferably used in terms of reactivity, stability, cost, and the like.

(D) Cellulose nanofibers are prepared by dissolving the resin component in the composition in an organic or inorganic solvent capable of dissolving the resin component of the composition, separating the cellulose, thoroughly washing with the solvent, and then separating the separated cellulose. It can be confirmed by thermal decomposition or hydrolysis treatment. Alternatively, it can be confirmed by directly performing ¹ H-NMR and ¹³ C-NMR measurements.

  In one aspect, the aqueous dispersion of cellulose nanofibers, and the amount of (D) cellulose nanofibers relative to the entire dried cellulose nanofibers are each preferably 1% by mass or more from the viewpoint of good redispersibility, It is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 50% by mass or less, preferably 40% by mass or less, more preferably from the viewpoint of obtaining sufficient mechanical properties in the resin composition and the resin molded product. Is 20% by mass or less.

  In one aspect, the blending amount of (D) cellulose nanofibers relative to the entire resin composition and resin molded product is preferably 1% by mass or more from the viewpoint of good mechanical properties, thermal stability and durability, respectively. , More preferably 3 mass% or more, further preferably 5 mass% or more, from the viewpoint of obtaining good moldability, preferably 50 mass% or less, more preferably 40 mass% or less, further preferably 20 mass% or less. Is.

The amount of (D) cellulose nanofibers in the aqueous dispersion of cellulose nanofibers and the dried cellulose nanofibers can be easily confirmed by a person skilled in the art by a general method. The confirmation method is not limited, but the following method can be exemplified. Water is added to the dried cellulose nanofibers to obtain a cellulose nanofiber aqueous dispersion. Centrifugation is performed on the aqueous dispersion of cellulose nanofibers. As a result, it is possible to separate the sediment (cellulose nanofiber and polyurethane) and the surface treatment agent dispersion liquid. A polyurethane-soluble solvent is added to the precipitate to separate soluble matter 1 (polyurethane) and insoluble matter 1 (cellulose nanofibers). Qualitative / quantitative analysis can be carried out by measuring the weight of the isolated cellulose nanofibers or by using various thermal decomposition GC-MS, ¹ H-NMR, or ¹³ C-NMR analyzers.

The amount of (D) cellulose nanofibers in the resin composition and the resin molded body can be easily confirmed by those skilled in the art by a general method. The confirmation method is not limited, but the following method can be exemplified. The resin composition is dissolved in a solvent that dissolves the resin using the resin composition and a fragment of the molded product, and the soluble content 1 (resin and surface treatment agent) and the insoluble content 1 (cellulose and polyurethane and surface treatment agent) To separate. After the separation, the insoluble matter 1 is dissolved in a polyurethane-soluble solvent to separate it into a soluble matter 2 (polyurethane and surface treatment agent) and an insoluble matter 2 (cellulose). The insoluble matter 2 can be qualitatively and quantitatively analyzed by using various analyzers such as thermal decomposition GC-MS, ¹ H-NMR, ¹³ C-NMR, and wide-angle X-ray diffraction.

≪ (F) Thermoplastic resin≫
The (F) thermoplastic resin that can be used in the present invention typically has a number average molecular weight of 5000 or more. The lower limit of the number average molecular weight of the thermoplastic resin (F) is preferably 5,500, more preferably 10,000, particularly preferably 13,000, and the upper limit is preferably 1,000,000, more preferably 500,000, and particularly preferably 300,000. The number average molecular weight of the thermoplastic resin (F) is a value measured in terms of standard polymethylmethacrylate using GPC (gel permeation chromatography). Examples of the (F) thermoplastic resin include a crystalline resin having a melting point in the range of 100 ° C to 350 ° C, or an amorphous resin having a glass transition temperature in the range of 100 to 250 ° C. The thermoplastic resin (F) may be composed of one or more polymers which may be homopolymers or copolymers.

  The melting point of the crystalline resin here is the peak top of the endothermic peak that appears when the temperature is raised from 23 ° C. at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC). Refers to temperature. When two or more endothermic peaks appear, it indicates the peak top temperature of the endothermic peak on the highest temperature side. The enthalpy of the endothermic peak at this time is preferably 10 J / g or more, and more preferably 20 J / g or more. Further, in the measurement, it is desirable to use a sample in which the sample is once heated to a temperature condition of melting point + 20 ° C. or higher to melt the resin, and then cooled to 23 ° C. at a temperature decreasing rate of 10 ° C./min.

  Further, the glass transition temperature of the amorphous resin referred to here is a value measured at an applied frequency of 10 Hz while increasing the temperature from 23 ° C. to 2 ° C./min using a dynamic viscoelasticity measuring device. In addition, it means the temperature at the peak top of the peak at which the storage elastic modulus greatly decreases and the loss elastic modulus becomes maximum. When two or more peaks of the loss elastic modulus appear, the peak top temperature of the peak on the highest temperature side is indicated. The measurement frequency at this time is preferably at least once every 20 seconds in order to improve the measurement accuracy. The method for preparing the measurement sample is not particularly limited, but from the viewpoint of eliminating the influence of molding strain, it is desirable to use a cut piece of a hot press molded product, and the size (width and thickness) of the cut piece is as small as possible. A smaller one is preferable from the viewpoint of heat conduction.

  (F) As the thermoplastic resin, a polyamide resin, a polyester resin, a polyacetal resin, a polycarbonate resin, a polyacrylic resin, a polyphenylene ether resin (polyphenylene ether is modified by blending or graft-polymerizing with another resin). Modified polyphenylene ether), polyarylate resin, polysulfone resin, polyphenylene sulfide resin, polyethersulfone resin, polyketone resin, polyphenylene ether ketone resin, polyimide resin, polyamideimide resin, polyetherimide Examples thereof include resins, polyurethane resins, polyolefin resins (for example, α-olefin (co) polymers), various ionomers, and the like.

  Preferred specific examples of the (F) thermoplastic resin include high-density polyethylene, low-density polyethylene (for example, linear low-density polyethylene), polypropylene, polymethylpentene, cyclic olefin resin, poly-1-butene, poly-1-pentene, Polymethylpentene, ethylene / α-olefin copolymer, ethylene / butene copolymer, EPR (ethylene-propylene copolymer), modified ethylene / butene copolymer, EEA (ethylene-ethyl acrylate copolymer), modified EEA, modified EPR, modified EPDM (ethylene-propylene-diene terpolymer), ionomer, α-olefin copolymer, modified IR (isoprene rubber), modified SEBS (styrene-ethylene-butylene-styrene copolymer) Halogenated isobutylene-paramethylstyrene copolymer, Tylene-acrylic acid modified product, ethylene-vinyl acetate copolymer and acid modified product thereof, copolymer of (ethylene and / or propylene) and (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester), (ethylene And / or propylene) and (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester), obtained by metallizing at least a part of the carboxyl group of the copolymer, a conjugated diene and a vinyl aromatic hydrocarbon Block copolymers, hydrides of block copolymers of conjugated dienes and vinyl aromatic hydrocarbons, copolymers of other conjugated diene compounds and non-conjugated olefins, natural rubber, various butadiene rubbers, various styrene-butadiene copolymers Combined rubber, isoprene rubber, butyl rubber, bromide of copolymer of isobutylene and p-methylstyrene, halogen Butyl rubber, acrylonitrile-butadiene rubber, chloroprene rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, isoprene-butadiene Copolymer rubber, chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, polysulfide rubber, silicone rubber, fluororubber, urethane rubber, polyvinyl chloride, polystyrene, polyacrylic acid ester, acrylic acid such as polymethacrylic acid ester, acrylonitrile Acrylonitrile-based copolymer as the main component, acrylonitrile-butanediene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, cellulose-based resin such as cellulose acetate, vinyl chloride Le / ethylene copolymer, vinyl chloride / vinyl acetate copolymer, ethylene / vinyl acetate copolymer, and ethylene / saponified like vinyl acetate copolymer.

  These may be used alone or in combination of two or more. When two or more kinds are used together, they may be used as a polymer alloy. Further, it is also possible to use a resin in which the above-mentioned thermoplastic resin is modified with at least one compound selected from unsaturated carboxylic acids, their acid anhydrides or their derivatives.

  Among these, from the viewpoint of heat resistance, moldability, designability and mechanical properties, polyolefin resin, polyamide resin, polyester resin, polyacetal resin, polyacrylic resin, polyphenylene ether resin, and polyphenylene sulfide resin. One or more resins selected from the group consisting of are preferred.

  Among these, one or more resins selected from the group consisting of polyolefin resins, polyamide resins, polyester resins, polyacetal resins, polyacrylic resins, polyphenylene ether resins, and polyphenylene sulfide resins, especially polyamides. One or more resins selected from the group consisting of resin and polyacetal resin are more preferable from the viewpoint of handleability and cost.

  A polyolefin resin is a polymer obtained by polymerizing a monomer unit containing olefins (for example, α-olefins). Specific examples of the polyolefin-based resin include, but are not limited to, low-density polyethylene (for example, linear low-density polyethylene), high-density polyethylene, ultra-low-density polyethylene, ultra-high-molecular-weight polyethylene, etc. Polypropylene-based (co) polymers such as polymer, polypropylene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-acrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene Examples thereof include a copolymer of α-olefin represented by glycidyl methacrylate copolymer and the like and another monomer unit.

  The most preferable polyolefin resin here is polypropylene. In particular, polypropylene having a melt mass flow rate (MFR) of 3 g / 10 minutes or more and 30 g / 10 minutes or less measured at 230 ° C. under a load of 21.2 N in accordance with ISO1133 is preferable. The lower limit of MFR is more preferably 5 g / 10 minutes, even more preferably 6 g / 10 minutes, and most preferably 8 g / 10 minutes. Further, the upper limit value is more preferably 25 g / 10 minutes, even more preferably 20 g / 10 minutes, and most preferably 18 g / 10 minutes. From the viewpoint of improving the toughness of the composition, the MFR is preferably not more than the above upper limit, and from the viewpoint of the fluidity of the composition, it is preferably not more than the above lower limit.

  In addition, an acid-modified polyolefin resin can also be suitably used in order to increase the affinity with cellulose. The acid can be appropriately selected from maleic acid, fumaric acid, succinic acid, phthalic acid and their anhydrides, and polycarboxylic acids such as citric acid. Among these, maleic acid or its anhydride is preferable because of its high modification rate. The modification method is not particularly limited, but a method in which the resin is melted and kneaded by heating it to a temperature equal to or higher than the melting point in the presence / absence of a peroxide is common. As the acid-modified polyolefin resin, all of the above-mentioned polyolefin resins can be used, but polypropylene can be preferably used.

  The acid-modified polyolefin resin may be used alone, but it is more preferable to use it by mixing it with an unmodified polyolefin resin in order to adjust the modification ratio of the composition. For example, when using a mixture of unmodified polypropylene and acid-modified polypropylene, the ratio of acid-modified polypropylene to the total polypropylene is preferably 0.5% by mass to 50% by mass. A more preferred lower limit is 1% by mass, further preferably 2% by mass, even more preferably 3% by mass, particularly preferably 4% by mass, and most preferably 5% by mass. The more preferable upper limit is 45% by mass, further preferably 40% by mass, even more preferably 35% by mass, particularly preferably 30% by mass, and most preferably 20% by mass. In order to maintain the interfacial strength with the cellulose, the lower limit or more is preferable, and in order to maintain the ductility as a resin, the upper limit or less is preferable.

  The melt mass flow rate (MFR) measured at 230 ° C. and a load of 21.2 N in accordance with the preferred ISO1133 of acid-modified polypropylene is 50 g / 10 minutes or more in order to enhance the affinity with the cellulose interface. preferable. A more preferable lower limit is 100 g / 10 minutes, still more preferably 150 g / 10 minutes, and most preferably 200 g / 10 minutes. There is no particular upper limit, but it is 500 g / 10 minutes from the viewpoint of maintaining mechanical strength. By setting the MFR within this range, it is possible to enjoy the advantage of being easily present at the interface between the cellulose and the resin.

  The polyamide-based resin preferable as the thermoplastic resin is not particularly limited, but is obtained by a polycondensation reaction of lactams such as polyamide 6, polyamide 11, polyamide 12; 1,6-hexanediamine, 2-methyl-1,5. -Pentanediamine, 1,7-heptanediamine, 2-methyl-1-6-hexanediamine, 1,8-octanediamine, 2-methyl-1,7-heptanediamine, 1,9-nonanediamine, 2-methyl- Diamines such as 1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, and m-xylylenediamine, butanedioic acid, pentanedioic acid, and hexanedioic acid. , Heptanedioic acid, octanedioic acid, nonanedioic acid, decanedioic acid, benzene-1,2-dicarboxylic acid, benzene Polyamide 6 obtained as a copolymer with dicarboxylic acids such as benzene-1,3-dicarboxylic acid, benzene-1,4 dicarboxylic acid, etc., cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, etc. , 6, polyamide 6,10, polyamide 6,11, polyamide 6,12, polyamide 6, T, polyamide 6, I, polyamide 9, T, polyamide 10, T, polyamide 2M5, T, polyamide MXD, 6, polyamide 6 , C, polyamide 2M5, C, etc .; and copolymers obtained by copolymerizing these (polyamide 6, T / 6, I, etc.) and the like;

  Among these polyamide resins, aliphatic polyamides such as polyamide 6, polyamide 11, polyamide 12, polyamide 6,6, polyamide 6,10, polyamide 6,11, polyamide 6,12, polyamide 6, C, polyamide 2M5, C More preferred are cycloaliphatic polyamides such as

  The terminal carboxyl group concentration of the polyamide resin is not particularly limited, but the lower limit value is preferably 20 μmol / g, more preferably 30 μmol / g. The upper limit of the terminal carboxyl group concentration is preferably 150 μmol / g, more preferably 100 μmol / g, further preferably 80 μmol / g.

  In the polyamide resin, the ratio of carboxyl terminal groups to all terminal groups ([COOH] / [total terminal groups]) is preferably 0.30 to 0.95. The lower limit of the carboxyl end group ratio is more preferably 0.35, even more preferably 0.40, and most preferably 0.45. The upper limit of the carboxyl terminal group ratio is more preferably 0.90, even more preferably 0.85, and most preferably 0.80. The carboxyl terminal group ratio is preferably 0.30 or more from the viewpoint of dispersibility of the (D) cellulose nanofibers in the composition, and is 0.95 or less from the viewpoint of the color tone of the resulting composition. Is desirable.

  A known method can be used as a method of adjusting the terminal group concentration of the polyamide resin. For example, a diamine compound, a monoamine compound, a dicarboxylic acid compound, a monocarboxylic acid compound, an acid anhydride, a monoisocyanate, a monoacid halide, a monoester, a monoalcohol, etc., such that a predetermined terminal group concentration is obtained during the polymerization of polyamide. Examples thereof include a method of adding an end adjuster that reacts with an end group to the polymerization liquid.

  Examples of the terminal regulator that reacts with the terminal amino group include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid. Alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid and phenylacetic acid Carboxylic acid; and a plurality of mixtures arbitrarily selected from them. Among these, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid from the viewpoints of reactivity, stability of the capped end, price, and the like. And one or more end modifiers selected from the group consisting of benzoic acid and acetic acid are most preferred.

  Examples of the terminal modifier that reacts with the terminal carboxyl group include aliphatic amines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine. Examples thereof include monoamines; cycloaliphatic amines such as cyclohexylamine and dicyclohexylamines; aromatic monoamines such as aniline, toluidine, diphenylamine, naphthylamine, and any mixture thereof. Among them, one or more terminals selected from the group consisting of butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine and aniline from the viewpoints of reactivity, boiling point, stability of sealed terminal, price and the like. Modifiers are preferred.

The concentrations of the amino terminal group and the carboxyl terminal group are preferably determined from the integrated value of the characteristic signal corresponding to each terminal group by ¹ H-NMR in terms of accuracy and simplicity. As a method for determining the concentration of those terminal groups, the method described in JP-A-7-228775 is specifically recommended. When this method is used, deuterated trifluoroacetic acid is useful as a measurement solvent. Further, the number of times of ¹ H-NMR integration requires at least 300 scans even when measured with a device having sufficient resolution. In addition, the concentration of the terminal group can be measured by a titration method as described in JP-A-2003-0555549. However, quantification by ¹ H-NMR is more preferable in order to minimize the influence of additives and lubricants that are mixed.

  The polyamide resin has an intrinsic viscosity [η] measured in concentrated sulfuric acid at 30 ° C. of preferably 0.6 to 2.0 dL / g, and 0.7 to 1.4 dL / g. Is more preferable, 0.7 to 1.2 dL / g is further preferable, and 0.7 to 1.0 dL / g is particularly preferable. Use of the above polyamide-based resin having an intrinsic viscosity in a preferable range, and particularly preferable range among them, greatly enhances the fluidity in the mold during injection molding of the resin composition and gives the effect of improving the appearance of the molded piece. be able to.

  In the present disclosure, “intrinsic viscosity” has the same meaning as a viscosity generally called an intrinsic viscosity. A specific method for obtaining this viscosity is to measure ηsp / c of several measurement solvents having different concentrations in 96% concentrated sulfuric acid under a temperature condition of 30 ° C., and measure each ηsp / c and concentration (c ) Is derived and the concentration is extrapolated to zero. The value extrapolated to zero is the intrinsic viscosity. Details thereof are described in, for example, pages 291 to 294 of Polymer Process Engineering (Prentice-Hall, Inc 1994).

  At this time, it is preferable from the viewpoint of accuracy that the number of several measurement solvents having different concentrations is at least 4. The recommended concentrations of different viscosity measuring solutions are preferably at least 4 points of 0.05 g / dL, 0.1 g / dL, 0.2 g / dL, 0.4 g / dL.

  Polyester resins preferable as the thermoplastic resin are not particularly limited, but include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene succinate (PBS), polybutylene succinate adipate ( PBSA), polybutylene adipate terephthalate (PBAT), polyarylate (PAR), polyhydroxyalkanoic acid (PHA) (polyester resin consisting of 3-hydroxyalkanoic acid), polylactic acid (PLA), polycarbonate (PC), etc. One kind or two or more kinds can be used. Among these, more preferred polyester resins include PET, PBS, PBSA, PBT, and PEN, and more preferred are PBS, PBSA, and PBT.

  Further, the polyester resin can freely change the terminal groups depending on the monomer ratio at the time of polymerization and the presence / absence and amount of the terminal stabilizer added. ([COOH] / [all terminal groups]) is preferably 0.30 to 0.95. The lower limit of the carboxyl terminal group ratio is more preferably 0.35, further preferably 0.40, and most preferably 0.45. The upper limit of the carboxyl terminal group ratio is more preferably 0.90, further preferably 0.85, and most preferably 0.80. The carboxyl terminal group ratio is preferably 0.30 or more from the viewpoint of dispersibility of the (D) cellulose nanofibers in the composition, and is 0.95 or less from the viewpoint of the color tone of the resulting composition. Is desirable.

  Preferred polyacetal resins as thermoplastic resins are homopolyacetals made from formaldehyde and copolyacetals containing trioxane as a main monomer and, for example, 1,3-dioxolane as a comonomer component, both of which can be used. However, from the viewpoint of thermal stability during processing, copolyacetal can be preferably used. In particular, the amount of the comonomer component (for example, 1,3-dioxolane) is preferably in the range of 0.01 to 4 mol%. A more preferable lower limit of the amount of comonomer component is 0.05 mol%, more preferably 0.1 mol%, and particularly preferably 0.2 mol%. The more preferable upper limit is 3.5 mol%, further preferably 3.0 mol%, particularly preferably 2.5 mol%, and most preferably 2.3 mol%. From the viewpoint of thermal stability during extrusion processing and molding processing, the lower limit is preferably within the above range, and the upper limit is preferably within the above range from the viewpoint of mechanical strength.

<< (E) Binder component >>
In one embodiment, the dispersion, the water-containing dispersion of cellulose nanofibers, the dried cellulose nanofibers, the cellulose nanofiber resin composition or the resin molded product contains (E) a binder component. The (E) binder component contributes to better durability of the cellulose nanofiber resin composition or the resin molded product. It should be noted that the (E) binder component is a component different from the (A) surface treatment agent, (B) polyurethane, and (F) thermoplastic resin, and thus is not particularly polyurethane. It typically has a number average molecular weight of 1000 or more. The (E) binder component may be composed of one or more polymers which may be homopolymers or copolymers. The (E) binder component is, for example, (F) a modified product of a polymer of the same kind as the thermoplastic resin (for example, an acid modified product), (F) a polymer of the same kind as the thermoplastic resin and having a different molecular weight, (F) heat It is different from the thermoplastic resin (F) because it is a polymer different from the plastic resin. The binder component (E) may be added, for example, by a method of kneading with the resin in the state of an aqueous dispersion or an aqueous solution. The (E) binder component may be a commercially available reagent or product.

  In an exemplary embodiment, the (E) binder component comprises a functional group (in the present disclosure, a “reactive group” that can chemically or physically bond or interact with (D) cellulose nanofibers and / or (F) a thermoplastic resin. Also referred to as "functional group"). Bonds typically include chemical bonds such as ionic and covalent bonds, and interactions typically result from intermolecular forces (eg, hydrogen bonds, van der Waals forces, and electrostatic attraction). Adsorption (chemical or physical adsorption). In one aspect, the reactive functional group contained in the binder component (E) is a group that exhibits binding or adsorptivity with at least a hydroxyl group. As the reactive functional group, a hydroxyl group, a carboxyl group, a formyl group, an acyl group, an amino group, an azo group, an adi group, an imino group, a carbonyl group, a thiocarbonyl group, a diimide group, a thiol group, an epoxy group, an isothiocyanate group. , Sulfone group, cyano group, nitro group, isonitrile group, vinyl group, allyl group, alkoxy group, acid anhydride group, carbon-carbon double bond, ester bond, thioester bond, ether bond, thioether bond, disulfide bond, amide A bond, an imide bond, a urethane bond, etc. are mentioned. One or more of these reactive functional groups can be present in the molecule.

  Among these, a hydroxyl group, a carboxyl group, a formyl group, an amino group, and a carbonyl group can be preferably used from the viewpoint of reactivity with (D) cellulose nanofibers and / or (F) thermoplastic resin.

  Suitable examples of the (E) binder component include, but are not limited to, polyamide-based resins, polyester-based resins, polyacetal-based resins, polycarbonate-based resins, polyphenylene ether-based resins (polyphenylene ether is blended or graft-polymerized with another resin). Modified polyphenylene ether is also included), polyarylate resin, polysulfone resin, polyphenylene sulfide resin, polyether sulfone resin, polyketone resin, polyphenylene ether ketone resin, polyimide resin, polyamideimide resin, poly Examples thereof include ether imide resins, polyolefin resins (for example, α-olefin (co) polymers), various ionomers, and the like.

  (E) Preferred specific examples of the binder component include high-density polyethylene, low-density polyethylene (for example, linear low-density polyethylene), acid-modified polyethylene, polyethylene wax, acid-modified polyethylene wax, polypropylene, polypropylene wax, acid-modified polypropylene, Acid-modified polypropylene wax, polymethylpentene, cyclic olefin resin, poly-1-butene, poly-1-pentene, polymethylpentene, ethylene / α-olefin copolymer, ethylene / butene copolymer, EPR (ethylene-propylene copolymer Polymer), modified ethylene / butene copolymer, EEA (ethylene-ethyl acrylate copolymer), modified EEA, modified EPR, modified EPDM (ethylene-propylene-diene terpolymer), ionomer, α-olefin copolymer Polymer, modified IR (isoprene rubber), modified SEBS (styrene-ethylene-butylene-styrene copolymer), halogenated isobutylene-paramethylstyrene copolymer, ethylene-acrylic acid modified product, ethylene-vinyl acetate copolymer And an acid-modified product thereof, a copolymer of (ethylene and / or propylene) and (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester), (ethylene and / or propylene) and (unsaturated carboxylic acid and / or (Unsaturated carboxylic acid ester) a polyolefin obtained by metallizing at least a part of the carboxyl group of the copolymer, a block copolymer of a conjugated diene and a vinyl aromatic hydrocarbon, a conjugated diene and a vinyl aromatic hydrocarbon Hydrogenated block copolymers, copolymers of other conjugated diene compounds with non-conjugated olefins, heaven Rubber, various butadiene rubbers, various styrene-butadiene copolymer rubbers, isoprene rubbers, butyl rubbers, bromides of copolymers of isobutylene and p-methylstyrene, halogenated butyl rubbers, acrylonitrile-butadiene rubbers, chloroprene rubbers, ethylene-propylene copolymers Polymer rubber, ethylene-propylene-diene copolymer rubber, styrene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, isoprene-butadiene copolymer rubber, chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber Acrylonitrile-based copolymers containing acrylic, acrylonitrile as the main component, polysulfide rubber, silicone rubber, fluororubber, polyvinyl chloride, polystyrene, polyacrylic acid ester, polymethacrylic acid ester, etc. Acrylonitrile-butanediene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, cellulose resin such as cellulose acetate, vinyl chloride / ethylene copolymer, vinyl chloride / vinyl acetate copolymer, ethylene / vinyl acetate copolymer , And saponified products of ethylene / vinyl acetate copolymer.

  Among these, from the viewpoint of reactivity with (F) thermoplastic resin and / or (D) cellulose nanofiber, acrylics such as polyamide, polyester, polyacrylic acid ester and polymethacrylic acid ester, and acrylonitrile containing acrylonitrile as a main component. A system copolymer, acid-modified polyethylene, acid-modified polypropylene and the like can be preferably used.

  The lower limit of the number average molecular weight of the (E) binder component is preferably 1000, more preferably 2000, further preferably 3000, and particularly preferably 5000. The upper limit of the number average molecular weight is not particularly limited, but is preferably 1,000,000 or less from the viewpoint of handleability. In particular, from the viewpoint of improving the binding or adsorption of the combination of the (E) binder component and the (A) surface treatment agent with the (F) thermoplastic resin and / or (D) cellulose nanofibers in the resin composition, The number average molecular weight of the binder component (E) is preferably within the above range.

  Mass ratio of the total amount of (B) polyurethane and (E) binder component to the (A) surface treatment agent in the resin composition (((B) polyurethane + (E) binder component) / (A) surface treatment agent) ) Is preferably 1.0 or more, more preferably 1.5 or more, still more preferably 2.5 or more, from the viewpoints of mechanical properties and thermal stability. (E) Binder component and (A) surface treatment From the viewpoint of satisfactorily obtaining the effect of the combination with the agent, it is preferably 100 or less, more preferably 50 or less, still more preferably 40 or less.

  The upper limit of the binder component (E) is preferably 200 parts by mass, more preferably 150 parts by mass, more preferably 100 parts by mass, and further preferably 50 parts by mass with respect to 100 parts by mass of the (F) thermoplastic resin. . The lower limit of the binder component (E) is preferably 0.01 parts by mass, more preferably 0.05 parts by mass, more preferably 0.1 parts by mass, and further preferably 5 parts by mass with respect to 100 parts by mass of the thermoplastic resin. It is a department. By setting the upper limit to the above range, the strength of the entire resin composition becomes good. By setting the lower limit to the above range, stronger adhesion can be obtained.

  In a typical embodiment, the (F) thermoplastic resin and the (E) binder component differ in molecular weight and / or functional group structure. Examples of preferable combinations of the (F) thermoplastic resin and the (E) binder component are polyamide resin and polyethylene glycol, polyamide resin and polyacrylic, and the like.

  In addition, the method of adding the (E) binder component when preparing the resin composition is not particularly limited, but includes (A) a surface treatment agent, (D) cellulose nanofibers, (E) a binder component, and ( F) A method of previously mixing and melt-kneading a thermoplastic resin, (F) a thermoplastic resin, (A) a surface treatment agent and (E) a binder component are added in advance, and after preliminary kneading if necessary, (D) cellulose nano A method of adding fibers and melt-kneading, a method of pre-mixing (A) a surface treating agent, (D) cellulose nanofibers and (E) binder components, and then (K) melt-kneading with a thermoplastic resin can be mentioned. . (D) A surface treatment agent and (E) a binder component are added to a dispersion liquid in which cellulose nanofibers are dispersed in water, followed by drying to prepare a cellulose preparation, and then the preparation is subjected to (F) heat treatment. The method of adding to the plastic resin is also effective.

≪Other ingredients≫
Next, other components that can be used in the present invention will be described in detail. In one embodiment, the aqueous dispersion of cellulose nanofibers further contains cellulose whiskers in addition to the cellulose fibers. In the present disclosure, a cellulose whisker is a crystalline cellulose that is made from pulp or the like as a raw material, and after cutting the raw material, the amorphous portion of the cellulose is dissolved in an acid such as hydrochloric acid or sulfuric acid, and has a length of / Indicates that the diameter ratio (L / D ratio) is less than 20. The average diameter of the cellulose whiskers may be preferably 1000 nm or less, or 500 nm or less, or 200 nm or less, and preferably 10 nm or more, or 20 nm or more, or 30 nm or more. The average diameter is a value measured by the same method as the average fiber diameter of (D) cellulose nanofibers.

  The upper limit of L / D of the cellulose whiskers is preferably 15, even more preferably 10, and most preferably 5. The lower limit is not particularly limited, but may be greater than 1. In order to exhibit good slidability of the resin composition, the L / D ratio of the cellulose whiskers is preferably within the above range. In one aspect, the cellulose whiskers may have the same properties as those described above for the (D) cellulose fiber (such as an unmodified or modified embodiment) except for the size thereof.

In each of the aqueous dispersion of cellulose nanofibers, the dried cellulose nanofibers, the resin composition and the resin molded product, the blending amount of the cellulose whiskers with respect to 100 parts by mass of (D) cellulose nanofibers is preferably 0.1 parts by mass or more, Alternatively, it is 0.3 part by mass or more, or 0.5 part by mass or more, preferably 30 parts by mass or less, or 20 parts by mass or less, or 10 parts by mass or less.
In one embodiment, the blending amount of the cellulose nanofiber hydrous dispersion liquid and the cellulose whisker with respect to the entire dried cellulose nanofiber is preferably within the above range from the viewpoint of uniformly dispersing the cellulose nanofibers.
In one aspect, the blending amount of the cellulose whiskers with respect to the entire resin composition and the resin molded product is preferably within the above range from the viewpoint of making the orientation of the cellulose nanofibers non-uniform and obtaining uniform mechanical properties.
In one aspect, the blending amount of the cellulose whiskers with respect to 100 parts by mass of the (F) thermoplastic resin is preferably 0.5 parts by mass or more, or 0.8 parts by mass or more, or 1 from the viewpoint of maintaining the properties of the thermoplastic resin. It is 0.0 part by mass or more, preferably 20 parts by mass or less, or 10 parts by mass or less, or 5 parts by mass or less.

  Further, the resin composition of the present embodiment may contain various stabilizers conventionally used in thermoplastic resins within the range not impairing the purpose of the present embodiment. Examples of the stabilizer include, but are not limited to, the following surfactants, inorganic fillers, heat stabilizers and lubricating oils. These may be used alone or in combination of two or more. These may be commercially available reagents or products.

  The surfactant is a monomer and is different from the surface treatment agent (A) or the like in at least this respect. The surfactant contributes to improving the dispersibility of the (D) cellulose nanofibers in the (F) thermoplastic resin. In each of the aqueous dispersion of cellulose nanofibers, the dried cellulose nanofibers, the resin composition and the resin molded product, the preferable amount of the surfactant is 50 parts by mass or less based on 100 parts by mass of (D) cellulose nanofibers. . A more preferable upper limit is 45 parts by mass, still more preferably 40 parts by mass, even more preferably 35 parts by mass, and particularly preferably 30 parts by mass. Since the surfactant is an additional component, its lower limit is not particularly limited, but from the viewpoint of improving the handling property, it is preferably 0.1 part by mass, more preferably 0 part by mass, relative to 100 parts by mass of the (D) cellulose nanofiber. 0.5 parts by mass, most preferably 1 part by mass. The surfactant may be a commercially available reagent or product.

  The method of adding the surfactant when preparing the cellulose nanofiber resin composition is not particularly limited, but (D) cellulose nanofiber, (F) thermoplastic resin, and surfactant are premixed. Melt-kneading, (F) adding a surfactant in advance to the thermoplastic resin, pre-kneading if necessary, and then (D) adding cellulose nanofibers and melt-kneading, (D) cellulose nanofibers Examples include a method of previously mixing with a surfactant and then melt-kneading with the thermoplastic resin (F). (D) A method in which a surfactant is added to a dispersion liquid in which cellulose nanofibers are dispersed in water and dried to prepare a cellulose preparation, and then the preparation is added to (F) a thermoplastic resin is also effective. is there.

  Typical surfactants include those having a basic skeleton of carbon atoms and a functional group composed of an element selected from carbon, hydrogen, oxygen, nitrogen, chlorine, sulfur and phosphorus. As long as the molecule has the above-mentioned structure, a compound in which an inorganic compound and the above functional group are chemically bonded is also preferable.

  The surfactant may be used alone or as a mixture of two or more kinds. In the case of a mixture, the characteristic value of the surfactant of the present disclosure (for example, static surface tension, dynamic surface tension, SP value) means the value of the mixture.

  The static surface tension of the surfactant is preferably 20 mN / m or more. This static surface tension refers to the surface tension measured by the Wilhelmy method. When using a liquid surfactant at room temperature, the value measured at 25 ° C. is used. When a solid or semi-solid surface active agent is used at room temperature, the surface active agent is heated to a temperature equal to or higher than the melting point, measured in a molten state, and the value corrected to 25 ° C. is used. In addition, in this indication, room temperature means 25 degreeC. Further, the surfactant may be dissolved or diluted in an organic solvent, water or the like for the purpose of facilitating the addition. The above-mentioned static surface tension in this case means the static surface tension of the surfactant itself used.

  When the static surface tension of the surfactant is within the above range, the dispersibility of the (D) cellulose nanofibers in the resin composition is further improved. Although the reason is not clear, the hydrophilic functional group in the surfactant coats the surface of the (D) cellulose nanofiber through a hydrogen bond or the like with a hydroxyl group or a reactive group of the (D) cellulose nanofiber, It is considered that this is because the formation of the interface between the thermoplastic resin (F) and the cellulose nanofibers (D) is inhibited. Since the hydrophilic group of the surfactant is arranged on the (D) cellulose nanofiber side, the (F) thermoplastic resin side has a hydrophobic atmosphere, so that the (F) thermoplastic resin and (D) cellulose nanofiber are This is thought to be due to the increased affinity of.

  The lower limit of the preferred static surface tension of the surfactant is 23 mN / m, more preferably 25 mN / m, even more preferably 30 mN / m, even more preferably 35 mN / m, most preferably 39 mN / m. The preferred upper limit of the static surface tension of the surfactant is 72.8 mN / m, more preferably 60 mN / m, even more preferably 50 mN / m, most preferably 45 mN / m.

  Both the affinity of the surfactant for the (F) thermoplastic resin and the affinity for the (D) cellulose nanofiber are compatible with each other, and the fine dispersion of the (D) cellulose nanofiber in the (F) thermoplastic resin and the resin composition. From the viewpoint of exhibiting properties such as fluidity of the product, improvement of strength and elongation of the resin molded product, it is preferable to set the static surface tension of the surfactant within a specific range.

  The static surface tension of the surfactant referred to in the present disclosure can be measured by using a commercially available surface tension measuring device. Specifically, it can be measured by the Wilhelmy method using an automatic surface tension measuring device (for example, Kyowa Interface Science Co., Ltd., trade name "CBVP-Z type", using an attached glass cell). At this time, when the surfactant is liquid at room temperature, it is charged in the attached stainless petri dish so that the height from the bottom to the liquid surface is 7 mm to 9 mm, and the temperature is adjusted to 25 ° C. ± 1 ° C. and then measured. , Is calculated by the following formula.

γ = (P−mg + shρg) / Lcosθ
Here, γ: static surface tension, P: balancing force, m: mass of plate, g: gravitational constant, L: perimeter of plate, θ: contact angle between plate and liquid, s: cross sectional area of plate, h: ( (To the point where the forces are balanced) The depth of sinking from the liquid surface, ρ: density of the liquid.

  Since the surface tension of a solid substance at room temperature cannot be measured by the above method, the surface tension measured at the temperature of the melting point + 5 ° C. is used for convenience. When the melting point is an unknown substance, first, the melting point is measured by a visual melting point measuring method (JIS K6220), heated to a temperature equal to or higher than the melting point to melt, and then adjusted to a temperature of melting point + 5 ° C. by the above-mentioned Wilhelmy method. It is possible by measuring the surface tension.

  The dynamic surface tension of the surfactant is preferably 60 mN / m or less. The more preferable upper limit of the dynamic surface tension is 55 mN / m, 50 mN / m is more preferable, 45 mN / m is further preferable, and 40 mN / m is particularly preferable. The preferable lower limit of the dynamic surface tension of the surfactant is 10 mN / m. A more preferable lower limit is 15 mN / m, and 20 mN / m is the most preferable.

  The dynamic surface tension referred to here is the maximum bubble pressure method (the maximum pressure (maximum bubble pressure) when bubbles are generated by flowing air through a thin tube (hereinafter referred to as a probe) inserted in a liquid, and the surface tension is measured. Is the surface tension measured by the method of calculating. Specifically, a surfactant is used as 5% by mass to dissolve or disperse in ion-exchanged water to prepare a measurement solution, and the temperature is adjusted to 25 ° C., and then a dynamic surface tensiometer (for example, product name Theta manufactured by Eiko Seiki Co., Ltd. Science t-60 type, using a probe (capillary TYPE I (made by peak resin), single mode), refers to the value of the surface tension measured at a bubble generation cycle of 10 Hz. The dynamic surface tension in each cycle is as follows. It is calculated by the formula.

σ = ΔP · r / 2
Here, σ: dynamic surface tension, ΔP: pressure difference (maximum pressure-minimum pressure), r: capillary radius.

  The dynamic surface tension measured by the maximum bubble pressure method means the dynamic surface tension of a surfactant in a fast-moving field. Surfactants usually form micelles in water. A low dynamic surface tension means that the diffusion rate of the surfactant molecule from the micelle state is high, and a high dynamic surface tension means that the diffusion rate of the molecule is slow.

  It is advantageous that the dynamic surface tension of the surfactant is equal to or lower than a specific value, because the effect of significantly improving the dispersion of the (D) cellulose nanofibers in the resin composition is exhibited. Although details of the reason for the improvement of the dispersibility are unknown, the surfactant having a low dynamic surface tension is excellent in diffusibility in the extruder, and thus (D) cellulose nanofibers and (F) thermoplastic resin It is considered that the ability to be localized at the interface of (3) and the good coating of the surface of the (D) cellulose nanofiber contribute to the effect of improving dispersibility. The effect of improving the dispersibility of the cellulose nanofiber (D), which is obtained by setting the dynamic surface tension of the surfactant to a specific value or less, exerts a remarkable effect of eliminating the strength defect of the molded body.

  As the surfactant, those having a boiling point higher than that of water are preferable. The boiling point higher than water refers to a boiling point higher than the boiling point at each pressure in the vapor pressure curve of water (for example, 100 ° C. under 1 atmosphere).

  By selecting a surfactant having a boiling point higher than that of water, for example, (D) cellulose nanofibers dispersed in water are dried in the presence of a surfactant to prepare a (D) cellulose nanofiber preparation. When obtained, the water and the surfactant are replaced in the process of water evaporation, and the surfactant is present on the surface of the (D) cellulose nanofiber, so that the aggregation of the (D) cellulose nanofiber is significantly increased. The effect of suppressing can be exhibited.

  From the viewpoint of handleability, a surfactant that is liquid at room temperature (that is, 25 ° C.) can be preferably used. The surfactant, which is liquid at room temperature, has an advantage that it is easily compatible with (D) cellulose nanofibers and easily penetrates into (F) thermoplastic resin.

  As the surfactant, those having a solubility parameter (SP value) of 7.25 or more can be more preferably used. When the surfactant has an SP value in this range, the dispersibility of the (D) cellulose nanofibers in the (F) thermoplastic resin is improved.

The SP value is dependent on both the cohesive energy density and the molar molecular weight of the substance according to the literature of FODERS (RF Foders: Polymer Engineering & Science, vol. 12 (10), p. 2359-2370 (1974)). However, it is considered that these depend on the type and number of the substituents of the substance, and according to the document of Ueda et al. (Paint Research, No. 152, Oct. 2010), the existing ones shown in the examples described later are used. SP values (cal / cm ³ ) ^1/2 for major solvents have been published.

  The SP value of the surfactant can be experimentally determined from the boundary between soluble and insoluble when the surfactant is dissolved in various solvents having known SP values. For example, it can be determined whether or not the total amount is dissolved when 1 mL of the surfactant is dissolved for 1 hour at room temperature under stirrer stirring in various solvents (10 mL) having different SP values in the tables shown in the examples. . For example, when the surfactant is soluble in diethyl ether, the SP value of the surfactant is 7.25 or more.

  Examples of the surfactant include compounds having a chemical structure in which a hydrophilic substituent and a hydrophobic substituent are covalently bonded, and those used in various applications such as food and industry can be used. For example, the following may be used alone or in combination of two or more. In a particularly preferred embodiment, the surfactant is a surfactant having a particular dynamic surface tension as described above.

  As the surfactant, any of an anionic surfactant, a nonionic surfactant, a zwitterionic surfactant, and a cationic surfactant can be used, but they have an affinity with cellulose nanofibers. In this respect, anionic surfactants and nonionic surfactants are preferable, and nonionic surfactants are more preferable.

  Examples of the anionic surfactant include fatty acid-based (anion) fatty acid sodium, fatty acid potassium, sodium alphasulfofatty acid ester sodium, and the like, and linear alkylbenzene-based agent includes linear alkylbenzene sulfonate sodium and the like. Examples of the alcohol (anion) type include sodium alkyl sulfate ester, sodium alkyl ether sulfate, and the like, such as alpha olefin type sodium alpha olefin sulfonate, and normal paraffin type sodium alkyl sulfonate. It is also possible to use one kind or a mixture of two or more kinds.

  Examples of the nonionic surfactant include fatty acid-based (nonionic) glycolipids such as sucrose fatty acid ester, sorbitan fatty acid ester, and polyoxyethylene sorbitan fatty acid ester, and fatty acid alkanolamide. Examples of the ion) include polyoxyethylene alkyl ether and the like, and examples of the alkylphenol type include polyoxyethylene alkylphenyl ether and the like, and it is possible to use one kind or a mixture of two or more kinds thereof.

  Examples of the zwitterionic surfactant include alkylamino fatty acid sodium as the amino acid type, alkyl betaine as the betaine type, alkylamine oxide as the amine oxide type, and one or two of them. It is also possible to use a mixture of two or more species.

  Examples of the cationic surfactant include alkyl trimethyl ammonium salt and dialkyl dimethyl ammonium salt as the quaternary ammonium salt type, and it is possible to use one kind or a mixture of two or more kinds thereof. .

  Surfactants may be derivatives of fats and oils. Examples of oils and fats include esters of fatty acids and glycerin, and usually those in the form of triglyceride (tri-O-acylglycerin). Dry oils, semi-dry oils, non-dry oils are classified in order from fatty oils that are easily oxidized and solidified, and those used in various applications such as food and industry can be used. They are used alone or in combination of two or more.

  Examples of fats and oils include animal and vegetable oils such as terpine oil, tall oil, rosin, white squeezing oil, corn oil, soybean oil, sesame oil, rapeseed oil (canola oil), rice oil, bran oil, camellia oil, safflower oil (safflower oil). , Coconut oil (palm kernel oil), cottonseed oil, sunflower oil, perilla oil (sesame oil), linseed oil, olive oil, peanut oil, almond oil, avocado oil, hazelnut oil, walnut oil, grape seed oil, mustard oil, Lettuce oil, fish oil, whale oil, shark oil, liver oil, cocoa butter, peanut butter, palm oil, lard (pork fat), het (beef fat), chicken oil, rabbit fat, sheep fat, horse fat, schmalz, milk fat (butter, butter, Gee, etc.), hydrogenated oil (margarine, shortening, etc.), castor oil (vegetable oil) and the like.

  Among the above-mentioned animal and vegetable oils, terpine oil, tall oil, and rosin are particularly preferable from the viewpoint of affinity for the surface of cellulose nanofibers and uniform coating property.

  Terpine oil (also called terbine oil) is an essential oil obtained by steam distillation of chips of Pinaceae or pine resin (matsuya) obtained from those trees, and is also called pine essential oil or turpentine. Say. Examples of terpine oils include gum turpentine oil (obtained by steam distillation of pine resin), wood turpentine oil (obtained by steam distillation or dry distillation of Pinus family tree chips), and turpentine sulfate. Oil (obtained by distilling chips during heat treatment during sulfate pulp production), turpentine sulfite (obtained by distilling chips during heat treatment during sulfite pulp production), and almost colorless It is a pale yellow liquid containing mainly α-pinene and β-pinene other than turpentine sulfite oil. Unlike other turpentine oils, turpentine sulfite oil has p-cymene as the main component. As long as it contains the above-mentioned components, it is contained in the terpine oil, and any one of them can be used as the surfactant of the present invention.

  Tall oil is an oil containing resin and fatty acid as main components, which is a by-product when kraft pulp is made from pine wood as a raw material. As the tall oil, tall fat containing oleic acid and linoleic acid as main components or tall rosin containing a diterpenoid compound having 20 carbon atoms such as abietic acid as a main component may be used.

  Rosin is a residue that remains after distilling turpentine essential oil by collecting pine nuts and other balsams, which are sap of Pinaceae plants, and is a natural resin containing rosin acid (abietic acid, parastoric acid, isopimaric acid, etc.) as the main component. Is. Also called colophony or colophony. Among them, tall rosin, wood rosin and gum rosin can be preferably used. A rosin derivative obtained by subjecting these rosins to various stabilizing treatments, esterification treatments, purification treatments and the like can be used as a surfactant. The stabilization treatment means subjecting the above rosins to hydrogenation, disproportionation, dehydrogenation, polymerization treatment and the like. The esterification treatment refers to a treatment of reacting the rosin or the rosin subjected to the stabilization treatment with various alcohols to form a rosin ester. For the production of this rosin ester, various known alcohols or epoxy compounds can be used. Examples of the alcohol include monohydric alcohols such as n-octyl alcohol, 2-ethylhexyl alcohol, decyl alcohol and lauryl alcohol; dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and neopentyl glycol; Trihydric alcohols such as glycerin, trimethylolethane, trimethylolpropane, and cyclohexanedimethanol; and tetrahydric alcohols such as pentaerythritol and diglycerin. Also, isopentyldiol, ethylhexanediol, erythrulose, ozonated glycerin, caprylyl glycol, glycol, (C15-18) glycol, (C20-30) glycol, glycerin, diethylene glycol, diglycerin, dithiaoctanediol, DPG, Thioglycerin, 1,10-decanediol, decylene glycol, triethylene glycol, chryimethylgidroxymethylcyclohexanol, phytantriol, phenoxypropanediol, 1,2-butanediol, 2,3-butanediol, butylethyl Multivalent compounds such as propanediol, BG, PG, 1,2-hexanediol, hexylene glycol, pentylene glycol, methylpropanediol, menthanediol, lauryl glycol Alcohol may be used. Further, those classified as sugar alcohols such as inositol, erythritol, xylitol, sorbitol, maltitol, mannitol and lactitol are also included in the polyhydric alcohol.

  Further, as the alcohol, an alcoholic water-soluble polymer can be used. As the alcoholic water-soluble polymer, polysaccharides / mucopolysaccharides, those classified as starch, those classified as polysaccharide derivatives, those classified as natural resins, those classified as cellulose and derivatives, proteins・ Peptides classified, those classified as peptide derivatives, those classified as synthetic homopolymers, those classified as acrylic (methacrylic acid) acid copolymers, those classified as urethane polymers, Examples thereof include those classified as laminates, those classified as cationized polymers, those classified as other synthetic polymers, and those which are water-soluble at room temperature can be used. More specifically, sodium polyacrylate, cellulose ether, calcium alginate, carboxyvinyl polymer, ethylene / acrylic acid copolymer, vinylpyrrolidone polymer, vinyl alcohol / vinylpyrrolidone copolymer, nitrogen-substituted acrylamide polymer, poly Acrylamide, cationic polymer such as cationized guar gum, dimethyl acrylic ammonium polymer, acrylic acid methacrylic acid acrylic copolymer, POE / POP copolymer, polyvinyl alcohol, pullulan, agar, gelatin, tamarind seed polysaccharide, xanthan gum, carrageenan , High methoxyl pectin, low methoxyl pectin, guar gum, gum arabic, cellulose whiskers, arabinogalactan, karaya gum, tragacanth gum, algin , Albumin, casein, curdlan, gellan gum, dextran, cellulose (those not cellulose fibers and cellulose whiskers of the present disclosure), polyethylene imine, polyethylene glycol, cationized silicone polymer and the like.

  Among the above-mentioned various rosin esters, the coating property of the surface of the cellulose nanofibers and the dispersibility of the cellulose preparation in the resin tend to be further promoted. Therefore, those in which a rosin and a water-soluble polymer are esterified are preferable, and Particularly preferred is an esterified product of ethylene glycol with polyethylene glycol (also referred to as rosin ethylene oxide adduct, polyoxyethylene glycol resin acid ester, or polyoxyethylene rosin acid ester).

  The hydrogenated castor oil-type surfactant is, for example, hydrogenated from castor oil (castor oil, castor oil, castor bean oil), which is one of the vegetable oils collected from castor seeds of the Euphorbiaceae family. As the hydrophobic group, a compound in which a hydroxyl group in the structure and a hydrophilic group such as a PEO chain are covalently bonded can be mentioned. The components of castor oil are glycerides of unsaturated fatty acids (87% ricinoleic acid, 7% oleic acid, 3% linoleic acid) and a small amount of saturated fatty acids (3% palmitic acid, stearic acid, etc.). In addition, as a typical structure of the POE group, there are those having ethylene oxide (EO) residues of 4 to 40, and typical examples thereof are those having 15 to 30. 15-30 are preferable, as for the EO residue of nonylphenol ethoxylate, 15-25 are more preferable, and 15-20 are especially preferable.

  Examples of the mineral oil derivative include greases such as calcium soap-based grease, calcium composite soap-based grease, sodium soap-based grease, aluminum soap-based grease, lithium soap-based grease and the like.

  The surfactant may be an alkylphenyl type compound, and examples thereof include alkylphenol ethoxylates, that is, compounds obtained by ethoxylating alkylphenol with ethylene oxide. Alkylphenol ethoxylates are nonionic surfactants. It is also called poly (oxyethylene) alkylphenyl ether because the hydrophilic polyoxyethylene (POE) chain and the hydrophobic alkylphenol group are linked by an ether bond. Generally, a series of products having different average chain lengths are commercially available as a mixture of many compounds having different alkyl chain lengths and POE chain lengths. Alkyl chain lengths having 6 to 12 carbon atoms (excluding phenyl group) are commercially available, and typical alkyl group structures include nonylphenol ethoxylate and octylphenol ethoxylate. Further, a typical POE group structure has an ethylene oxide (EO) residue of 5 to 40, and a typical structure thereof is 15 to 30. 15-30 are preferable, as for the EO residue of nonylphenol ethoxylate, 15-25 are more preferable, and 15-20 are especially preferable.

  The surfactant may be a β-naphthyl type compound, for example, β mono-substitution in which a carbon atom at the 2 or 3 or 6 or 7 position of the aromatic ring is bonded to a hydroxyl group by including naphthalene in a part of its chemical structure. Examples thereof include compounds in which a body and a hydrophilic group such as a PEO chain are covalently bonded. In addition, as a typical structure of the POE group, there are those having ethylene oxide (EO) residues of 4 to 40, and typical examples thereof are those having 15 to 30. 15-30 are preferable, as for EO residue, 15-25 are more preferable, and 15-20 are especially preferable.

The surfactant may be a bisphenol A type compound, and for example, bisphenol A (chemical formula: (CH ₃ ) ₂ C (C ₆ H ₄ OH) ₂ ) is included in a part of its chemical structure, and its structure Examples thereof include compounds in which two phenol groups in the inside and a hydrophilic group such as PEO chain are covalently bonded. In addition, as a typical structure of the POE group, there are those having ethylene oxide (EO) residues of 4 to 40, and typical examples thereof are those having 15 to 30. 15-30 are preferable, as for the EO residue of nonylphenol ethoxylate, 15-25 are more preferable, and 15-20 are especially preferable. This EO residue refers to the average value of two ether bonds, if two are present in one molecule.

  The surfactant may be a styrenated phenyl type compound. For example, a styrenated phenyl group is included in a part of its chemical structure, and a phenol group in the structure and a hydrophilic group such as a PEO chain are covalently bonded. The compound which did is mentioned. The styrenated phenyl group has a structure in which 1 to 3 molecules of styrene are added to the benzene ring of the phenol residue. In addition, as a typical structure of the POE group, there are those having ethylene oxide (EO) residues of 4 to 40, and typical examples thereof are those having 15 to 30. 15-30 are preferable, as for the EO residue of nonylphenol ethoxylate, 15-25 are more preferable, and 15-20 are especially preferable. This EO residue refers to the average value of two ether bonds, if two are present in one molecule.

  Specific preferred examples of the surfactant include, for example, acylamino acid salts such as acylglutamates, sodium laurate, sodium palmitate, sodium lauryl sulfate, higher alkyl sulfate ester salts such as potassium lauryl sulfate, and polyoxyethylene lauryl. Alkyl ether sulfates such as triethanolamine sulfate, sodium polyoxyethylene lauryl sulfate, anionic surfactants such as N-acyl sarcosinate such as sodium lauroyl sarcosine; alkyls such as stearyl trimethyl ammonium chloride and lauryl trimethyl ammonium chloride Trimethylammonium salt, distearyldimethylammonium chloride dialkyldimethylammonium salt, (N, N'-dimethyl-3,5-methylenepiperidinium) chloride, cetium chloride Alkylpyridinium salts such as pitidinium, alkyl quaternary ammonium salts, alkylamine salts such as polyoxyethylene alkylamine, cationic surfactants such as polyamine fatty acid derivatives and amyl alcohol fatty acid derivatives; 2-undecyl-N, N, N- (Hydroxyethylcarboxymethyl) 2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt and other imidazoline-based amphoteric surfactants, 2-heptadecyl-N-carboxymethyl- Amphoteric surfactants such as N-hydroxyethylimidazolinium betaine, betaine lauryldimethylaminoacetic acid betaine, alkyl betaine, amidobetaine, sulfobataine and other betaine-based amphoteric surfactants, sorbitan nomooleate, sorbi Monomoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, penta-2-ethylhexyl diglycerol sorbitan, tetra-2-ethylhexyl diglycerol sorbitan, etc. Sorbitan fatty acid esters, glyceryl monostearate, α, α'-glyceryl pyroglutamate oleate, glycerin monostearate glycerin polyglycerin fatty acids such as malic acid, propylene glycol fatty acid esters such as propylene glycol monostearate, hardening Castor oil derivative, glycerin alkyl ether, polyoxyethylene-sorbitan monostearate, polyoxyethylene-sorbitan monooleate Polyoxyethylene-sorbitan tetraoleate and other polyoxyethylene-sorbitan fatty acid esters, polyoxyethylene-sorbit monolaurate, polyoxyethylene-sorbit monooleate, polyoxyethylene-sorbit pentaoleate, polyoxyethylene- Polyoxyethylene-glycerin fatty acid esters such as sorbit monostearate, polyoxyethylene-glycerin monoisostearate, polyoxyethylene-glycerin triisostearate, polyoxyethylene monooleate, polyoxyethylene distearate, poly Oxyethylene monodioleate, polyoxyethylene fatty acid esters such as ethylene glycol distearate, polyoxyethylene hydrogenated castor oil, polyoxyethylene Castor oil, polyoxyethylene hydrogenated castor oil monoisostearate, polyoxyethylene hydrogenated castor oil triisostearate, polyoxyethylene hydrogenated castor oil monopyroglutamic acid monoisostearate diester, polyoxyethylene hydrogenated castor oil maleic acid and other poly Nonionic surfactants such as oxyethylene castor oil hydrogenated castor oil derivatives and the like can be mentioned.

  Among the above, a surfactant having a polyoxyethylene chain, a carboxylic acid, or a hydroxyl group as a hydrophilic group is preferable in terms of affinity with cellulose nanofibers, and a polyoxyethylene-based interface having a polyoxyethylene chain as a hydrophilic group is preferable. Activators (polyoxyethylene derivatives) are more preferable, and nonionic polyoxyethylene derivatives are even more preferable. The polyoxyethylene chain length of the polyoxyethylene derivative is preferably 3 or more, more preferably 5 or more, further preferably 10 or more, and particularly preferably 15 or more. The longer the chain length, the higher the affinity with the cellulose nanofibers, but in balance with the coating property (localization to the interface between the resin and the cellulose nanofibers), the upper limit is preferably 60 or less, 50 The following is more preferable, 40 or less is further preferable, 30 or less is particularly preferable, and 20 or less is the most preferable.

  When cellulose nanofibers are mixed with a hydrophobic resin (for example, polyolefin, polyphenylene ether, etc.), it is preferable to use one having a polyoxypropylene chain as a hydrophilic group instead of the polyoxyethylene chain. The polyoxypropylene chain length is preferably 3 or more, more preferably 5 or more, further preferably 10 or more, and particularly preferably 15 or more. The longer the chain length, the higher the affinity with cellulose nanofibers, but in balance with the coating property, the upper limit is preferably 60 or less, more preferably 50 or less, further preferably 40 or less, particularly 30 or less. 20 or less is most preferable.

  Among the above-mentioned surfactants, particularly, as the hydrophobic group, alkyl ether type, alkyl phenyl ether type, rosin ester type, bisphenol A type, β naphthyl type, styrenated phenyl type, and hardened castor oil type have affinity with the resin. Since it is high, it can be preferably used. The preferable alkyl chain length (the number of carbons excluding the phenyl group in the case of alkylphenyl) is preferably 5 or more, more preferably 10 or more, further preferably 12 or more, particularly preferably 16 or more. When the resin is a polyolefin, the higher the carbon number, the higher the affinity with the resin is, so the upper limit is not set, but it is preferably 30, and more preferably 25.

  Among these hydrophobic groups, those having a cyclic structure or those having a bulky and polyfunctional structure are preferable, and those having a cyclic structure include alkylphenyl ether type, rosin ester type, bisphenol A type, β-naphthyl type, Styrenated phenyl type is preferable, and as the one having a polyfunctional structure, hardened castor oil type is particularly preferable. Among these, rosin ester type and hardened castor oil type are most preferable.

  Therefore, in a particularly preferred embodiment, the surfactant is one or more selected from the group consisting of rosin derivatives, alkylphenyl derivatives, bisphenol A derivatives, β-naphthyl derivatives, styrenated phenyl derivatives, and hydrogenated castor oil derivatives.

  The blending amount of the surfactant with respect to 100 parts by mass of the (F) thermoplastic resin is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass, from the viewpoint of obtaining good mechanical properties, thermal stability and durability. It is at least parts by mass, more preferably at least 0.5 parts by mass, and from the viewpoint of obtaining good moldability, it is preferably at most 200 parts by mass, more preferably at most 100 parts by mass, still more preferably at most 10 parts by mass.

  The inorganic filler is not limited to the following, but may be at least one selected from fibrous particles, plate-like particles, inorganic pigments and the like. In one aspect, the fibrous particles and the plate-like particles mentioned here are particles having an average aspect ratio of 5 or more. The addition amount of the above-mentioned inorganic filler is not particularly limited, but it is preferably in the range of 0.002 to 50 parts by mass with respect to 100 parts by mass of the thermoplastic resin. When the addition amount of the inorganic filler is within the above range, the handleability of the resin composition can be improved.

  As the heat stabilizer, an antioxidant (for example, a hindered phenol antioxidant) is preferable from the viewpoint of improving the heat stability of the resin molded body.

  The addition amount of the antioxidant is not particularly limited, but it is preferable that the amount of the antioxidant, for example, a hindered phenolic antioxidant is 0.1 to 2 parts by mass with respect to 100 parts by mass of the thermoplastic resin. . When the added amount of the stabilizer is within the above range, the handleability of the resin composition can be improved.

  The lower limit of the molecular weight of the lubricating oil is preferably 100, more preferably 400, even more preferably 500. The upper limit is preferably 5 million, more preferably 2 million, and even more preferably 1 million. The lower limit of the melting point of the lubricating oil is preferably -50 ° C, more preferably -30 ° C, and even more preferably -20 ° C. The upper limit of the melting point of the lubricating oil is preferably 50 ° C, more preferably 30 ° C, even more preferably 20 ° C. When the molecular weight is 100 or more, the slidability of the lubricating oil tends to be good. Further, when the molecular weight is 5,000,000 or less, particularly 1,000,000 or less, the dispersion of the lubricating oil becomes good and the abrasion resistance tends to be improved. Further, when the melting point is -50 ° C or higher, the fluidity of the lubricating oil existing on the surface of the molded body is maintained, and the abrasion resistance of the molded body tends to be improved by suppressing the abrasive wear. Further, when the melting point is 50 ° C. or less, it tends to be easily kneaded with the thermoplastic resin, and the dispersibility of the lubricating oil tends to be improved. From the above viewpoint, the molecular weight and the melting point of the lubricating oil are preferably within the above ranges. In a preferred embodiment, the melting point is 2.5 ° C below the pour point of the lubricating oil. The pour point can be measured according to JIS K2269.

  Lubricating oil that can be used in the present embodiment is not limited to the following, as long as it is a substance that can improve the friction and wear characteristics of the thermoplastic resin molded body, for example, engine oil and cylinder oil Natural oils or paraffinic oils (such as Diana Process Oil PS32 manufactured by Idemitsu Kosan Co., Ltd.), naphthenic oils (such as Diana Process Oil NS90S manufactured by Idemitsu Kosan Co., Ltd.) and aroma oils (Diana Process Oil manufactured by Idemitsu Kosan Co., Ltd.) AC12 and the like), silicone-based oils (G30 series manufactured by Shin-Etsu Chemical Co., Ltd.) (silicone oil represented by polydimethylsiloxane, silicone gum, modified silicone gum) and the like, and they are generally commercially available. From the lubricating oil Nde, as such or may be used appropriately in the formulation if desired. Of these, paraffin-based oils and silicone-based oils are preferable because they are excellent in terms of slidability and are easily available industrially. These lubricating oils may be used alone or in combination.

  The lower limit of the content of the lubricating oil with respect to 100 parts by mass of the thermoplastic resin is not particularly limited, but is preferably 0.1 parts by mass, more preferably 0.2 parts by mass, and further preferably 0.3 parts by mass. The upper limit of the content is not particularly limited, but is preferably 5.0 parts by mass, more preferably 4.5 parts by mass, and further preferably 4.2 parts by mass. When the content of the lubricating oil is within the above range, the abrasion resistance of the cellulose nanofiber resin composition tends to be improved. In particular, when the content of the lubricating oil is 0.1 part by mass or more, sufficient slidability can be ensured and abrasion resistance tends to be improved. When the content of the lubricating oil is 5.0 parts by mass or less, softening of the resin can be suppressed, and the strength of the cellulose nanofiber resin composition that can withstand applications such as gears tends to be secured.

  When the range of the content of the lubricating oil in the cellulose nanofiber resin composition of the present embodiment is adjusted as described above, it is preferable from the viewpoint of improving the wear characteristics during sliding and being excellent in stable sliding property.

≪Tensile yield strength improvement rate≫
In the resin composition of the present invention, the tensile yield strength tends to be dramatically improved as compared with the thermoplastic resin (F) alone. The tensile yield strength improvement rate is the mass content a of the (D) cellulose nanofibers in the resin composition (that is, the value when the total mass of the resin composition is 1), the tensile yield strength b of the resin composition, and (F) From the tensile yield strength c of the thermoplastic resin, the following formula (1):
Tensile yield strength improvement rate = (b / c-1) / a (1)
Is a value obtained according to. The larger this value, the better the dispersibility of the (D) cellulose nanofibers in the resin composition, and the cellulose effectively functions as a filler.

  The lower limit of the tensile yield strength improvement rate is preferably 0.6, more preferably 0.7, further preferably 0.8, further preferably 0.9, and further preferably 1.0. The tensile yield strength improvement rate is most preferably greater than 1.0. The upper limit of the tensile yield strength improvement rate is not particularly limited, but from the viewpoint of ease of production, it is preferably 30.0, more preferably 20.0.

≪Bending elastic modulus improvement rate≫
In the resin composition of the present invention, the flexural modulus tends to be dramatically improved as compared with the (F) thermoplastic resin alone. The flexural modulus improvement rate is calculated from the following equation (from the mass content a of the cellulose nanofibers (D) in the resin composition, the flexural modulus d of the resin composition, and the flexural modulus e of the (F) thermoplastic resin: 2):
Bending elastic modulus improvement rate = (d / e-1) / a (2)
Is a value obtained according to. The larger this value, the better the dispersibility of the (D) cellulose nanofibers in the resin composition, and the (D) cellulose nanofibers effectively function as a filler. The lower limit of the flexural modulus improvement rate is preferably 2.3, more preferably 2.5, further preferably 2.8, and most preferably 3.0. The flexural modulus improvement rate is most preferably greater than 3.0. The upper limit of the flexural modulus improvement rate is not particularly limited, but from the viewpoint of ease of production, it is preferably 30.0, and more preferably 20.0.

<< Production of Cellulose Nanofiber Resin Composition >>
In one embodiment, a cellulose nanofiber resin composition is prepared by preparing a water-containing dispersion of cellulose nanofibers or a dried cellulose nanofiber, and at least (F) the water-containing dispersion of cellulose nanofibers or the dried cellulose nanofiber. It can be manufactured by a method including kneading with a thermoplastic resin.

  The apparatus for producing the resin composition of the present embodiment is not particularly limited, and a generally practiced kneader can be applied. Although the kneader is not limited to the following, for example, a single-screw or multi-screw kneading extruder, a roll, a Banbury mixer, or the like may be used. Above all, a twin-screw extruder equipped with a pressure reducing device and a side feeder facility is preferable.

  The resin composition of the present invention can be provided in various shapes. Specific examples thereof include a resin pellet shape, a sheet shape, a fiber shape, a plate shape, a rod shape, and the like, but the resin pellet shape is more preferable from the viewpoint of easy post-processing and easy transportation. Preferable pellet shapes at this time include a round shape, an elliptical shape, a cylindrical shape, and the like, which differ depending on the cutting method at the time of extrusion processing. Pellets that are cut by a cutting method called underwater cut are often round, and pellets that are cut by a cutting method called hot cut are often round or elliptical, and cut called a strand cut. The pellets cut by the method are often cylindrical. In the case of round pellets, the preferable size is 1 mm or more and 3 mm or less in terms of pellet diameter. Moreover, in the case of a cylindrical pellet, a preferable diameter is 1 mm or more and 3 mm or less, and a preferable length is 2 mm or more and 10 mm or less. The above diameter and length are preferably at least the lower limit from the viewpoint of operation stability during extrusion, and are preferably at most the upper limit from the viewpoint of biting into the molding machine during post-processing.

The following method may be mentioned as a specific example of the method for producing the resin composition.
[Example 1-1]
Using a single-screw or twin-screw extruder, melt-kneading a mixture containing (F) thermoplastic resin, (D) cellulose nanofiber, (A) surface treatment agent, (B) polyurethane, and, if necessary, optional components. Then, the mixture is extruded into a strand, cooled and solidified in a water bath to obtain a pellet-shaped molded body.
[Example 1-2]
Using a single-screw or twin-screw extruder, melt-kneading a mixture containing (F) thermoplastic resin, (D) cellulose nanofiber, (A) surface treatment agent, (B) polyurethane, and, if necessary, optional components. Then, it is extruded into a rod shape or a cylindrical shape and cooled to obtain an extruded body.
[Example 1-3]
Using a single-screw or twin-screw extruder, melt-kneading a mixture containing (F) thermoplastic resin, (D) cellulose nanofiber, (A) surface treatment agent, (B) polyurethane, and, if necessary, optional components. Then, a method of obtaining an extruded sheet or a film-shaped molded product from a T die.

Further, the following methods may be mentioned as specific examples of the method of melt-kneading the mixture of (F) thermoplastic resin, (D) cellulose nanofiber, (A) surface treatment agent and (B) polyurethane.
[Example 2-1]
(F) a thermoplastic resin and (D) cellulose nanofibers mixed in a desired ratio, (A) a surface treatment agent, and (B) a cellulose nanofiber-containing aqueous dispersion or a dried cellulose nanofiber containing polyurethane. Method of batch melt kneading.
[Example 2-2]
(F) A thermoplastic resin and optionally (A) a surface treatment agent are melt-kneaded and then mixed in a desired ratio (D) cellulose nanofibers, (A) a surface treatment agent and (B) a cellulose nanoparticle containing a polyurethane. A method in which a water-containing dispersion liquid of fibers or a dried cellulose nanofiber is added and further melt-kneaded.
[Example 2-3]
Cellulose nanofiber hydrous containing (D) cellulose nanofibers, (A) surface treatment agent and (B) polyurethane mixed in a desired ratio after melt-kneading (F) a thermoplastic resin and (B) polyurethane as required. A method of further melt-kneading the dispersion or the dried cellulose nanofibers.
[Example 2-4]
A cellulose nanofiber aqueous dispersion containing (F) a thermoplastic resin and optionally (D) cellulose nanofibers, (A) a surface treatment agent, and (B) polyurethane was melt-kneaded and then mixed at a desired ratio (D). ) A method of further melt-kneading a dried cellulose nanofiber containing cellulose nanofiber, (A) surface treatment agent and (B) polyurethane.
[Example 2-5]
At least two of the additions of the embodiments of [Example 2-1] to [Example 2-4] described above are performed by dividing the mixture into Top and Side at an arbitrary ratio using a single-screw or twin-screw extruder, and melt kneading. how to.

≪Materials≫
The resin composition of this embodiment can be molded into the following member forms. The method for molding the resin composition is not particularly limited, and a known molding method can be applied. For example, extrusion molding, injection molding, vacuum molding, blow molding, injection compression molding, decorative molding, other material molding, gas assist injection molding, foam injection molding, low pressure molding, ultra-thin wall injection molding (ultra high-speed injection molding), It can be molded by any of molding methods such as in-mold composite molding (insert molding, outsert molding).

  As the application of the member of the present embodiment obtained from the above-mentioned resin composition, the application which is required to have characteristics such as high paintability, sliding resistance, and small dimensional change due to heat after molding is suitable.

  The use of the member of the present embodiment is not limited to the following, but examples thereof include uses of general thermoplastic resin compositions. Specific examples of such applications include, but are not limited to, cams, sliders, levers, arms, clutches, felt clutches, idler gears, pulleys, rollers, rollers, key stems, key tops, shutters. , Reels, shafts, joints, shafts, bearings, guides, and other mechanical parts; outsert-molded resin parts, insert-molded resin parts, chassis, trays, side plates, printers, and copiers Parts for automation equipment; video tape recorder (VTR), video movie, digital video camera, camera, and parts for cameras or video equipment represented by digital cameras; cassette player, DAT, LD (Laser disk), MD (Mini disk) , D (Compact disk) [including CD-ROM (Read only memory), CD-R (Recordable) and CD-RW (Rewritable)], DVD (Digital versatile disk) [DVD-ROM, DVD-R, DVD + R, DVD -RW, DVD + RW, DVD-R DL, DVD + R DL, DVD-RAM (Random access memory), including DVD-Audio], Blu-ray (registered trademark) Disc, HD-DVD, other optical disk drive; MFD ( Music, video or other typified by Multi Function Display (MO), MO (Magneto-Optical Disk), navigation system and mobile personal computer. Examples include communication equipment parts typified by information equipment, mobile phones, and facsimiles; electric equipment parts; electronic equipment parts, etc. The molded body of the present embodiment is used as a vehicle part for a gasoline tank, a fuel, and the like. Fuel components such as pump modules, valves and gasoline tank flanges; Door components such as door locks, door handles, window regulators and speaker grills; seat belt slip rings, press buttons, etc. Seatbelt peripheral parts; Combi switch parts, switches, clips, etc .; Mechanical parts for inserting and removing the mechanical pencil tip, mechanical pencil core; Washbasins, drains, and drain plug opening / closing mechanism parts; Automatic Vending machine opening / closing lock mechanism, product discharge mechanism parts; cords for clothing Tops, adjusters, buttons; watering nozzles, watering hose connection joints; stair railings, and building materials that are the support for floor materials; disposable cameras, toys, fasteners, chains, conveyors, buckles, sports equipment, vending machines , Furniture, musical instruments, industrial machine parts (for example, electromagnetic equipment housings, roll materials, transfer arms, medical equipment members, etc.), general machine parts, automobile / railroad / vehicle parts (eg outer panels, chassis, aerodynamic members) , Seats, friction materials inside transmissions, etc., ship members (eg hulls, seats, etc.), aviation related parts (eg fuselage, main wing, tail wings, moving wings, fairings, cowls, doors, seats, interior materials, etc.), Spacecraft, artificial satellite members (motor case, main wing, structure, antenna, etc.), electronic / electrical parts (for example, personal computer case, mobile phone) Telephone housings, OA equipment, AV equipment, telephones, facsimiles, home appliances, toys, etc.), construction / civil engineering materials (for example, reinforcing bar substitute materials, truss structures, cables for suspension bridges), daily necessities, sports / leisure goods. (For example, golf club shafts, fishing rods, rackets for tennis and badminton), casing members for wind power generation, and containers / packaging members, for example, high-pressure containers filled with hydrogen gas such as those used in fuel cells. Can be a material for

  Further, when the member of the present embodiment is a resin composite film, it is suitable for reinforcing a laminated board in a printed wiring board. In addition, for example, generators, transformers, rectifiers, circuit breakers, insulating cylinders in control units, insulating levers, arc extinguishing plates, operating rods, insulating spacers, cases, wind tunnels, end bells, wind louvers, switch boxes in standard electrical products , Cases, crossbars, insulated shafts, fan blades, mechanical parts, transparent resin substrates, speaker diaphragms, eta diaphragms, TV screens, fluorescent light covers, antennas for communication equipment and aerospace, horn covers, radomes, cases, Mechanical parts, wiring boards, aircraft, rockets, satellite electronic devices, railway parts, ship parts, bathtubs, septic tanks, corrosion resistant equipment, chairs, safety caps, pipes, tank trucks, cooling towers, floating breakwaters, underground It can also be suitably used as an industrial part typified by a buried tank and container housing equipment.

<< Bonding / Adsorption >>
In the resin composition of the present embodiment, the (A) surface treatment agent, (B) polyurethane, and / or (E) binder component is combined with (D) cellulose nanofibers and / or (F) thermoplastic resin (for example, It may be ionic bond, chemical bond such as covalent bond) or adsorbed (for example, chemisorption or physical adsorption). A typical example of physical adsorption is that the adsorbate ((E) binder component and (A) surface treatment agent) works between the solid adsorbent ((D) cellulose nanofibers and / or (F) thermoplastic resin). This is a phenomenon in which the solid adsorbent is concentrated on the surface by the Van der Waals force. In general, the Van der Waals force is a remarkably weak interaction as compared with a chemical bond (ionic bond, covalent bond, etc.), and thus physically adsorbed molecules are easily desorbed by a physical operation such as heating and depressurization.

  The physical adsorption phenomenon can be easily confirmed by those skilled in the art by a general method. The confirmation method is not limited, but the following method can be exemplified.

  First, the surface analysis of a molded body made of the resin composition is performed. Confirm the components in the vicinity of the (F) thermoplastic resin or (D) cellulose nanofibers of the molded article by infrared spectroscopy analysis, time-of-flight secondary ion mass spectrometry, local pyrolysis GC-MS analysis, etc. Can be done.

  Next, the following operations are performed. The (F) thermoplastic resin of the resin composition is dissolved. The solution and (D) cellulose nanofibers are separated, and the cellulose nanofibers are isolated. The solution (that is, the solution in which the thermoplastic resin (F) is dissolved) is reprecipitated, the thermoplastic resin (F) is taken out, and then the solution is dried and solidified. The dried component is subjected to component analysis by various methods, and if the component matches the component detected by the surface analysis, it can be confirmed that the component is a component related to physical adsorption.

  On the other hand, chemical bonds are irreversible depending on physical operations, unlike physical adsorption. When (E) the binder component and (A) the surface treatment agent are chemically bonded to (D) cellulose nanofibers and / or (F) thermoplastic resin, (D) cellulose nanofibers and (F) thermoplastic resin The binder component (E) and the surface treatment agent (A) can be easily decomposed by thermal decomposition, hydrolysis, alkali decomposition or the like.

  The chemical bonding phenomenon can be easily confirmed by those skilled in the art by a general method. The confirmation method is not limited, but the following method can be exemplified.

First, the (F) thermoplastic resin and the (D) cellulose nanofibers of the resin composition are isolated. First, the thermoplastic resin (F) of the resin composition is dissolved. The solution and (D) cellulose nanofibers are separated to isolate the cellulose nanofibers. The solution (that is, the solution in which the thermoplastic resin (F) is dissolved) is reprecipitated, the thermoplastic resin (F) is taken out, and then the solution is dried and solidified. By directly analyzing the isolated (F) thermoplastic resin and (D) cellulose nanofibers by ¹ H-NMR or ¹³ C-NMR, the components chemically bonded can be confirmed.

Next, the following operations are performed. The isolated (D) cellulose nanofibers and (F) thermoplastic resin are pyrolyzed, hydrolyzed, alkali-decomposed, etc., and the decomposed components are analyzed by infrared spectroscopy, GC-MS analysis, LC-MS analysis. The structure of the component before decomposition is determined by analysis by time-of-flight secondary ion mass spectrometry, ¹ H-NMR, ¹³ C-NMR and the like. If the components detected before and after the decomposition match, it can be confirmed that the component is a chemical bond-related component.

≪Linear expansion coefficient≫
Since the resin composition of the present embodiment contains (D) cellulose nanofibers having an average fiber diameter of 1000 nm or less, it is possible to exhibit lower linear expansion properties than conventional molded products. Specifically, the linear expansion coefficient in the temperature range of 0 ° C. to 60 ° C. of the resin molded body is preferably 60 ppm / K or less. The linear expansion coefficient is more preferably 50 ppm / K or less, even more preferably 45 ppm / K or less, even more preferably 40 ppm / K or less, and most preferably 35 ppm / K or less. The lower limit of the linear expansion coefficient is not particularly limited, but from the viewpoint of ease of production, it is preferably 5 ppm / K, more preferably 10 ppm / K.

<< Paintability >>
Since the resin composition of the present embodiment contains (D) cellulose nanofibers, (A) surface treatment agent, and (B) polyurethane, it is possible to exhibit better coatability than conventional molded products. Although the cause of such excellent coating properties has not been elucidated, the coating components penetrate into the interface portion where (D) cellulose nanofibers, (A) surface treatment agent and (B) polyurethane are in close contact, It is presumed that the surface appearance is excellent.

The present invention will be further described based on examples, but the present invention is not limited to these examples.
≪Raw materials and evaluation method≫
The raw materials used and the evaluation method will be described below.

≪ (A) Surface treatment agent≫
(A-1) In a 2 L autoclave, 11 parts by mass of polypropylene oxide (Mn2000) and 0.6 parts by mass of KOH as a catalyst were added, and after nitrogen substitution, 100 parts by mass of polyethylene oxide (Mn9000) was added, and the mixture was mixed at 4 ° C at 160 ° C. It was introduced sequentially over time. After the reaction was completed, it was neutralized with 1.2 parts by mass of lactic acid to obtain a-1.
(A-2) Into a 2 L autoclave, 25 parts by mass of polypropylene oxide (Mn3250) and 0.6 part by mass of KOH as a catalyst were put, and after nitrogen substitution, 100 parts by mass of polyethylene oxide (Mn6375) was added, and the mixture was mixed at 160 ° C. for 4 hours. It was introduced sequentially over time. After the reaction was completed, it was neutralized with 1.2 parts by mass of lactic acid to obtain a-2.
(A-3) In a 2 L autoclave, 28 parts by mass of polypropylene oxide (Mn1750) and 0.6 part by mass of KOH as a catalyst were added, and after nitrogen substitution, 100 parts by mass of polyethylene oxide (Mn3125) was added, and the mixture was mixed at 4 ° C at 160 ° C. It was introduced sequentially over time. After the reaction was completed, it was neutralized with 1.2 parts by mass of lactic acid to obtain a-3.
(A-4) 130 parts by mass of polypropylene oxide (Mn2000) and 0.6 part by mass of KOH as a catalyst were put into a 2 L autoclave, and after nitrogen substitution, 100 parts by mass of polyethylene oxide (Mn750) was added, and the mixture was mixed at 4 ° C at 160 ° C. It was introduced sequentially over time. After the reaction was completed, it was neutralized with 1.2 parts by mass of lactic acid to obtain a-4.
(A-5) 180 parts by mass of polypropylene oxide (Mn2000) and 0.6 part by mass of KOH as a catalyst were put into a 2 L autoclave, and after nitrogen substitution, 100 parts by mass of polyethylene oxide (Mn550) was added, and the mixture was mixed at 4 ° C at 160 ° C. It was introduced sequentially over time. After the reaction was completed, it was neutralized with 1.2 parts by mass of lactic acid to obtain a-5.
(A-6) Into a 2 L autoclave, 270 parts by mass of polypropylene oxide (Mn1750) and 0.6 part by mass of KOH as a catalyst were added, and after nitrogen substitution, 100 parts by mass of polyethylene oxide (Mn325) was added, and the mixture was mixed at 4 ° C. at 160 ° C. It was introduced sequentially over time. After the reaction was completed, it was neutralized with 1.2 parts by mass of lactic acid to obtain a-6.

(A-7) In a 2 L autoclave, 140 parts by mass of polypropylene oxide (Mn1000) and 0.6 parts by mass of KOH as a catalyst were added, and after nitrogen substitution, 100 parts by mass of polyethylene oxide (Mn350) was added, and the mixture was mixed at 4 ° C at 160 ° C. It was introduced sequentially over time. After the reaction was completed, it was neutralized with 1.2 parts by mass of lactic acid to obtain a-7.
(A-8) 700 parts by mass of polypropylene oxide (Mn1750) and 0.6 parts by mass of KOH as a catalyst were placed in a 2 L autoclave, and after nitrogen substitution, 100 parts by mass of polyethylene oxide (Mn125) were added, and the mixture was heated at 160 ° C. for 4 hours. It was introduced sequentially over time. After the reaction was completed, it was neutralized with 1.2 parts by mass of lactic acid to obtain a-8.
(A-9) Polyethylene oxide (Mn31000) was used.
(A-10) Polyethylene oxide (Mn150) was used.
(A-11) 100 parts by mass of glycerin (Mn92) and 0.6 parts by mass of KOH as a catalyst were placed in a 2 L autoclave and nitrogen substitution was carried out, and then 340 parts by mass of polyethylene oxide (Mn325) were successively added at 160 ° C. for 4 hours. Introduced. After completion of the reaction, 680 parts by mass of polypropylene oxide (Mn650) was added, and the mixture was successively introduced at 160 ° C. over 4 hours. After the reaction was completed, it was neutralized with 1.2 parts by mass of lactic acid to obtain a-11.
(A-12) 100 parts by mass of pentaerythritol (Mn136) and 0.6 parts by mass of KOH as a catalyst were placed in a 2 L autoclave and the atmosphere was replaced with nitrogen. Then, 330 parts by mass of polyethylene oxide (Mn450) was added at 160 ° C. for 4 hours. Introduced sequentially. After completion of the reaction, 660 parts by mass of polypropylene oxide (Mn900) was added, and the mixture was successively introduced at 160 ° C. for 4 hours. After the reaction was completed, it was neutralized with 1.2 parts by mass of lactic acid to obtain a-12.

<(A) Measurement of molecular weight of surface treatment agent>
For each surface treatment agent, a molecular weight of 10,000 or more was measured by GPC, and a molecular weight of less than 10,000 was measured by HPLC under the following conditions.
Each surface treatment agent was measured under the following conditions.

[GPC measurement]
Those that were solid at room temperature were heated to a temperature equal to or higher than the melting point to melt them, and then dissolved in water for measurement.
Device name: HLC-8320GPC EcoSEC (manufactured by Tosoh Corporation)
Column: Shodex GPC KD-802 + KD-80 (Showa Denko KK)
Eluent: 0.01M LiBr in DMF
Flow rate: 1.0 mL / min
Detector: RI
Measurement temperature: 50 ° C

[HPLC measurement]
Those that were solid at room temperature were heated to a temperature equal to or higher than the melting point to melt them, and then dissolved in water for measurement.
Device name: HP-1260 (Agilent Technology Co., Ltd.)
Column: TSKgel ODS-80Ts (manufactured by Tosoh Corporation)
Mobile phase: Water / acetonitrile Solvent gradient with mobile phase Detector: Evaporative light scattering detector (ELSD)
Measurement temperature: 40 ° C
Flow rate: 1 mL / min
Sample concentration: 1 mg / mL
Injection volume: 10 μL

<(A) Melting point of surface treatment agent>
Those that were solid at room temperature were heated to a temperature equal to or higher than the melting point, melted, and then enclosed in an aluminum pan for measurement.
Device name: DSC8500 manufactured by Perkin Elmer Co., Ltd. Measurement temperature: -60 to 100 ° C

<Cloud point of (A) surface treatment agent>
Those that were solid at room temperature were heated to a temperature above the melting point to melt them, and then dissolved in water to give samples.

Device name: SV-10A manufactured by A & D Co., Ltd. Measurement concentration: 0.5% by mass, 1.0% by mass, 5% by mass
Measurement temperature: 0 to 90 ° C
Those which did not show a cloud point by the above method were sealed in a glass-made visible and airtight container. After that, the temperature was raised, and the cloudy point of the deposited aqueous solution was visually confirmed and the cloudy point was measured.

≪ (B) Polyurethane≫
The polyurethanes listed in Table 2 were used.

<< (C) Water-soluble organic solvent >>
The solvents listed in Table 3 were used. For the relative permittivity of c-2, the numbers described in Ip 770 to 777, revised edition, 5th edition, edited by Chemical Society of Japan, were used. c-1 and c-3 were measured using the HEWLETT PACKARD company LCR meter HP4284A (liquid measuring electrode HP 16452A, solid measuring electrode HP 16451B).

≪ (D) Cellulose nanofiber≫
(D-1) Cellulose A
After cutting the linter pulp, it is heated in hot water at 120 ° C. or higher for 3 hours using an autoclave, and the purified pulp from which the hemicellulose portion has been removed is squeezed and the solid content in pure water becomes 1.5% by mass. As described above, the fibers were highly shortened and fibrillated by beating, and then defibrated with a high pressure homogenizer (operating pressure: 85 MPa, 10 times treatment) at the same concentration to obtain defibrated cellulose. Here, in the beating process, a disc refiner is used, and a beating blade having a high defibration function (hereinafter referred to as a defibration blade) is treated for 2.5 hours with a beating blade having a high cutting function (hereinafter referred to as a cutting blade). Cellulose A was obtained by further beating for 2 hours.
(D-2) Cellulose B
Cellulose B was produced by the method described in [0108] Example 1 of WO 2017/159823.

<Polymerization degree of cellulose component>
It was measured by a reduced specific viscosity method using a copper ethylenediamine solution specified in the crystalline cellulose confirmation test (3) of "14th Revised Japanese Pharmacopoeia" (published by Hirokawa Shoten).
<Crystal form and crystallinity of cellulose component>
An X-ray diffractometer (manufactured by Rigaku Corporation, multipurpose X-ray diffractometer) was used to measure a diffraction pattern (at room temperature) by the powder method, and the crystallinity was calculated by the Segal method. The crystal form was also measured from the obtained X-ray diffraction image.

<L / D of cellulose component>
The cellulose component was made into a pure water suspension at a concentration of 1% by mass, and a high shear homogenizer (manufactured by Nippon Seiki Co., Ltd., trade name “Excel Auto Homogenizer ED-7”, processing condition: rotation speed 15,000 rpm × 5 minutes). The water dispersion dispersed in 1. was diluted with pure water to 0.1 to 0.5% by mass, cast on mica, and air-dried to obtain when measured with an atomic force microscope (AFM). The ratio (L / D) when the major axis (L) and the minor axis (D) of the particle image to be formed was calculated and calculated as the average value of 100 to 150 particles.

<Average diameter of cellulose component>
Cellulose component as solid content of 40% by mass in a planetary mixer (manufactured by Shinagawa Kogyo Co., Ltd., trade name "5DM-03-R", stirring blade is hook type) at 126 rpm at room temperature and atmospheric pressure for 30 minutes. Kneaded Then, a pure water suspension having a solid content of 0.5% by mass was prepared, and a high shear homogenizer (manufactured by Nippon Seiki Co., Ltd., trade name "Excel Auto Homogenizer ED-7", processing condition: rotation speed 15,000 rpm. X 5 minutes) and then centrifuged (Kubota Shoji Co., Ltd., trade name "6800 type centrifuge", rotor type RA-400 type, processing conditions: centrifugal force of 39200 m ² / s for 10 minutes Was collected, and the supernatant was centrifuged at 116000 m ² / s for 45 minutes). Volume obtained by laser diffraction / scattering particle size distribution analyzer (manufactured by Horiba, Ltd., trade name “LA-910”, ultrasonic treatment 1 minute, refractive index 1.20) using the supernatant after centrifugation. The cumulative 50% particle size (volume average particle size) in the frequency particle size distribution was measured, and this value was taken as the average size.

≪ (F) Thermoplastic resin≫
(F-1) UBE Nylon 1013B manufactured by Ube Industries, Ltd.
(F-2) Prime Polymer Co., Ltd. Prime Polypro J105G
(F-3) Tenac TM 4520 manufactured by Asahi Kasei Corporation

<< Production-1 Dispersion >>
(A) The surface treatment agent was added to distilled water in an environment of 20 ° C., placed in a closed container and allowed to stand overnight to dissolve. The next day, it was confirmed that the solution was uniform, and (B) polyurethane was added to the obtained (A) surface treatment agent aqueous solution, and the mixture was stirred for 10 minutes using a high power general-purpose stirrer BLh3000 manufactured by Shinto Scientific Co., Ltd. A uniform dispersion was obtained.

<< Production-2 Cellulose Nanofiber Aqueous Dispersion >>
The dispersion liquid obtained in the previous production was put into a cellulose nanofiber slurry (solid content: 10 to 20 wt%), and stirred for 10 minutes using a high power general-purpose stirrer BLh3000 manufactured by Shinto Scientific Co., Ltd. to obtain uniform cellulose nanofibers. A water-containing dispersion was obtained.

<< Production-3 Dried Cellulose Nanofiber >>
The aqueous dispersion of cellulose nanofibers obtained in the above production was dried under reduced pressure at 40 ° C. for 1 hour while stirring using ACM-5LVT manufactured by Kodaira Seisakusho Co., Ltd. to obtain a uniform crumb-like lump. This was dried using Yamato Scientific Co., Ltd. Inert Oven DN43HI in a nitrogen atmosphere at 120 ° C. for 24 hours to obtain a dried cellulose nanofiber.

<< Manufacturing-4 Resin composition >>
Using a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd. TEM-26SS extruder (L / D = 48, with vent), the polyamide-based material is 260 ° C., the polypropylene-based material is 190 ° C., and the polyoxymethylene-based material is The cylinder temperature is set to 200 ° C., (F) the thermoplastic resin is supplied from the extruder main throat part from the quantitative feeder, and the cellulose nanofiber-containing aqueous dispersion or the dried cellulose nanofiber is supplied from the extruder side part to the quantitative feeder. The resin kneaded product was extruded in a strand form under the conditions of an extrusion rate of 15 kg / hour and a screw rotation speed of 250 rpm, quenched by a strand bath, and cut by a strand cutter to obtain a pellet-shaped resin composition.

≪Manufacture-5 molded product≫
Using an injection molding machine, a multipurpose test piece conforming to ISO294-3 was molded.
Polyamide-based material: Conditions based on JIS K6920-2 Polypropylene-based material: Conditions based on JIS K6921-2 Polyoxymethylene-based material: Conditions based on JIS K7364-2 Raw material resin (that is, thermoplastic resin alone) and resin composition For each of the products (that is, the cellulose nanofiber resin composition), the tensile yield strength and tensile elongation at break were measured according to ISO527, and the flexural modulus was measured according to ISO179.
Since the polyamide-based material changes due to moisture absorption, it was stored in an aluminum moisture-proof bag immediately after molding to suppress moisture absorption.

≪Characteristics evaluation conditions / mechanical properties measurement≫
<Dispersion liquid visual inspection>
After the stirring of the dispersion liquid obtained in Production-1 was finished, the dispersion liquid was placed in a 20 ml Laboran screw tube bottle manufactured by As One Co., Ltd., and the color of the dispersion liquid was observed.
<Dispersion sedimentation inspection>
After completion of stirring the dispersion liquid obtained in Production-1, the dispersion liquid was placed in a 20 ml Laboran screw tube bottle manufactured by As One Co., Ltd., and the dispersion liquid was allowed to stand for 48 hours. The appearance of the sedimentation of the dispersion after standing was visually inspected.
A: Evenly dispersed and no sedimentation was observed.
B: Dispersed, but some sedimentation is observed.
C: Sedimentation is confirmed.

<Cellulose nanofiber water-containing dispersion dilution inspection>
The water-containing dispersion of cellulose nanofibers obtained in Production-2 was placed in a 20 ml Laboran screw tube bottle manufactured by As One Co., Ltd. and diluted with distilled water to a cellulose concentration of 0.1% by mass. After stirring to make a uniform aqueous dispersion of cellulose nanofibers, one drop was dropped on a slide glass, and a cover glass was placed on the drop. The cover glass was pressed, and the water-containing dispersion liquid of cellulose nanofibers protruding from the cover glass was removed by using Kimwipe manufactured by Nippon Paper Crecia Co., Ltd. The aqueous dispersion of cellulose nanofibers between the slide glass and the cover glass was visually observed using VHX1000 and VH-Z100UR manufactured by KEYENCE CORPORATION.
A: The particles are uniformly dispersed and no aggregation is observed.
B: Although dispersed, some aggregation is observed.
C: Aggregation is confirmed.

<Redispersion test of dried cellulose nanofibers>
The dried cellulose nanofibers obtained in Production-3 were put in a 20 ml Laboran screw tube bottle manufactured by As One Co., Ltd., and diluted with distilled water to a cellulose concentration of 1% by mass. After standing for 24 hours, the mixture was stirred again to obtain a uniform aqueous dispersion of cellulose nanofibers, which was then visually inspected.
A: Evenly dispersed.
B: Although dispersed, some aggregation is observed.
C: Aggregation is confirmed.

<Resin molded product linear expansion coefficient>
A cubic sample having a length of 4 mm, a width of 4 mm, and a length of 4 mm was cut out from a central portion of the multipurpose test piece with a precision cutting saw, measured at a measurement temperature range of -40 to 100 ° C in accordance with ISO11359-2, and 0 ° C to The expansion coefficient between 60 ° C was calculated. It was evaluated that the lower the linear expansion coefficient, the better the dispersibility of the cellulose nanofibers in the resin.

<Resin molding wear resistance>
Regarding the multipurpose test piece obtained in << Manufacture-5 >>, a reciprocating friction wear tester (AFT-15MS type manufactured by Toyo Seimitsu Co., Ltd.) was used, and a SUS304 test piece (sphere having a diameter of 5 mm) was used as a mating material. A sliding test was carried out at a linear velocity of 50 mm / sec, a reciprocating distance of 50 mm, a load of 9.8 N, a reciprocating number of 10,000 times, a temperature of 23 ° C. and a humidity of 50%. The amount of wear was determined by measuring the amount of wear (wear depth) of the sample after the sliding test using a confocal microscope (OPTELICS (registered trademark) H1200, manufactured by Lasertec Corporation). The wear depth was the average of the numerical values measured at n = 4. The measurement points are the points spaced 12.5 mm apart from the end of the wear mark. It was also evaluated that the lower the wear depth, the better the wear characteristics.

<Resin molding paintability>
The multi-purpose test piece obtained in << Manufacture-5 >> is coated with Aquaplanit # 240 (black) manufactured by Dainippon Paint Co., Ltd. in a spray gun (W-300-141G) for water-based paint. Then, it was dried at 80 ° C. for 30 minutes. After drying, it was left standing in a constant temperature and humidity environment of 23 ° C. and 50% for 48 hours, and a visual appearance inspection was performed.
A: Surface gloss and excellent appearance.
B: The surface gloss is partly smeared, but the appearance is excellent.
C: Some appearance defects (steps, craters, whitening, roughening, scratches, repellants, blisters, cracks) are present.
D: The surface appearance has a lot of roughness.
E: Roughness is recognized on the surface appearance and cracks are present.

[Dispersion Examples 1-1 to 1-20 and Comparative Examples 1-1 to 1-6]
Each of the dispersions was obtained by using the surface treatment agent (A) and the polyurethane (B) in the proportions shown in Table 5 by the method described in Production-1. The obtained dispersion liquid was evaluated according to the above-described evaluation method.

[Cellulose Aqueous Dispersion Examples 2-1 to 2-20-2 and Comparative Examples 2-1 to 2-6]
Using the dispersions obtained in the above Examples (described in Table 5), water-containing cellulose dispersions (described in Table 6) were obtained by the method described in Production-2. The obtained cellulose hydrous dispersion was evaluated according to the above-described evaluation method.

[Cellulose Dry Body Examples 3-1 to 3-20-2 and Comparative Examples 3-1 to 3-6]
Using the aqueous cellulose dispersion (described in Table 6) obtained in the previous example, each dried cellulose product (described in Table 7) was obtained by the method described in Production-3. The obtained dried cellulose product was evaluated according to the evaluation method described above. In Example 3-4-2, the cellulose nanofiber-containing aqueous dispersion of Example 2-4 obtained in the previous production was stirred at 40 ° C. at 0.4 ° C. with stirring using ACM-5LVT manufactured by Kodaira Seisakusho. After drying under reduced pressure for 5 hours, a uniform crumb-like mass was obtained. This was dried for 5 hours in a nitrogen atmosphere at 120 ° C. using Inert Oven DN43HI manufactured by Yamato Scientific Co., Ltd. to obtain a dried cellulose nanofiber. In Example 3-4-3, the cellulose nanofiber-containing aqueous dispersion of Example 2-4 obtained in the previous production was stirred at 40 ° C. at 0.4 ° C. with stirring using ACM-5LVT manufactured by Kodaira Seisakusho. After drying under reduced pressure for 5 hours, a uniform crumb-like mass was obtained. This was dried for 2 hours at 120 ° C. in a nitrogen atmosphere using Inert Oven DN43HI manufactured by Yamato Scientific Co., Ltd. to obtain a dried cellulose nanofiber.

[Resin Compositions Examples 4-1 to 4-63 and Comparative Examples 4-1 to 4-10]
Using the aqueous cellulose dispersion (described in Table 6) and the dried cellulose product (described in Table 7) obtained in the above Examples, a resin composition (described in Tables 8 to 18) was obtained by the method described in Production-4. It was The obtained composition was molded by the method described in Production-5. Examples and comparative examples described in Tables 6 and 7 (Examples 2-1 to 2-20-2 and Comparative examples 2-1 to 2-6, Examples 3-1 to 3-20-2 and Comparative example 3) -1 to 3-6) not shown in Tables 8 to 18 were produced by the method described in Production 1 to 3 except that (F) the thermoplastic resin was used in the proportions shown in each table. . Then, a composition and a molded product were obtained by the methods described in Production-4 and -5. In Examples 4-58 to 4-63 of Table 18, (B) polyurethane and (F) thermoplastic resin were stirred and dried to make them uniform, and then the mixture was supplied from the main throat section of the extruder by a quantitative feeder, (A) A water-containing dispersion of cellulose nanofibers containing a surface treatment agent is supplied from the side of the extruder using a quantitative feeder, and the resin kneaded product is extruded in a strand shape under the conditions of an extrusion rate of 15 kg / hour and a screw rotation speed of 250 rpm. Then, it was quenched with a strand bath and cut with a strand cutter to obtain a pellet-shaped resin composition. Then, a composition and a molded product were obtained by the method described in Production-5. Each of the above-mentioned molded products was evaluated according to the evaluation method described above.

  As described above, it is understood that the cellulose nanofiber dispersion liquid can be dispersed without agglomerating the cellulose nanofibers by mixing each component in an appropriate type and amount. Further, it can be seen that the aqueous dispersion of cellulose nanofibers and the dried cellulose nanofibers can be easily redispersed in water and have excellent dispersibility in resin. It can be seen that the resin composition and the resin molded article are excellent in coating properties and abrasion resistance in practical use while giving excellent mechanical properties and thermal properties.

  The dispersion according to the present invention can be dispersed without agglomerating the cellulose nanofibers, and the cellulose nanofiber-containing aqueous dispersion and the dried cellulose nanofibers can be easily redispersed in water and have excellent dispersibility in a resin. Since the resin composition and the resin molded article have excellent coating properties and wear resistance in actual applications while giving excellent mechanical properties and thermal properties, they are suitably applied to various applications where these properties are required. It

Claims (42)

(A) a surface treating agent which is a water-soluble polymer having a hydrophilic segment and a hydrophobic segment and having a number average molecular weight of 200 to 30,000,
(B) polyurethane and water,
A dispersion liquid containing.   The dispersion according to claim 1, further comprising (C) a water-soluble organic solvent. (A) a surface treating agent which is a water-soluble polymer having a hydrophilic segment and a hydrophobic segment and having a number average molecular weight of 200 to 30,000,
(B) polyurethane,
(D) Cellulose nanofibers having an average fiber diameter of 1000 nm or less, and water,
A water-containing dispersion of cellulose nanofibers. (A) 0.1 to 100 parts by mass of the surface treatment agent,
(B) 0.1 to 100 parts by mass of polyurethane,
The cellulose nanofiber water-containing dispersion according to claim 3, comprising (D) 100 parts by mass of cellulose nanofiber, and water.   The cellulose nanofiber water-containing dispersion liquid according to claim 3 or 4, wherein the (A) surface treatment agent has an HLB value of 0.1 or more and less than 8.0.   The cellulose nanofiber aqueous dispersion according to any one of claims 3 to 5, wherein the surface treatment agent (A) has a cloud point of 10 ° C or higher.   The cellulose nanofiber aqueous dispersion according to any one of claims 3 to 6, wherein the hydrophilic segment contains a polyoxyethylene block and the hydrophobic segment contains a polyoxypropylene block.   The cellulose nanoparticle according to any one of claims 3 to 7, wherein the molecular structure of the surface treatment agent (A) is one selected from an ABA-type triblock structure, a three-branched structure, and a four-branched structure. Fiber-containing water dispersion.   The cellulose nanofiber aqueous dispersion according to claim 8, wherein the molecular structure of the surface treatment agent (A) is a triblock structure of hydrophilic segment-hydrophobic segment-hydrophilic segment.   The cellulose nanofiber according to any one of claims 3 to 9, wherein a molecular weight ratio of the hydrophilic segment and the hydrophobic segment (hydrophobic segment molecular weight / hydrophilic segment molecular weight) is 0.1 to 3. Aqueous dispersion.   The cellulose nanofiber aqueous dispersion according to any one of claims 3 to 10, wherein the surface treatment agent (A) is a nonionic surfactant.   The aqueous dispersion of cellulose nanofibers according to claim 11, wherein the surface treatment agent (A) is an ether type nonionic surfactant.   The cellulose nanofiber aqueous dispersion according to any one of claims 3 to 12, wherein the polyurethane (B) has a soft segment and a hard segment.   The cellulose nanofiber aqueous dispersion according to any one of claims 3 to 13, wherein the (B) polyurethane is a modified polyurethane having a blocked isocyanate group.   The cellulose nanofiber aqueous dispersion according to any one of claims 3 to 14, further comprising (C) a water-soluble organic solvent.   The aqueous dispersion of cellulose nanofibers according to claim 3, further comprising (E) a binder component.   A dried cellulose nanofiber, which is a dried product of the aqueous dispersion of cellulose nanofiber according to any one of claims 3 to 16. A water-containing dispersion of cellulose nanofibers according to any one of claims 3 to 16, or a dried cellulose nanofiber according to claim 17, and (F) a thermoplastic resin.
A cellulose nanofiber composition comprising: (A) 0.1 to 50% by mass of a surface treatment agent which is a water-soluble polymer having a hydrophilic segment and a hydrophobic segment and a number average molecular weight of 200 to 30,000;
(B) 0.1 to 50% by mass of polyurethane,
(D) 1 to 50% by mass of cellulose nanofibers having an average fiber diameter of 1000 nm or less, and (F) 1 to 98.8% by mass of a thermoplastic resin,
A cellulose nanofiber resin composition containing the same.   The cellulose nanofiber resin composition according to claim 18 or 19, wherein the surface treating agent (A) has an HLB value of 0.1 or more and less than 8.0.   The cellulose nanofiber resin composition according to any one of claims 18 to 20, wherein the surface treatment agent (A) has a cloud point of 10 ° C or higher.   The cellulose nanofiber resin composition according to any one of claims 18 to 21, wherein the hydrophilic segment contains a polyoxyethylene block and the hydrophobic segment contains a polyoxypropylene block.   The cellulose nanoparticle according to any one of claims 18 to 22, wherein the molecular structure of the surface treatment agent (A) is one selected from an ABA type triblock structure, a three-branched structure, and a four-branched structure. Fiber resin composition.   The cellulose nanofiber resin composition according to claim 23, wherein the molecular structure of the surface treatment agent (A) is a triblock structure of hydrophilic segment-hydrophobic segment-hydrophilic segment.   The cellulose nanofiber according to any one of claims 18 to 24, wherein a molecular weight ratio of the hydrophilic segment and the hydrophobic segment (hydrophobic segment molecular weight / hydrophilic segment molecular weight) is 0.1 to 3. Resin composition.   The cellulose nanofiber resin composition according to any one of claims 18 to 25, wherein the surface treatment agent (A) is a nonionic surfactant.   The cellulose nanofiber resin composition according to claim 26, wherein the surface treating agent (A) is an ether type nonionic surfactant. (B) polyurethane has a soft segment and a hard segment,
The cellulose nanofiber resin composition according to any one of claims 18 to 27, wherein (B) polyurethane is bonded to (D) cellulose nanofiber and / or (F) thermoplastic resin. (F) 0.1 to 200 parts by mass of the surface treatment agent and (D) 1 to 200 parts by mass of the cellulose nanofiber, relative to 100 parts by mass of the thermoplastic resin,
The cellulose nanofiber resin composition according to any one of claims 18 to 28, wherein the (A) surface treatment agent has a number average molecular weight of 200 to 25,000.   The cellulose nanofiber resin composition according to any one of claims 18 to 29, which further comprises water and is in the form of a water-containing dispersion.   The cellulose nanofiber resin composition according to claim 30, further comprising (C) a water-soluble organic solvent.   The cellulose nanofiber resin composition according to any one of claims 18 to 29, which is in the form of a dried product.   The cellulose nanofiber resin composition according to any one of claims 18 to 32, further comprising (E) a binder component.   (D) 0.1 to 100 parts by mass of the surface treatment agent (A) and 0.1 to 100 parts by mass of the polyurethane component (B) and the binder component (E) based on 100 parts by mass of the cellulose nanofibers. The cellulose nanofiber resin composition according to any one of claims 18 to 33.   The cellulose nanofiber resin composition according to claim 33 or 34, wherein the binder component (E) is bound or adsorbed to the cellulose nanofiber (D).   The cellulose nanofiber resin composition according to any one of claims 33 to 35, wherein the binder component (E) is bound or adsorbed to the thermoplastic resin (F).   (F) The thermoplastic resin comprises a polyolefin resin, a polyamide resin, a polyester resin, a polyacetal resin, a polyacrylic resin, a polyphenylene ether resin, a polyphenylene sulfide resin, and a mixture of any two or more thereof. The cellulose nanofiber resin composition according to any one of claims 18 to 36, which is selected from the group. From the mass content a of (D) cellulose nanofibers in the cellulose nanofiber resin composition, the tensile yield strength b of the resin composition, and the tensile yield strength c of the thermoplastic resin (F), the following formula (1) ):
Tensile yield strength improvement rate = (b / c-1) / a (1)
The cellulose nanofiber resin composition according to any one of claims 18 to 37, wherein the tensile yield strength improvement rate obtained according to the above is greater than 1.0. From the mass content a of (D) cellulose nanofibers in the cellulose nanofiber resin composition, the flexural modulus d of the resin composition, and the flexural modulus e of the (F) thermoplastic resin, the following formula (2) ):
Flexural modulus improvement rate = (d / e-1) / a
The cellulose nanofiber resin composition according to any one of claims 18 to 38, wherein the flexural modulus improvement rate obtained according to the above is greater than 3.0.   A resin molded body formed from the cellulose nanofiber resin composition according to any one of claims 18 to 39. A method for producing the cellulose nanofiber resin composition according to any one of claims 18 to 39,
At least (A) a surface treating agent which is a water-soluble polymer having a hydrophilic segment and a hydrophobic segment and a number average molecular weight of 200 to 30,000, (B) polyurethane, (D) cellulose nanofiber, and (F) ) A method comprising kneading with a thermoplastic resin. A method for producing the cellulose nanofiber resin composition according to any one of claims 18 to 39,
Preparing the cellulose nanofiber water-containing aqueous dispersion according to any one of claims 3 to 16 or the cellulose nanofiber dried body according to claim 17, and the cellulose nanofiber water-containing dispersion or the cellulose nanofibers. Kneading the dried material and at least (F) a thermoplastic resin,
Including the method.