JP7266995B2 - Cellulose nanofiber composition - Google Patents

Description

The present invention relates to cellulose nanofiber compositions.

Thermoplastic resins are light and have excellent processability, so they are widely used in various fields such as automobile parts, electric/electronic parts, office equipment housings, and precision parts. However, resins alone are often insufficient in mechanical properties, slidability, thermal stability, dimensional stability, etc., and composites of resins and various inorganic materials are generally used.

A resin composition in which a thermoplastic resin is reinforced with a reinforcing material, which is an inorganic filler such as glass fiber, carbon fiber, talc, or clay, has a high specific gravity, so there is a problem that the weight of the resulting resin molding becomes large. Therefore, in recent years, cellulose, which has a low environmental impact, has been used as a new reinforcing material for resins.

Cellulose is known to have a high modulus of elasticity comparable to that of aramid fibers and a coefficient of linear expansion lower than that of glass fibers. In addition, 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/cm ³ ) and talc (density 2.7 g/cm 3 ) are commonly used as reinforcing materials for thermoplastic resins. cm ³ ), it is an overwhelmingly light material.

There are a wide variety of cellulose materials, including those made from trees, as well as those made from hemp, cotton, kenaf, cassava, and the like. Furthermore, bacterial cellulose and the like typified by nata de coco are also known. Natural resources that serve as raw materials for these materials exist in large quantities on the earth, and for effective use of these resources, a technique for utilizing cellulose as a filler in resins is attracting attention.

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

In order to incorporate CNF into resin, it is necessary to dry and powderize CNF, but in the process of separating CNF from water, the finely dispersed state becomes a strong aggregate, making it difficult to redisperse. be. This cohesive force is expressed by hydrogen bonding of the hydroxyl groups of cellulose, and is said to be very strong.

Therefore, in order to sufficiently express the performance of CNF, it is necessary to relax the hydrogen bonding due to the hydroxyl groups of cellulose. Moreover, even if relaxation of hydrogen bonds can be achieved, it is difficult to maintain the fibrillated state (nanometer size (that is, less than 1 μm)) in the resin.

Therefore, it is generally known to use a surface treatment agent to dry the CNF and disperse it in the resin. It is known that CNF alone and surface treatment agent alone have heat resistance when dried in an air atmosphere at, for example, 150°C. For this reason, a technique in which the surface of CNF is coated with a surface treatment agent and dried at around 150° C. is generally adopted. However, the higher the coatability of the surface treatment agent, the thinner the surface treatment agent is spread by CNF, resulting in an increase in surface area. On the other hand, it is generally known that the susceptibility to oxidative degradation changes dramatically when the surface area is significantly increased (as in the relationship between iron and steel wool, for example). That is, a new problem has arisen that the surface area of the surface treatment agent is increased and the heat resistance is lowered by drying the surface treatment agent in a composite with CNF. The extent to which this problem occurs varies depending on the surface area of CNF and the easiness of coating with a surface treatment agent, and is directly linked to the extent of variation in the quality of the dry CNF powder and the variation in performance of the CNF resin composition. Therefore, it is difficult to add the dried CNF to the resin and finely disperse the CNF to exhibit excellent performance.

Compositions in which these CNFs are used as fillers and are composited with various resins have been proposed. For example, Patent Literatures 1 and 2 describe techniques for compounding cellulose and resin using a dispersant.

Japanese Patent No. 5797129 WO2018/123150

Patent Document 1 describes a technique for dispersing cellulose nanofibers using an ether-type nonionic surfactant having an HLB value of 8 to 13, and by adding a surfactant to a low-concentration CNF slurry, even after stirring The excellent dispersibility of CNF for a certain period of time and the use of polypropylene are described. However, Patent Document 1 does not mention the thermal stability of the dried cellulose nanofibers. In addition, the dispersion obtained by the technique described in Patent Document 1 is such that lumps of cellulose nanofibers can be confirmed even by X-ray CT, so the effect of improving mechanical properties and thermal properties is very small. Moreover, Patent Document 1 does not mention the slidability, odor resistance, and moldability of thermoplastic resins.

Patent document 2 describes a technique for dispersing cellulose using an organic component, but even patent document 2 does not mention the thermal stability of dried cellulose nanofibers. The effect of improving the mechanical properties and thermal properties obtained by the technique described in Patent Document 2 is very small, and Patent Document 2 does not mention the slidability, odor resistance, and moldability of thermoplastic resins. . Therefore, the techniques described in these patent documents face the problem that they are not suitable for practical use.

That is, at present, a sufficient amount of cellulose is finely dispersed in the resin composition to develop the desired mechanical properties of the resin molded body, and high mechanical properties and thermal properties (especially reduced thermal expansion) cellulose nanofiber composition (e.g., cellulose nanofiber water-containing dispersion and cellulose nanofiber dry body) has not been obtained.

The present invention solves the above problems, and can be obtained as a water-containing dispersion in which cellulose nanofibers can be dispersed without aggregation in a system using water as a main medium by a simple method, and has excellent heat resistance, Cellulose nanofibers, which have excellent dispersibility in water, organic solvents and resins, and which can be obtained as a dry body that imparts sufficient mechanical properties, thermal properties, abrasion resistance and excellent moldability to resin compositions. It is intended to provide a composition.

In order to solve the above-mentioned problems, the present inventors have made intensive studies and found that the above-mentioned problems can be solved by using cellulose nanofibers, a specific surface treatment agent, and a specific antioxidant. This discovery led to the completion of the present invention.

That is, the present invention includes the following aspects.
[1] A cellulose nanofiber composition containing (A) cellulose nanofibers, (B) a surface treatment agent, and (C) an antioxidant.
[2] The cellulose nanofiber composition according to Aspect 1 above, which contains 0.01 to 100 parts by mass of (C) antioxidant with respect to 100 parts by mass of (B) surface treating agent.
[3] The cellulose nanofiber composition according to Aspect 1 or 2 above, wherein (B) the surface treatment agent has a number average molecular weight of 200 to 30,000.
[4] The cellulose nanofiber composition according to any one of the above aspects 1 to 3, wherein (B) the surface treating agent has a cloud point of 10°C or higher.
[5] The cellulose nanofiber composition according to any one of aspects 1 to 4 above, wherein (A) contains 0.1 to 100 parts by mass of a surface treatment agent with respect to 100 parts by mass of cellulose nanofibers.
[6] The cellulose nanofiber composition according to any one of the above aspects 1 to 5, wherein (B) the HLB value of the surface treatment agent is 0.1 or more and less than 12.
[7] Aspects 1 to 6 above, wherein (C) the antioxidant is selected from the group consisting of a hindered phenol antioxidant, a sulfur antioxidant, and a phosphorus antioxidant. cellulose nanofiber composition.
[8] The cellulose nanofiber composition according to any one of the above aspects 1 to 7, wherein (B) the surface treating agent is a nonionic surfactant.
[9] The cellulose nanofiber composition according to any one of the above aspects 1 to 8, wherein (B) the surface treating agent has a PEG block as a hydrophilic group and a PPG block as a hydrophobic group in the molecule.
[10] (B) The cellulose according to any one of aspects 1 to 9, wherein the molecular structure of the surface treatment agent is one selected from an ABA-type triblock structure, a tri-branched structure, and a tetra-branched structure. Nanofiber composition.
[11] The cellulose nanofiber composition according to any one of the above aspects 1 to 10, which is in the form of a water-containing dispersion.
[12] The cellulose nanofiber composition according to aspect 11 above, further comprising (D) a water-soluble organic solvent.
[13] The cellulose nanofiber composition according to any one of the above aspects 1 to 10, which is in the form of a dry body.
[14] A cellulose nanofiber resin composition comprising (E) a thermoplastic resin, (A) cellulose nanofibers, (B) a surface treatment agent, and (C) an antioxidant.
[15] The cellulose nanofiber resin composition according to aspect 14 above, further comprising water.
[16] (E) 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 these. 16. The cellulose nanofiber resin composition according to aspect 14 or 15 above, which is selected from the group consisting of mixtures.
[17] A resin molded product obtained by molding the cellulose nanofiber resin composition according to any one of aspects 14 to 16 above.

According to the present invention, it can be obtained as a water-containing dispersion that can be easily redispersed in water and an organic solvent after drying and that gives excellent dispersibility of cellulose nanofibers in a resin, or it can be obtained without deterioration during production. A dry body that is inhibited and imparts satisfactory mechanical and thermal properties to a resin composition when dispersed in a resin to produce the resin composition, while providing excellent abrasion resistance and moldability in practical applications. A cellulose nanofiber composition is provided, which can be obtained as

Illustrative embodiments of the present invention will be specifically described below, but the present invention is not limited to these embodiments.

One aspect of the present invention provides a cellulose nanofiber composition comprising (A) cellulose nanofibers, (B) a surface treatment agent, and (C) an antioxidant. Another aspect of the present invention provides a cellulose nanofiber resin composition (hereinafter referred to as , also simply referred to as a “resin composition”), and a resin molding obtained by molding the resin composition. The cellulose nanofiber composition and the resin composition may each be, for example, in a form containing water (for example, in the form of a water-containing dispersion) or in the form of a dry body.

≪(A) Cellulose nanofibers≫
Next, (A) cellulose nanofibers that can be used in the present invention will be described in detail.

(A) Cellulose nanofibers are cellulose with an average fiber diameter of 1000 nm or less. Suitable examples of (A) cellulose nanofibers are not particularly limited, but for example, cellulose nanofibers made from cellulose pulp or one or more of these modified celluloses can be used. Among these, one or more modified celluloses are preferably used from the viewpoint of stability and performance. (A) The average fiber diameter of the cellulose nanofibers is 1000 nm or less, preferably 500 nm or less, more preferably 200 nm or less, from the viewpoint of obtaining good mechanical strength (especially tensile modulus) of the resin molding. The average fiber diameter is preferably as small as possible, but from the viewpoint of ease of processing, it is preferably 10 nm or more, more preferably 20 nm or more, and even more preferably 30 nm or more. The above-mentioned average fiber diameter is a value obtained as a sphere-converted diameter (volume average particle diameter) of particles when the accumulated volume is 50% by a laser diffraction/scattering method particle size distribution meter.

The average fiber diameter can be measured by the following method. (A) With cellulose nanofiber as a solid content of 40% by mass, in a planetary mixer (for example, Shinagawa Kogyosho Co., Ltd., 5DM-03-R, stirring blades are hook type) at 126 rpm, 30 at room temperature and normal pressure. Knead for minutes, then make a pure water suspension at a concentration of 0.5% by mass, and use a high shear homogenizer (for example, Nippon Seiki Co., Ltd., product name "Excel Auto Homogenizer ED-7" processing conditions), rotation speed Dispersed at 15,000 rpm for 5 minutes, using a centrifuge (for example, manufactured by Kubota Shoji Co., Ltd., trade name "6800 type centrifuge", rotor type RA-400 type), treatment conditions: centrifugal force 39200 m ² / After centrifugation at 116,000 m ² /s for 45 minutes, the supernatant is collected, and the supernatant after centrifugation is collected. Using this supernatant liquid, a laser diffraction/scattering method particle size distribution analyzer (for example, manufactured by Horiba Ltd., trade name "LA-910" or trade name "LA-950", ultrasonic treatment for 1 minute, refractive index of 1.00). 20) The cumulative 50% particle diameter in the volume frequency particle size distribution obtained in (i.e., the diameter of the particles when the cumulative volume is 50% of the total volume of the particles) is the volume average particle diameter. .

In a typical embodiment, (A) the cellulose nanofibers have an L/D ratio of 20 or more. The lower limit of L/D of cellulose nanofibers is preferably 30, more preferably 40, more preferably 50, and even more preferably 100. Although the upper limit is not particularly limited, it is preferably 10,000 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 range described above.

In the present disclosure, the length, diameter, and L/D ratio of cellulose nanofibers are determined by subjecting each aqueous dispersion of cellulose nanofibers to a high-shear homogenizer (for example, Nippon Seiki Co., Ltd., trade name "Excel Auto Homogenizer ED"). -7”), treatment conditions: a water dispersion dispersed at a rotation speed of 15,000 rpm for 5 minutes, diluted with pure water to 0.1 to 0.5% by mass, cast on mica, and air-dried The resulting product is used as a measurement sample, and measured with an optical microscope, high-resolution scanning microscope (SEM), or atomic force microscope (AFM). Specifically, the length (L) and diameter (D) of 100 randomly selected cellulose nanofibers in an observation field whose magnification is adjusted so that at least 100 cellulose nanofibers can be observed. is measured and the ratio (L/D) is calculated. Moreover, the length and diameter of the cellulose nanofibers of the present disclosure are the number average values of the 100 cellulose fibers.

The length, diameter, and L/D ratio of each of the cellulose nanofibers in the resin composition and the resin molding are determined by dissolving the resin component in the composition in an organic or inorganic solvent capable of dissolving the resin component in the composition. After separating the cellulose and sufficiently washing with the solvent, an aqueous dispersion is prepared by replacing the solvent with pure water or a dispersible organic solvent, and the cellulose concentration is adjusted to 0.1 to 0.5% by mass. It can be confirmed by diluting it with pure water, casting it on mica, air-drying it, and measuring it as a measurement sample by the above-described measurement method. At this time, 100 or more randomly selected cellulose fibers are measured.

(A) Cellulose nanofibers are obtained by treating pulp or the like with hot water at 100°C or higher, hydrolyzing the hemicellulose portion to make it brittle, and then pulverizing using a high-pressure homogenizer, microfluidizer, ball mill, disc mill, or the like. It may be cellulose defibrated by a method. In one aspect, (A) the cellulose nanofibers may have an L/D ratio of 30 or more and are not classified as cellulose pulp (i.e., those having an L/D ratio of 40 or more and a fiber diameter exceeding 1000 nm). .

(A) Modified cellulose nanofibers in the present disclosure include one or more modifiers selected from an esterifying agent, a silylating agent, an isocyanate compound, a halogenated alkylating agent, an alkylene oxide and/or a glycidyl compound. Modified ones are included. In a preferred embodiment, (A) the cellulose nanofiber is an unmodified product or an oxoacid-modified group (that is, a site where the hydroxyl group of cellulose is converted with an oxoacid (e.g., carboxylic acid) or a salt thereof (e.g., carboxylate)). Non-containing modifications, examples of which are preferred modifications are modifications with the modifiers listed above.

Esterifying agents as modifiers include (A) organic compounds having at least one functional group capable of reacting with and esterifying hydroxyl groups on the surface of cellulose nanofibers. Esterification can be carried out by the method described in paragraph [0108] of WO2017/159823. Esterifying agents may be commercially available reagents or products.

Preferable examples of the esterifying agent include, but are not limited to, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, iso Aliphatic monocarboxylic acids such as butyric acid; Alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; Aromatics such as benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid monocarboxylic acids; and any mixtures thereof, and any symmetrical anhydrides (acetic anhydride, maleic anhydride, cyclohexane-carboxylic anhydride, benzene-sulfonic anhydride) selected from these, mixed anhydride (butyric-valeric anhydride), cyclic anhydride (succinic anhydride, phthalic anhydride, naphthalene-1,8:4,5-tetracarboxylic dianhydride, cyclohexane-1,2,3, 4-tetracarboxylic acid 3,4-anhydride), ester acid anhydrides (acetic acid 3-(ethoxycarbonyl)propanoic anhydride, benzoylethyl carbonate), and the like.

Among these, 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 preferably be used.

Silylating agents as modifiers include Si-containing compounds having at least one reactive group capable of reacting with the surface hydroxyl groups of cellulose or groups after hydrolysis thereof. Silylating agents may be commercially available reagents or products.

Suitable examples of the silylating agent include, but are not limited to, chlorodimethylisopropylsilane, chlorodimethylbutylsilane, chlorodimethyloctylsilane, chlorodimethyldodecylsilane, chlorodimethyloctadecylsilane, chlorodimethylphenylsilane, 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 silazane or 1,3-di(para-t-butylphenethyl)tetramethyldisilazane, N-trimethylsilylacetamide, N-methyldiphenylsilylacetamide, N-triethylsilylacetamide, t-butyldiphenylmethoxysilane, octadecyldimethylmethoxysilane, dimethyloctylmethoxysilane, octylmethyldimethoxysilane, octyltrimethoxysilane, trimethylethoxysilane, octyltriethoxysilane, and the like.

Among these, hexamethyldisilazane, octadecyldimethylmethoxysilane, dimethyloctylmethoxysilane, and trimethylethoxysilane are preferably used in terms of reactivity, stability, price, and the like.

Haloalkylating agents as modifiers include organic compounds having at least one functional group capable of reacting with and haloalkylating hydroxyl groups on the surface of cellulose. Halogenated alkylating agents may be commercially available reagents or products.

Preferred examples of the halogenated alkylating agent include, but are not limited to, chloropropane, chlorobutane, bromopropane, bromohexane, bromoheptane, iodomethane, iodoethane, iodooctane, iodooctadecane, iodobenzene, and the like. Among these, bromohexane and iodooctane are preferably used in terms of reactivity, stability, price, and the like.

The isocyanate compound as a modifier includes (A) an organic compound having at least one isocyanate group capable of reacting with a hydroxyl group on the surface of the cellulose nanofiber. The isocyanate compound may be a blocked isocyanate compound capable of regenerating the isocyanate group by elimination of the blocking group at a specific temperature. and polymethylene polyphenyl polyisocyanate (polymeric MDI). These may be commercially available reagents or products.

Suitable examples of isocyanate compounds include, but are not particularly 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′-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, the above isocyanate compounds Reaction with oxime blocking agent, phenol blocking agent, lactam blocking agent, alcohol blocking agent, active methylene blocking agent, amine blocking agent, pyrazole blocking agent, bisulfite blocking agent, or imidazole blocking agent and the like.

Among these, TDI, MDI, hexamethylene diisocyanate, and blocked isocyanate made from modified hexamethylene diisocyanate and hexamethylene diisocyanate are preferably used from the viewpoint of reactivity, stability, price, 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 still more preferably 150°C, from the viewpoint of reactivity and stability. The lower limit is preferably 70°C, more preferably 80°C, and even more preferably 110°C. Blocking agents whose dissociation temperature of the blocking group falls within this range include methyl ethyl ketone oxime, ortho-secondary butylphenol, caprolactam, sodium bisulfite, 3,5-dimethylpyrazole, 2-methylimidazole and the like.

Alkylene oxide and/or glycidyl compounds as modifiers include organic compounds having at least one alkylene oxide group, glycidyl group and/or epoxy group capable of reacting with hydroxyl groups on the surface of cellulose. Alkylene oxide and/or glycidyl compounds may be commercially available reagents or products.

Preferred examples of the alkylene oxide and/or glycidyl compound are not particularly limited, but examples include methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, 2-methyloctyl glycidyl ether, phenyl glycidyl ether, p -glycidyl ethers such as tertiary butylphenyl glycidyl ether, sec-butylphenyl glycidyl ether, n-butylphenyl glycidyl ether, phenylphenol glycidyl ether, cresyl glycidyl ether and dibromocresyl glycidyl ether; glycidyl acetate, glycidyl stearate and the like; 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 triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, polyglycerol polyglycidyl ether, diglycerol polyglycidyl ether Examples include polyhydric alcohol glycidyl ethers such as ethers.

Among these, 2-methyloctylglycidyl ether, hexamethylene glycol diglycidyl ether, and pentaerythritol tetraglycidyl ether are preferably used from the viewpoints of reactivity, stability, price, and the like.

(A) Cellulose nanofibers are obtained 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 removing 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.

The amount of (A) cellulose nanofibers in the entire cellulose nanofiber composition (e.g., water-containing dispersion and dry body), which is one embodiment, is preferably 1% by mass or more from the viewpoint of good redispersibility. , preferably 5% by mass or more, more preferably 10% by mass or more, and from the viewpoint of obtaining sufficient mechanical properties in the resin composition and the resin molded article, preferably 50% by mass or less, preferably 40% by mass or less, and more Preferably, it is 20% by mass or less.

The content of (A) cellulose nanofibers in the entire resin composition and resin molding, which is one embodiment, is preferably 1% by mass or more from the viewpoint of good mechanical properties, thermal stability and durability, respectively. , More preferably 3% by mass or more, more preferably 5% by mass or more, and from the viewpoint of obtaining good moldability, preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 20% by mass or less is.

The amount of (A) cellulose nanofibers in the cellulose nanofiber composition (for example, water-containing dispersion and dry matter) can be easily confirmed by those skilled in the art by common methods. Although the confirmation method is not limited, the following methods can be exemplified. Water is added to the dried cellulose nanofibers to obtain a cellulose nanofiber water-containing dispersion. Centrifugation is performed with respect to the cellulose nanofiber water-containing dispersion. This enables separation into sediments (cellulose nanofibers and polyurethane) and the surface treatment agent dispersion. A washing solvent is added to the sediment, and suction filtration is performed to separate the insoluble matter 1 (cellulose nanofibers). The content can be calculated by drying the isolated cellulose nanofibers and measuring the weight. In addition, the isolated cellulose nanofibers can be qualitatively and quantitatively analyzed by using various analyzers such as pyrolysis GC-MS, ¹ H-NMR, or ¹³ C-NMR.

The amount of (A) cellulose nanofibers in the resin composition and resin molding can be easily confirmed by those skilled in the art by a general method. Although the confirmation method is not limited, the following methods can be exemplified. The resin composition is dissolved in a solvent that dissolves the resin using the resin composition and the fragments of the molded body, and the soluble content 1 (resin and surface treatment agent) and the insoluble content 1 (cellulose and surface treatment agent) are separated. do. After the separation, the insoluble matter 1 is dissolved in a surface treatment agent-dissolving solvent to separate into a soluble matter 2 (surface treatment agent) and an insoluble matter 2 (cellulose). A washing solvent is added to the insoluble matter 2 (cellulose), suction filtration is performed, and cellulose nanofibers are separated. The content can be calculated by drying the isolated cellulose nanofibers and measuring the weight. The isolated cellulose nanofibers can be qualitatively and quantitatively analyzed by using various analyzers such as pyrolysis GC-MS, ¹ H-NMR or ¹³ C-NMR, and wide-angle X-ray diffraction.

<<(B) Surface treatment agent>>
The (B) surface treatment agent of the present disclosure is a water-soluble polymer in one aspect, and has a hydrophilic segment and a hydrophobic segment in one aspect. In one aspect, (B) the surface treatment agent is a nonionic surfactant. In one embodiment, (B) the surface treatment agent has a number average molecular weight of 200 to 30,000. In the present disclosure, "water-soluble" means that 0.1 g or more dissolves in 100 g of water at 23°C. (B) The surface treatment agent is, for example, (E) a modified polymer of the same type as the thermoplastic resin of the present disclosure (e.g., an acid modified product, a copolymer), (E) a polymer different from the thermoplastic resin, etc. It differs from (E) thermoplastic resins in one way. In a typical embodiment, (E) the thermoplastic resin is not water soluble and (B) the surface treatment agent is water soluble. (B) The surface treatment agent may be mixed with (A) cellulose nanofibers in the form of an aqueous dispersion containing the surface treatment agent (B) at a high concentration, for example. (B) Surface treatment agents may be commercially available reagents or products.

(B) The hydrophilic segment of the surface treatment agent has good affinity with the surface of cellulose. The hydrophobic segment can suppress aggregation of cellulose through the hydrophilic segment. Therefore, in (B) the surface treatment agent, 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 (e.g., one or more hydrophilic groups selected from a hydroxyl group, a carboxyl group, a carbonyl group, an amino group, an ammonium group, an amide group, a sulfo group, etc.) (A) is a portion that exhibits good affinity with cellulose nanofibers. The hydrophilic segment includes a segment of polyethylene glycol (that is, a segment of a plurality of 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, a segment of poly Acrylic acid segment, carboxyvinyl polymer segment, cationized guar gum segment, hydroxyethyl cellulose segment, methyl cellulose segment, carboxymethyl cellulose segment, polyurethane flexible segment (soft segment) (specifically, diol segment), etc. I can give an example. In a preferred embodiment, the hydrophilic segment contains oxyethylene units.

Examples of the hydrophobic segment include a segment having an alkylene oxide unit with 3 or more carbon atoms (eg, PPG block), a segment containing the following polymer structure, and the like:
Acrylic polymer, styrene resin, vinyl chloride resin, vinylidene chloride resin, polyolefin resin, polyhexamethylene adipamide (nylon 6,6), polyhexamethylene azelamide (nylon 6,9), polyhexamethylene Organic dicarboxylic acids with 4 to 12 carbon atoms and 2 to 13 carbon atoms, such as sebacamide (nylon 6,10), polyhexamethylene dodecanoamide (nylon 6,12), polybis(4-aminocyclohexyl)methandodecane, etc. polycondensates with organic diamines, polycondensates of ω-amino acids (such as ω-aminoundecanoic acid) (such as polyundecaneamide (11 nylon), etc.), and polycapramides, which are ring-opening polymers of ε-aminocaprolactam ( 6 nylon), polylauric lactam (12 nylon), which is a ring-opening polymer of ε-aminolaurolactam, amino acid lactams containing ring-opening polymers of lactams, polymers composed of diamines and dicarboxylic acids, polyacetals resins, polycarbonate resins, polyester resins, polyphenylene sulfide resins, polysulfone resins, polyetherketone resins, polyimide resins, fluorine resins, hydrophobic silicone resins, melamine resins, epoxy resins, phenol resins resin.

In a preferred embodiment, (B) the surface treatment agent has a PEG block as a hydrophilic group and a PPG block as a hydrophobic group in its molecule.

(B) The surface treatment agent can have a graft copolymer structure and/or a block copolymer structure. These may be used individually by 1 type, and may use 2 or more types together. When two or more are used in combination, they may be used as a polymer alloy. Partially modified products or terminally modified products (acid-modified) of these copolymers may also be used.

(B) The structure of the surface treatment agent is not particularly limited. coalescing, ABAB-type block copolymer, ABABA-type block copolymer, BABAB-type copolymer, tri-branched copolymer containing A and B, tetra-branched copolymer containing A and B, A and B star-shaped copolymers containing A and B, monocyclic copolymers containing A and B, polycyclic copolymers containing A and B, cage-shaped copolymers containing A and B, and the like.

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

(B) Suitable examples of the surface treatment agent include compounds that provide a hydrophilic segment (e.g., polyethylene glycol), compounds that provide a hydrophobic segment (e.g., polypropylene glycol, poly(tetramethylene ether) glycol (PTMEG), 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 singly or in combination of two or more. When two or more are used in combination, they may be used as a polymer alloy. In addition, modified copolymers (for example, modified with at least one compound selected from unsaturated carboxylic acids, their acid anhydrides and their derivatives) can also be used.

Among these, copolymers of polyethylene glycol and polypropylene glycol, copolymers of polyethylene glycol and poly(tetramethylene ether) glycol (PTMEG), and mixtures thereof are preferred from the viewpoint of heat resistance (odor resistance) and mechanical properties. A copolymer of polyethylene glycol and polypropylene glycol is preferred, and a copolymer of polyethylene glycol and polypropylene glycol is more preferred from the viewpoint of handleability and cost.

In a typical embodiment, (B) the surface treatment agent 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 moiety is increased, the temperature at which the aqueous solution was transparent or translucent (this temperature is called the cloud point) ), a phenomenon of clouding is observed. That is, when an aqueous solution that is transparent or translucent at low temperatures is heated, the solubility of the nonionic surfactant drops sharply at a certain temperature, causing the previously dissolved surfactants to aggregate and become cloudy. and separate from the water. This is presumably because the nonionic surfactant loses its hydrating power at high temperatures (the hydrogen bond between the polyether chain and water breaks and the solubility in water sharply drops). The cloud point tends to be lower as the polyether chain is longer. Since it dissolves in water at any ratio at a temperature below the clouding point, the clouding point is a measure of the hydrophilicity of the surface treatment agent (B).

(B) The cloud point of the surface treatment agent 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) surface treatment agent is 0.5% by mass, 1.0% by mass, and 5% by mass. Adjust and measure in the temperature range of 0 to 100°C. At this time, the part showing the inflection point (increasing change in viscosity or the point at which the aqueous solution becomes cloudy) at each concentration is defined as the cloud point.

(B) The lower limit of the cloud point of the surface treatment agent is preferably 10°C, more preferably 20°C, and most preferably 30°C, from the viewpoint of handleability. Although the upper limit of the cloud point is not particularly limited, it is preferably 120°C, more preferably 110°C, still more preferably 100°C, and most preferably 60°C. (A) In order to ensure good affinity with cellulose nanofibers, the cloud point of (B) the surface treatment agent is desirably within the above range.

(B) The lower limit of the melting point of the surface treatment agent is preferably −35° C., more preferably −10° C., most preferably 0° C., from the viewpoint of not plasticizing the resin composition, and the upper limit is preferably 70°C, more preferably 30°C, and most preferably 10°C from the viewpoint of operability.

(B) The lower limit of the mass ratio of the hydrophilic segment to the hydrophobic segment (hydrophobic segment molecular weight/hydrophilic segment molecular weight) of the surface treatment agent is not particularly limited, but is preferably 0, more preferably 0.1. , more preferably 0.5, and most preferably 1. In addition, 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 199, more preferably 100, more preferably 100, from the viewpoint of solubility in water. 50, most preferably 20. (A) In order to ensure good affinity with cellulose nanofibers, the ratio of (B) the surface treatment agent is preferably within the above range.

(B) The lower limit of the number average molecular weight of the surface treatment agent is preferably 200, more preferably 250, from the viewpoint of improving odor resistance during preparation of the resin composition and moldability during molding. Preferably 300, most preferably 500. The upper limit of the number average molecular weight is preferably 30,000, more preferably 25,000, still more preferably 23,000, still more preferably 20,000, even more preferably 10,000, and most preferably 5,000 from the viewpoint of handleability. (A) In order to ensure good affinity with cellulose nanofibers, the number average molecular weight of (B) the surface treatment agent is preferably within the above range.

(B) The lower limit of the molecular weight of the hydrophilic segment of the surface treatment agent is preferably 100, more preferably 150, and most preferably 200, from the viewpoint of affinity with cellulose nanofibers. is preferably 20,000, more preferably 15,000, and most preferably 10,000, from the viewpoint of the solubility of

(B) The lower limit of the molecular weight of the hydrophobic segment of the surface treatment agent is preferably 100, more preferably 150, and most preferably 200, from the viewpoint of the dispersibility of the cellulose nanofibers in the resin, and the upper limit is water. It is preferably 10,000, more preferably 5,000, and most preferably 4,000 from the viewpoint of solubility in .

In one aspect of the cellulose nanofiber composition (eg, water-containing dispersion and dry matter), the preferred amount of (B) the surface treatment agent is 0.1 to 50% by mass relative to the entire composition. The upper limit is more preferably 20% by mass, still more preferably 10% by mass, even more preferably 5% by mass, and particularly preferably 3% by mass. Although the lower limit is not particularly limited, it is preferably 0.2% by mass, more preferably 0.5% by mass, and most preferably 1% by mass.

In each of the resin composition and the resin molded article, the preferred amount of the (B) surface treatment agent is in the range of 0.1 to 50% by mass of the (B) surface treatment agent with respect to the entire resin composition or resin molded article. is within. The upper limit is more preferably 18% by mass, still more preferably 15% by mass, even more preferably 10% by mass, and particularly preferably 5% by mass. Although the lower limit is not particularly limited, it 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 surface treatment agent (B) 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 (B) the surface treatment agent as above, the dispersibility of (A) cellulose nanofibers in (E) thermoplastic resin can be enhanced.

In each of the cellulose nanofiber-containing composition (e.g., water-containing dispersion and dried body), resin composition, and resin molding, the preferred amount of (B) surface treatment agent is (A) per 100 parts by mass of cellulose nanofibers. On the other hand, the amount of (B) the surface treatment agent is in the range of 0.1 to 100 parts by mass. The upper limit is more preferably 99 parts by mass, more preferably 90 parts by mass, more preferably 80 parts by mass, still more preferably 70 parts by mass, still more preferably 50 parts by mass, and particularly preferably 40 parts by mass. Although the lower limit is not particularly limited, it is preferably 0.1 parts by mass, more preferably 0.5 parts by mass, and most preferably 1 part by mass. By setting the upper limit of the surface treatment agent (B) to the above range, it is possible to suppress plasticization in the resin composition and the resin molding, and to maintain good strength. Further, by setting the lower limit amount of the (B) surface treatment agent to the above, the redispersibility of the (A) cellulose nanofibers can be enhanced.

The (B) surface treatment agent of the present disclosure preferably has an HLB value of 0.1 or more and less than 12. In the present disclosure, the HLB value can be obtained from the Griffin method formula below. In the following formula 1, "sum of formula weights of hydrophilic groups/molecular weight" is mass % of hydrophilic groups.
Formula 1) Griffin method: HLB value = 20 x (sum of formula weights of hydrophilic groups/molecular weight)

In the surface treatment agent (B) of the present disclosure, the lower limit of the HLB value is not particularly limited from the viewpoint of easy solubility in water, but is preferably 0.1, more preferably 0.2, and most 1 is preferred. In addition, the upper limit of the HLB value is preferably less than 12, more preferably 10, still more preferably 8, still more preferably 7.5, from the viewpoint of redispersibility in water and organic solvents. and most preferably 7. The HLB value of the surface treatment agent (B) is preferably within the range described above for excellent redispersibility in water and organic solvents. Further, excellent redispersibility in organic solvents means excellent dispersibility in resins. The HLB value is a value that indicates the balance between hydrophobicity and hydrophilicity of a surfactant, and takes values from 1 to 20. The smaller the value, the stronger the hydrophobicity, and the larger the value, the stronger the hydrophilicity. indicates that

The amount of (B) the surface treatment agent in the cellulose nanofiber composition (eg, water-containing dispersion and dried body) can be easily confirmed by those skilled in the art by a general method. Although the confirmation method is not limited, the following methods can be exemplified. Water is added to the dried cellulose nanofibers to obtain a cellulose nanofiber water-containing dispersion. Centrifugation is performed with respect to the cellulose nanofiber water-containing dispersion. As a result, the sediment (cellulose nanofibers) and the surface treatment agent dispersion can be separated. By concentrating (drying, air-drying, drying under reduced pressure, etc.) the surface-treating agent dispersion, (B) the surface-treating agent can be quantified. The (B) surface-treating agent after concentration can be identified and measured for molecular weight by various analyzers such as pyrolysis GC-MS, ¹ H-NMR, or ¹³ C-NMR.

In each of the resin composition and the resin molding, the amount of (B) the surface treatment agent can be easily confirmed by those skilled in the art by a general method. Although the confirmation method is not limited, the following methods can be exemplified. When the resin composition is dissolved in (E) a solvent that dissolves the thermoplastic resin, using a fragment of the resin composition or the resin molded body, the soluble component 1 (resin and surface treatment agent, antioxidant) and Insoluble matter 1 (cellulose and surface treatment agent) is separated. The soluble matter 1 is reprecipitated with a solvent that does not dissolve the resin but dissolves the surface treatment agent, thereby separating the insoluble matter 2 (resin) and the soluble matter 2 (surface treatment agent, antioxidant). Also, the insoluble matter 1 is dissolved in a surface treatment agent-dissolving solvent to separate into a soluble matter 3 (surface treatment agent, antioxidant) and an insoluble matter 3 (cellulose). By concentrating (drying, air-drying, vacuum drying, etc.) the soluble matter 2 and soluble matter 3, it is possible to quantify (B) the surface treatment agent. The (B) surface treatment agent after concentration can be identified and the molecular weight can be measured by the methods described above.

There is no particular limitation on the method of adding the surface treatment agent (B) when preparing the cellulose nanofiber composition. For example, the method for preparing the cellulose nanofiber aqueous dispersion is not limited to this, but (B) the surface treatment agent is dissolved in water, and (A) the cellulose nanofiber is added to the resulting surface treatment agent aqueous solution. A method of obtaining a cellulose nanofiber water-containing dispersion by adding and mixing, (A) dispersing cellulose nanofibers in water, adding (B) a surface treatment agent to the obtained (A) cellulose nanofiber dispersion, and a method of obtaining a dispersion by mixing.

In addition, the method of adding (B) the surface treatment agent when preparing the resin composition is not particularly limited, but (E) the thermoplastic resin, (A) cellulose nanofibers, and (B) the surface treatment agent A method of pre-mixing and melt-kneading, (E) a method of adding (B) a surface treatment agent in advance to a thermoplastic resin, preliminarily kneading if necessary, and then adding (A) cellulose nanofibers and melt-kneading, (A ) A method of pre-mixing cellulose nanofibers and (B) a surface treatment agent, and then (E) melt-kneading with a thermoplastic resin, (A) cellulose nanofibers are dispersed in water, and (A) surface A method of adding a treating agent and drying to prepare a dried cellulose, and then adding the dried cellulose to (E) a thermoplastic resin, and the like.

«(C) Antioxidant»
Next, the (C) antioxidant used in the present invention will be described in detail. (C) Antioxidants include (A) cellulose nanofibers and (B) surface treatment agents, and (E) heat in the resin composition when the resin composition is produced using the cellulose nanofiber composition. By suppressing oxidative deterioration of the plastic resin, it contributes to good heat resistance of the resin composition and the resin molding. In particular, the use of (C) an antioxidant suppresses the deterioration of (A) cellulose nanofibers (that is, a polymer having an extremely large surface area). It is extremely advantageous in improving heat resistance.

As antioxidant (C), various compounds that are understood by those skilled in the art to be useful as antioxidants for thermoplastic resins can be used. Antioxidants are effective by themselves to prevent oxidation deterioration of resins in the presence of oxygen. Antioxidants include radical scavengers and peroxide decomposers. Radical scavengers include hindered phenol-based antioxidants, hindered amine-based light stabilizers (HALS), and the like. Examples of peroxide decomposers include phosphorus antioxidants and sulfur antioxidants. The antioxidant may be a compound having two or more antioxidant action sites in the molecule. Examples of such compounds include compounds having both a hindered phenol structure and a thioether structure (which are included in both hindered phenol antioxidants and thioether antioxidants). These antioxidants can be used singly or in combination of two or more. For example, the antioxidant may be a composite antioxidant (ie, two or more antioxidants are appropriately pre-blended).

As the antioxidant, from the viewpoint of the effect of preventing deterioration due to heat, hindered phenol antioxidants, sulfur antioxidants, and phosphorus antioxidants are preferred, and phosphorus antioxidants and hindered phenol antioxidants are preferred. An antioxidant is more preferred, and a combined use of a phosphorus antioxidant and/or a hindered phenol antioxidant and a hindered amine light stabilizer (HALS) is even more preferred. (C) Antioxidant may be mixed with (A) cellulose nanofibers in the form of an aqueous dispersion containing (B) surface treatment agent at a high concentration, for example. (C) Antioxidants may be commercially available reagents or products.

When a phosphorus-based antioxidant and/or a hindered phenol-based antioxidant and a hindered amine-based light stabilizer (HALS) are used in combination, the ratio is not particularly limited, but (phosphorus-based antioxidant and hindered phenol-based The weight ratio of (total of antioxidants)/hindered amine light stabilizer (HALS) is preferably 1/5 to 2/1, more preferably 1/2 to 1/1.

A hindered phenol-based antioxidant is a compound having one or more phenol structures (especially, a phenol structure having a sterically hindering substituent) in the molecule. Hindered phenol-based antioxidants (which may have a structure also included in thioether-based antioxidants) include pentaerythritol tetrakis (3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate), thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate , N,N′-hexane-1,6-diylbis(3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)), benzenepropanoic acid, 3,5-bis(1,1- dimethyl-ethyl)-4-hydroxy-C7-C9 branched alkyl ester, 3,3′,3″,5,5′,5″-hexa-tert-butyl-α,α′,α″-(mesitylene-2 ,4,6-triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis-(3-(5-tert-butyl-4-hydroxy- m-tolyl) propionate), hexamethylenebis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), 1,3,5-tris(3,5-di-tert-butyl- 4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio) -1,3,5-triazin-2-ylamino)phenol, 4,6-bis(dodecylthiomethyl)-o-cresol, 3,4-dihydro-2,5,7,8-tetramethyl-2-( 4,8,12-trimethyltridecyl)-2H-1-benzopyran-6-ol, 2′,3-bis[[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyl]] Propionohydrazide, 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], di(tridecyl)3,3′-thio Dipropionate is mentioned.

Commercially available reagents include Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1098, Irganox 1135, Irganox 1330, Irganox 1520 L, Irganox 245, Irganox 259, Irganox 3114, Irganox ox565, Irganox1726, IrganoxE201, IrganoxMD1024 (these are available from BASF Japan Ltd., etc.), Adekastab AO412S, Adekastab AO503 (all available from ADEKA Corporation), SUMILIZERGS, SUMILIZERGM, SUMILIZERGA80 (all available from Sumitomo Chemical Co., Ltd.), and the like.

A phosphorus-based antioxidant is a compound having a phosphorus-containing structure such as a phosphite ester structure in the molecule. Phosphorus-based antioxidants may be phosphite-based or phosphonite-based. Phosphorus antioxidants include tris(2,4-di-tert-butylphenyl)phosphite, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro [ 5.5]undecane, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 2,2′-methylenebis(4,6-di-tert-butylphenyl)2-ethylhexylphosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra- C12-15-alkyl(propane-2,2-diylbis(4,1-phenylene))bis(phosphite), 2-ethylhexyldiphenylphosphite, isodecyldiphenylphosphite, triisodecylphosphite, triphenyl phosphite.

Commercially available reagents include Irgafos 168 (available from BASF Japan Ltd.), Adekastab PEP8, Adekastab PEP36, Adekastab HP10, Adekastab 2112, Adekastab 1178, Adekastab 1500, Adekastab C, Adekastab 135A, Adekastab 3010, Adekastab TPP (above , available from ADEKA Corporation) and the like.

Examples of sulfur-based antioxidants include compounds having a thioether structure (ie, thioether-based antioxidants) and compounds having a thioester structure (ie, thioester-based antioxidants). Thioether antioxidants include thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 4,6-bis(octylthiomethyl)-o-cresol, 2, 6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, 4,6-bis(dodecylthiomethyl)-o-cresol, 2 , 2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], di(tridecyl) 3,3′-thiodipropionate, etc. is mentioned. Thioester antioxidants include didodecyl-3,3'-thiodipropionate and dioctadecyl 3,3'-thiodipropionate.

Commercially available reagents include IrganoxPS800FL and IrganoxPS802FL (all available from BASF Japan Ltd.).

Hindered amine light stabilizers (HALS) are preferably compounds having a 2,2,6,6-tetramethylpiperidine structure in the molecule. Light stabilizers include [1,6-hexanediamine, N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)-polymer and 2,4,6-trichloro-1,3 ,5-triazine, the reaction product of N-butyl-1-butanamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine], poly[[6-[(1,1, 3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexane diyl [(2,2,6,6-tetramethyl-4-piperidinyl)imino]]), poly [[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5 -triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-5- piperidinyl)imino]]), the reaction product of butanedioic acid dimethyl ester with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, bis(1,2,2,6, 6-pentamethyl-4-piperidinyl)-2-butyl-2-(4-hydroxy-3,5-di-tert-butylbenzyl)propanedioate, bis(1,2,2,6,6-pentamethyl-4 -piperidyl) sebacate + methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, decanedioic acid, bis(2 ,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane, bis(1,2,2,6,6 -pentamethyl-4-piperidinyl)-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, phenol, 2-(2H-benzotriazol-2-yl)- 4-methyl-6-dodecyl-, branched and linear, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4- piperidinyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)butane-1,2,3,4 -tetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)butane-1,2,3,4-tetracarboxylate, 1,2,3,4-butanetetracarboxylic acid, tetra Methyl ester, 1,2,2,6,6-pentamethyl-4-piperidinol and β,β,β',β'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane- Reaction Products of 3,9-Diethanol, 1,2,3,4-Butanetetracarboxylic Acid, Tetramethyl Ester, 2,2,6,6-Tetramethyl-4-piperidinol and β,β,β',β '-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol reaction product, bis(1,2,2,6,6-pentamethyl-4- piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 1,2 , 2,6,6-pentamethyl-4-piperidyl methacrylate and 2,2,6,6-tetramethyl-4-piperidyl methacrylate.

Commercially available reagents include Chimassorb2020FDL, Chimassorb944FDL, Chimassorb944LD, Tinuvin622SF, TinuvinPA144, Tinuvin765, Tinuvin770DF, TinuvinXT55FB, Tinuvin111FDL, Tinuvin 783FDL, Tinuvin791FB, Tinuvin249, Tinuvin123, Tinuvin144, Tinuvin171, Tinuvin292, Tinuvin5100, Tinuvin770DF (above, BASF Japan Co., Ltd. ), ADEKA STAB LA52, ADEKA STAB LA57, ADEKA STAB LA63, ADEKA STAB LA68, ADEKA STAB LA72, ADEKA STAB LA77Y, ADEKA STAB LA81, ADEKA STAB LA82, ADEKA STAB LA87, ADEKA STAB LA402AF, ADEKA STAB LA502XP (above, ADEKA CORPORATION) available from), etc. is mentioned.

A composite antioxidant is typically a combination of a bisphenol antioxidant and a phosphorus antioxidant. Reagents commercially available as composite antioxidants include Adekastab A611, Adekastab A612, Adekastab A613, Adekastab A512, Adekastab AO15, Adekastab AO18, Adekastab AO37, Adekastab AO412S, Adekastab AO503, Adekastab A (the above, ADEKA Corporation (available from Sumitomo Chemical Co., Ltd.), SUMILIZERGP (available from Sumitomo Chemical Co., Ltd.), and the like.

Among them, pentaerythritol tetrakis (3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl)-propionate, N,N'-hexane-1,6-diylbis(3-(3,5-di-tert-butyl-4-hydroxyphenylpropionate) amide)), ethylenebis(oxyethylene)bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate), 2′,3-bis[[3-[3,5-di- tert-Butyl-4-hydroxyphenyl]propionyl]]propionohydrazide, and among commercially available reagents, Irganox 1010, Irganox 1076, Irganox 1098, Irganox 245, and IrganoxMD1024 (all available from BASF Japan Ltd.) are preferred.

(C) The lower limit of the molecular weight of the antioxidant is preferably 200, more preferably 250, and even more preferably 250, from the viewpoint of improving the odor during production of the resin composition and the moldability during molding. 300, most preferably 500. The upper limit of the molecular weight is preferably 10,000, more preferably 5,000, still more preferably 3,000, and most preferably 1,000 from the viewpoint of handleability. (B) In order to ensure good affinity with the surface treatment agent, it is desirable that the molecular weight of (C) the antioxidant is within the range described above.

In one aspect, the preferred amount of (C) antioxidant in the cellulose nanofiber composition (eg, water-containing dispersion and dry matter) is 0.1 to 20% by mass based on the total composition. The upper limit is more preferably 15% by mass, still more preferably 10% by mass, even more preferably 5% by mass, and particularly preferably 3% by mass. Although the lower limit is not particularly limited, it is preferably 0.0005% by mass, more preferably 0.005% by mass, and most preferably 0.01% by mass.

In each of the resin composition and the resin molded article, the preferred amount of the (C) antioxidant is in the range of 0.01 to 5% by mass of the (C) antioxidant with respect to the entire resin composition or resin molded article. is within. The upper limit is more preferably 4% by mass, still more preferably 3% by mass, still more preferably 2% by mass, and particularly preferably 1% by mass. Although the lower limit is not particularly limited, it is preferably 0.02% by mass, more preferably 0.03% by mass, and most preferably 0.05% by mass. By setting the upper limit amount of the antioxidant (C) to the above range, plasticization of the resin composition can be suppressed, and good strength can be maintained. In addition, by setting the lower limit amount of (C) antioxidant to the above, the heat resistance of (A) cellulose nanofibers in (E) thermoplastic resin can be enhanced.

In each of the cellulose nanofiber composition (e.g. water-containing dispersion and dried body), resin composition and resin molding, the preferred amount of (C) antioxidant is (B) per 100 parts by mass of the surface treatment agent, ( C) The antioxidant is in the amount range of 0.01 to 100 parts by weight. The upper limit is more preferably 60 parts by mass, more preferably 30 parts by mass, more preferably 15 parts by mass, more preferably 8 parts by mass, and particularly preferably 5 parts by mass. Although the lower limit is not particularly limited, it is preferably 0.02 parts by mass, more preferably 0.05 parts by mass, and most preferably 0.1 parts by mass. By setting the upper limit amount of the antioxidant (C) to the above range, it is possible to suppress plasticization in the resin composition and the resin molding, and to maintain good strength. In addition, by setting the lower limit amount of (C) the antioxidant as above, the heat resistance of the composition containing the cellulose nanofibers, the surface treatment agent, and the antioxidant can be enhanced.

The amount of (C) antioxidant in the cellulose nanofiber composition (for example, water-containing dispersion and dry matter) can be easily confirmed by those skilled in the art by a general method. Although the confirmation method is not limited, the following methods can be exemplified. The dried cellulose nanofibers are processed by adding (C) an antioxidant-soluble organic solvent, followed by extraction and washing. This extract or cleaning solution is concentrated, and the surface treatment agent and antioxidant are quantified. The (C) antioxidant after concentration can be identified and molecular weight measured by various analyzers such as pyrolysis GC-MS, ¹ H-NMR, or ¹³ C-NMR.

In each of the resin composition and the resin molding, the amount of (C) antioxidant can be easily confirmed by those skilled in the art by a general method. Although the confirmation method is not limited, the following methods can be exemplified. Using the resin composition or the broken pieces of the resin molded body, the soluble content 1 (resin, surface treatment agent, and antioxidant) when the resin composition is dissolved in (E) a solvent that dissolves the thermoplastic resin and insoluble matter 1 (cellulose, surface treatment agent and antioxidant) are separated. The soluble matter 1 is reprecipitated with a solvent that does not dissolve the resin but dissolves the surface treatment agent, thereby separating the insoluble matter 2 (resin) and the soluble matter 2 (surface treatment agent and antioxidant). Also, the insoluble matter 1 is dissolved in a solvent that dissolves the surface treatment agent and the antioxidant to separate the soluble matter 3 (surface treatment agent and antioxidant) and the insoluble matter 3 (cellulose). By concentrating (drying, air-drying, drying under reduced pressure, etc.) the soluble matter 2 and the soluble matter 3, it is possible to quantify (C) the antioxidant. The (C) antioxidant after concentration can be identified and the molecular weight can be measured by the method described above.

There is no particular limitation on the method for adding (C) the antioxidant when preparing the cellulose nanofiber composition. For example, the method for preparing a cellulose nanofiber water-containing dispersion is not limited to this, but (B) the surface treatment agent is dissolved in water, and the resulting surface treatment agent aqueous solution is added with (C) an antioxidant, (A) A method of obtaining a cellulose nanofiber water-containing dispersion by adding and mixing cellulose nanofibers, (A) dispersing cellulose nanofibers in water, and (B) A surface treatment agent, (C) a method of adding an antioxidant and mixing to obtain a dispersion, (C) dissolving the antioxidant in a solvent capable of dissolving it, and separately dissolving (B) the surface treatment agent in water a method of obtaining a cellulose nanofiber water-containing dispersion by adding and mixing (A) cellulose nanofibers after adding to the obtained surface treatment agent aqueous solution and mixing.

In addition, the addition method of (C) antioxidant when preparing the resin composition is not particularly limited, but (E) thermoplastic resin, (A) cellulose nanofiber, (B) surface treatment agent, and (C) a method of pre-mixing an antioxidant and melt-kneading; (E) adding (B) a surface treatment agent and (C) an antioxidant to a thermoplastic resin in advance; A method of adding cellulose nanofibers and melt-kneading, a method of premixing (A) cellulose nanofibers with (B) a surface treatment agent and (C) an antioxidant, and then (E) melt-kneading with a thermoplastic resin. , (A) Add (B) a surface treatment agent and (C) an antioxidant to a dispersion liquid in which cellulose nanofibers are dispersed in water, and dry to prepare a cellulose dry body. (E) a method of adding to a thermoplastic resin, and the like.

<<(D) Water-soluble organic solvent>>
Next, the (D) water-soluble organic solvent that can be used in the present invention will be described in detail. In one aspect, the cellulose nanofiber compositions (eg, aqueous dispersion and dry matter) may each contain (D) a water-soluble organic solvent. (D) Water-soluble organic solvents are solvents that have "water solubility" as defined in this disclosure. (D) The water-soluble organic solvent dissolves the (B) surface treatment agent present on the surface of (A) the cellulose nanofibers, and uniformly applies the (B) surface treatment agent to the (A) cellulose nanofibers. Advantages, and furthermore, the advantage of improving the re-dispersion of the dried cellulose nanofibers in water can be provided. (D) The water-soluble organic solvent may be a protic organic solvent or an aprotic organic solvent.

A protic organic solvent is an organic solvent that has a relatively acidic hydrogen atom bonded to an oxygen atom and serves as a hydrogen bond donor. On the other hand, an aprotic organic solvent is an organic solvent that does not have a highly acidic hydrogen atom. (D) The water-soluble organic solvent may be a commercially available reagent or product.

Specific examples of water-soluble organic solvents (D) that can be suitably used 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, triethylene glycol butyl methyl ether and the like. Examples of protic organic solvents include 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, triethylene glycol. Ethylene glycol monomethyl ether, polyethylene glycol monomethyl ether and the like can be mentioned.

Among these, from the viewpoint of heat resistance and availability, aprotic organic solvents such as diethylene glycol dimethyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, hexamethylphosphorus Santriamide, dimethyl sulfoxide, sulfolane and triethylene glycol dimethyl ether are preferred, and N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane and triethylene glycol dimethyl ether are It is more preferable from the viewpoint of handleability and cost.

From the viewpoint of heat resistance and availability, protic organic solvents such as 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 used from the viewpoint of handling and cost. more preferred.

In a typical embodiment, the lower limit of the molecular weight of (D) the water-soluble organic solvent is 50, preferably 100, more preferably 300, and most preferably 1,000. Although the upper limit of the number average molecular weight is not particularly limited, it is preferably 2000 or less from the viewpoint of handleability. From the viewpoint of dissolving the (B) surface treatment agent and improving the bonding or adsorption with the (E) thermoplastic resin and/or (A) cellulose nanofibers in the resin composition, it is preferable to be within the above range. desirable.

In a typical embodiment, the lower limit of the boiling point of (D) 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 boiling point is 300°C, more preferably 290°C, more preferably 280°C, more preferably 260°C, most preferably 240°C. (D) Since the lower limit of the boiling point of the water-soluble organic solvent is in the above range, although it is estimated, in the dried cellulose nanofibers, the water vaporizes first (B) the surface treatment agent and (D) the water-soluble organic solvent. An environment is formed in which the solvent coexists. Such an environment is advantageous for dissolving the (B) surface treatment agent present on the surface of (A) the cellulose nanofibers and uniformly applying the (B) surface treatment agent to the (A) cellulose nanofibers. There is, to improve the redispersion of the dried cellulose nanofibers in water and organic solvents, and to improve the dispersion of the cellulose nanofiber composition (e.g., water-containing dispersion and dried body) in the resin composition. contribute to On the other hand, since the upper limit of the boiling point of the water-soluble organic solvent (D) is within the above range, the water-soluble organic solvent (D) can be sufficiently vaporized during the production of the resin composition. This tends to suppress the plasticization of the resin composition by (D) the water-soluble organic solvent and maintain good strength.

In a typical embodiment, the lower limit of the dielectric constant at 25° C. of (D) the water-soluble organic solvent is 1, preferably 2, more preferably 3, more preferably 5, and most Seven is preferred. Also, the upper limit of the dielectric constant at 25° C. is preferably 80, more preferably 70, still more preferably 60, and most preferably 50. If the dielectric constant of (D) the water-soluble organic solvent is in the above range, it is possible to uniformly disperse the surface treatment agent (B) in the dispersion liquid, and even in the process of drying, (B) Precipitation is thought to be suppressed even above the cloud point of the surface treatment agent.

In one embodiment of the cellulose nanofiber water-containing dispersion, the preferred amount of (D) the water-soluble organic solvent is 0.1 to 100 parts by mass of the (D) water-soluble organic solvent per 100 parts by mass of (A) cellulose nanofibers. part amount. The upper limit is more preferably 80 parts by mass, still more preferably 50 parts by mass, and particularly preferably 20 parts by mass. Although the lower limit is not particularly limited, it is preferably 0.5 parts by mass, more preferably 1 part by mass, and most preferably 5 parts by mass. (D) By setting the upper limit amount of the water-soluble organic solvent to the above, the surface treatment agent can be uniformly coated on the cellulose nanofibers. (D) The water-soluble organic solvent can enhance the redispersibility of the dried cellulose nanofibers in water. In addition, there is a tendency that the cellulose nanofiber composition (for example, water-containing dispersion and dried body) is well dispersed in the resin composition.

In one embodiment of the dried cellulose nanofibers, the content of (D) the water-soluble organic solvent is in the range of 0 to 10000 ppm based on the mass of the entire dried body. The upper limit is more preferably 5000 ppm, still more preferably 3000 ppm, still more preferably 2500 ppm, particularly preferably 1500 ppm. Although the lower limit is not particularly limited, it is preferably 100 ppm, more preferably 150 ppm, and most preferably 300 ppm. (D) When the upper limit amount of the water-soluble organic solvent is as above, the cellulose nanofibers tend to be uniformly coated with the surface treatment agent. Further, when the lower limit amount of (D) the water-soluble organic solvent is as above, the redispersibility of the dried cellulose nanofibers in water and the dispersibility in the resin composition tend to be good.

In one aspect of the resin composition and the resin molded article, the content of (D) the water-soluble organic solvent is based on the mass of the entire resin composition or resin molded article, and (D) the water-soluble organic solvent is in the range of 0 to 5000 ppm. is within. The upper limit is more preferably 4000 ppm, still more preferably 3500 ppm, still more preferably 2500 ppm, and particularly preferably 1000 ppm. Although the lower limit is not particularly limited, it 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 (D) above, the plasticization of the thermoplastic resin (E) can be suppressed and the strength can be maintained satisfactorily. Further, by setting the lower limit amount of (D) the water-soluble organic solvent as above, the dispersibility of (A) cellulose nanofibers in (E) thermoplastic resin can be enhanced.

The amount of (D) the water-soluble organic solvent in the cellulose nanofiber composition (for example, the water-containing dispersion and the dried product) can be easily confirmed by a person skilled in the art by a general method. Although the confirmation method is not limited, the following methods can be exemplified. A cellulose nanofiber composition (for example, a water-containing dispersion or a dry body) is subjected to direct pyrolysis GCMS measurement, and (D) the water-soluble organic solvent can be qualitatively identified from the chromatogram and mass spectrum. Using the (D) water-soluble organic solvent detected at this time, the content in the cellulose nanofiber composition (for example, a water-containing dispersion and a dry body) can be quantified by creating a calibration curve under the same conditions. I can.

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

«(E) Thermoplastic resin»
The (E) thermoplastic resin that can be used in the present invention typically has a number average molecular weight of 5,000 or more. The number average molecular weight of the present disclosure is a value measured in terms of standard polymethyl methacrylate using GPC (gel permeation chromatography). (E) Thermoplastic resins include crystalline resins having a melting point in the range of 100°C to 350°C, and amorphous resins having a glass transition temperature in the range of 100°C to 250°C. (E) The thermoplastic resin may be composed of one or more polymers which may be homopolymers or copolymers.

The melting point of the crystalline resin referred to here is the peak top of the endothermic peak that appears when the temperature is raised from 23° C. at a rate of 10° C./min using a differential scanning calorimeter (DSC). means temperature. When two or more endothermic peaks appear, the peak top temperature of the endothermic peak on the highest temperature side is indicated. The enthalpy of the endothermic peak at this time is desirably 10 J/g or more, more desirably 20 J/g or more. In the measurement, it is desirable to use a sample obtained by heating the sample once to a temperature condition of 20° C. or more above the melting point to melt the resin and then cooling it to 23° C. at a rate of 10° C./min.

In addition, the glass transition temperature of the amorphous resin referred to here is measured at an applied frequency of 10 Hz while increasing the temperature from 23 ° C. at a rate of 2 ° C./min using a dynamic viscoelasticity measuring device. Secondly, it is the peak top temperature of the peak at which the storage modulus is greatly reduced and the loss modulus is maximized. When two or more loss modulus peaks appear, the peak top temperature of the peak on the highest temperature side is indicated. In order to improve the measurement accuracy, it is desirable that the measurement frequency is at least once every 20 seconds. In addition, although there is no particular limitation on the method of preparing a sample for measurement, it is desirable to use a piece cut out of a hot press molded product from the viewpoint of eliminating the influence of molding distortion, 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.

(E) Thermoplastic resins include polyamide-based resins, polyester-based resins, polyacetal-based resins, polycarbonate-based resins, polyacrylic-based resins, polyphenylene ether-based resins (polyphenylene ether is blended with other resins or modified by graft polymerization. modified polyphenylene ether), polyarylate-based resin, polysulfone-based resin, polyphenylene sulfide-based resin, polyethersulfone-based resin, polyketone-based resin, polyphenylene ether ketone-based resin, polyimide-based resin, polyamideimide-based resin, polyetherimide resins, polyurethane resins, polyolefin resins (eg α-olefin (co)polymers), various ionomers, and the like.

(E) Preferred specific examples of thermoplastic resins include high-density polyethylene, low-density polyethylene (eg linear low-density polyethylene), polypropylene, polymethylpentene, cyclic olefin resins, 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, ethylene-acrylic acid modified product, ethylene-vinyl acetate copolymer and its acid-modified product, (ethylene and/or propylene) and (unsaturated carboxylic acid and/or unsaturated At least part of the carboxyl groups of the copolymer of (ethylene and/or propylene) and (unsaturated carboxylic acid and/or unsaturated carboxylic acid ester) are obtained by metal salting block copolymers of conjugated dienes and vinyl aromatic hydrocarbons, 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 copolymer rubbers, isoprene rubber, butyl rubber, 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 , acrylic such as polysulfide rubber, silicone rubber, fluororubber, urethane rubber, polyvinyl chloride, polystyrene, polyacrylate, polymethacrylate, acrylonitrile-based copolymer, acrylonitrile-butanediene-styrene (ABS) resin, acrylonitrile styrene (AS) resin, cellulosic resin such as cellulose acetate, vinyl chloride/ethylene copolymer, vinyl chloride/vinyl acetate copolymer, ethylene/vinyl acetate copolymer, and ethylene/acetic acid saponified products of vinyl copolymers, and the like.

These may be used individually by 1 type, and may use 2 or more types together. When two or more are used in combination, they may be used as a polymer alloy. In addition, the above thermoplastic resins modified with at least one compound selected from unsaturated carboxylic acids, their acid anhydrides and their derivatives can also be used.

Among these, polyolefin resins, polyamide resins, polyester resins, polyacetal resins, polyacrylic resins, polyphenylene ether resins, and polyphenylene sulfide resins are considered from the viewpoint of heat resistance, moldability, design properties and mechanical properties. 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, particularly polyamides One or more resins selected from the group consisting of polyacetal-based resins and polyacetal-based resins are more preferable from the viewpoint of handleability and cost.

Polyolefin resins are polymers obtained by polymerizing monomer units containing olefins (eg, α-olefins). Specific examples of polyolefin-based resins are not particularly limited, but ethylene-based (co)polymers exemplified by low-density polyethylene (e.g., linear low-density polyethylene), high-density polyethylene, ultra-low-density polyethylene, ultra-high molecular weight polyethylene, etc. Polypropylene (co)polymers exemplified by coalescence, polypropylene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-acrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene -Copolymers of α-olefins represented by glycidyl methacrylate copolymers and other monomer units.

Polypropylene is the most preferred polyolefin resin. Particularly preferred is a polypropylene having a melt mass flow rate (MFR) of 3 g/10 min or more and 30 g/10 min or less, measured at 230° C. under a load of 21.2 N according to ISO1133. The lower limit of MFR is more preferably 5 g/10 minutes, still more preferably 6 g/10 minutes, and most preferably 8 g/10 minutes. Also, the upper limit is more preferably 25 g/10 minutes, still more preferably 20 g/10 minutes, and most preferably 18 g/10 minutes. The MFR desirably does not exceed the above upper limit from the viewpoint of improving the toughness of the composition, and preferably does not exceed the above lower limit from the viewpoint of the fluidity of the composition.

Acid-modified polyolefin resins are also suitable for use in order to increase 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 the modification rate can be easily increased. The modification method is not particularly limited, but a common method is to melt and knead the resin by heating it to the melting point or higher in the presence/absence of a peroxide. As the polyolefin resin to be acid-modified, all the polyolefin resins described above can be used, but polypropylene is particularly suitable for use.

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

The melt mass flow rate (MFR) of the acid-modified polypropylene, measured at 230° C. and a load of 21.2 N according to ISO 1133, is preferably 50 g/10 minutes or more in order to increase the affinity with the cellulose interface. preferable. A more preferred lower limit is 100 g/10 min, even more preferably 150 g/10 min, and most preferably 200 g/10 min. Although there is no particular upper limit, it is 500 g/10 minutes for maintenance of mechanical strength. By setting the MFR within this range, it is possible to enjoy the advantage of being more likely to exist at the interface between the cellulose and the resin.

Polyamide-based resins preferable as thermoplastic resins are not particularly limited, but are obtained by 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-1,3-dicarboxylic acid, benzene-1,4-dicarboxylic acid, etc., cyclohexane-1,3- Polyamide 6,6, polyamide 6,10, polyamide 6,11, polyamide 6,12, polyamide 6,T, polyamide obtained as a copolymer with dicarboxylic acids such as dicarboxylic acid and cyclohexane-1,4-dicarboxylic acid 6,I, polyamide 9,T, polyamide 10,T, polyamide 2M5,T, polyamide MXD,6, polyamide 6,C, polyamide 2M5,C, etc.; copolymers such as polyamide 6, T/6, I);

Among these polyamide resins, aliphatic polyamides such as polyamide 6, polyamide 11, polyamide 12, polyamide 6,6, polyamide 6,10, polyamide 6,11, and polyamide 6,12, and polyamide 6,C and polyamide 2M5,C Alicyclic polyamides such as

The terminal carboxyl group concentration of the polyamide-based resin is not particularly limited, but the lower limit is preferably 20 μmol/g, more preferably 30 μmol/g. Also, the upper limit of the terminal carboxyl group concentration is preferably 150 μmol/g, more preferably 100 μmol/g, and still more 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 carboxyl end group ratio lower limit is more preferably 0.35, still more preferably 0.40, and most preferably 0.45. The upper limit of the carboxyl terminal group ratio is more preferably 0.90, still more preferably 0.85, and most preferably 0.80. The carboxyl terminal group ratio is desirably 0.30 or more from the viewpoint of the dispersibility of (A) the cellulose nanofibers in the resin composition, and is preferably 0.95 or less from the viewpoint of the color tone of the resulting resin composition. It is desirable to

A known method can be used as a method for adjusting the terminal group concentration of the polyamide-based 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., can be used to achieve a predetermined terminal group concentration during the polymerization of the polyamide. A method of adding a terminal adjuster that reacts with the terminal group to the polymerization liquid can be used.

Terminal modifiers that react with terminal amino groups 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 isobutyric acid. Alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; Benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenylacetic acid and other aromatic monocarboxylic acids carboxylic acid; and a plurality of mixtures arbitrarily selected from these. Among these, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, and stearic acid are preferred in terms of reactivity, stability of blocked ends, and price. and benzoic acid are preferred, with acetic acid being most preferred.

Terminal modifiers that react with terminal carboxyl groups include, for example, aliphatic monoamines; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine, and any mixtures thereof. Among them, one or more terminals selected from the group consisting of butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine and aniline from the viewpoint of reactivity, boiling point, stability of capped terminals, price, etc. Modifiers are preferred.

The concentrations of these amino terminal groups and carboxyl terminal groups are preferably determined from the integrated values of characteristic signals corresponding to each terminal group by ¹ H-NMR from the viewpoint of accuracy and simplicity. As a method for determining the concentration of these terminal groups, specifically, the method described in JP-A-7-228775 is recommended. When using this method, deuterated trifluoroacetic acid is useful as a measurement solvent. In addition, the number of ¹ H-NMR integrations must be at least 300 scans even when measured with an instrument having sufficient resolution. In addition, the terminal group concentration can also be measured by a titration method as described in JP-A-2003-055549. However, quantification by ¹ H-NMR is more preferable in order to minimize the influence of mixed additives, lubricants, and the like.

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

In the present disclosure, "intrinsic viscosity" is synonymous with viscosity generally called intrinsic viscosity. A specific method for obtaining this viscosity is to measure the ηsp/c of several measurement solvents with different concentrations in 96% concentrated sulfuric acid at a temperature of 30°C, and measure the respective ηsp/c and concentration (c ) and extrapolate the concentration to zero. This value extrapolated to zero is the intrinsic viscosity. These details are described, for example, in Polymer Process Engineering (Prentice-Hall, Inc. 1994), pages 291-294.

At this time, it is desirable from the viewpoint of accuracy that the points for several measurement solvents having different concentrations should be at least 4 points. The concentrations of the different viscometric solutions recommended are preferably at least 4 points: 0.05 g/dL, 0.1 g/dL, 0.2 g/dL, 0.4 g/dL.

Preferred polyester resins as thermoplastic resins 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 composed of 3-hydroxyalkanoic acid), polylactic acid (PLA), polycarbonate (PC), etc. 1 type(s) or 2 or more types can be used. Among these, more preferred polyester resins include PET, PBS, PBSA, PBT, and PEN, and more preferred are PBS, PBSA, and PBT.

In addition, the terminal groups of the polyester resin can be freely changed depending on the monomer ratio during polymerization and the presence or absence and amount of addition of a terminal stabilizer. ([COOH]/[total terminal groups]) is preferably 0.30 to 0.95. The lower limit of the carboxyl terminal group ratio is more preferably 0.35, still more preferably 0.40, and most preferably 0.45. Also, the upper limit of the carboxyl terminal group ratio is more preferably 0.90, still more preferably 0.85, and most preferably 0.80. The carboxyl terminal group ratio is desirably 0.30 or more from the viewpoint of dispersibility of (A) cellulose nanofibers in the composition, and 0.95 or less from the viewpoint of the color tone of the resulting composition. is desirable.

Polyacetal-based resins that are preferable as thermoplastic resins generally include homopolyacetal made from formaldehyde and copolyacetal 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 comonomer component (eg, 1,3-dioxolane) is preferably within the range of 0.01 to 4 mol %. A more preferable lower limit of the comonomer component amount is 0.05 mol %, more preferably 0.1 mol %, and particularly preferably 0.2 mol %. A more preferred upper limit is 3.5 mol %, more preferably 3.0 mol %, particularly preferably 2.5 mol %, most preferably 2.3 mol %. From the viewpoint of thermal stability during extrusion and molding, the lower limit is preferably within the above range, and from the viewpoint of mechanical strength, the upper limit is preferably within the above range.

≪Other ingredients≫
Next, other components that can be used in the present invention are described in detail. The resin composition of the present embodiment can contain various stabilizers conventionally used for thermoplastic resins within a range that does not impair the purpose of the present embodiment. Examples of stabilizers include, but are not limited to, the following inorganic fillers, lubricating oils, and the like. These may be used alone or in combination of two or more. These can be used by purchasing commercially available reagents and products.

The inorganic filler is, but is not limited to, at least one compound selected from the group consisting of fibrous particles and/or plate-like particles and inorganic pigments. The fibrous particles and plate-like particles referred to herein are particles having an average aspect ratio of 5 or more among the fibrous particles and plate-like particles present in the resin molding. The amount of the inorganic filler added is not particularly limited, but it is preferable that the inorganic filler is in the range of 0.002 to 50 parts by mass with respect to 100 parts by mass of the (E) thermoplastic resin. By setting the amount of the stabilizer to be added within the above range, the handleability of the resin composition can be enhanced.

The lower limit of the molecular weight of the lubricating oil is preferably 100, more preferably 400, even more preferably 500. Moreover, 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, and even more preferably 20°C. A molecular weight of 100 or more tends to improve the slidability of the lubricating oil. Further, by setting the molecular weight to 1,000,000 or less, there is a tendency that the lubricating oil can be well dispersed and the wear resistance is improved. Further, by setting the melting point to −50° C. or higher, the fluidity of the lubricating oil present on the surface of the molded article is maintained, and abrasive wear is suppressed, thereby tending to improve the wear resistance of the molded article. Further, by setting the melting point to 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 point of view, the molecular weight and melting point of the lubricating oil are preferably within the above ranges. The above melting point is 2.5° C. lower than the pour point of the lubricating oil. The pour point can be measured according to JIS K2269.

The lubricating oil that can be used in the present embodiment is not limited to the following, but any substance that can improve the friction and wear characteristics of the thermoplastic resin molded body, such as engine oil, cylinder oil, etc. or paraffin oil (Idemitsu Kosan Co., Ltd. Diana Process Oil PS32, etc.), naphthenic oil (Idemitsu Kosan Co., Ltd. Diana Process Oil NS90S, etc.), aroma oil (Idemitsu Kosan Co., Ltd. Diana Process Oil AC12, etc.), silicone oils (Shin-Etsu Chemical Co., Ltd. G30 series, etc.) (e.g., silicone oils represented by polydimethylsiloxane, silicone gums, modified silicone gums, etc.) can be mentioned. A suitable lubricating oil may be selected from commercially available lubricating oils and used as it is or, if desired, it may be blended as appropriate. Among these, paraffin-based oils and silicone-based oils are preferred because they are excellent from the viewpoint of slidability and are readily available industrially. These lubricating oils may be used alone or in combination of two or more.

(E) 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, 0.3 parts by mass is further preferable. The upper limit of the content is also not particularly limited, but is preferably 5.0 parts by mass, more preferably 4.5 parts by mass, and even more preferably 4.2 parts by mass. When the content of the lubricating oil is within the range described above, the abrasion resistance of the cellulose-containing resin composition tends to improve. In particular, when the lubricating oil content is 0.1 parts by mass or more, sufficient slidability can be ensured, and wear resistance tends to improve. Further, 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-containing resin composition that can withstand uses such as gears tends to be ensured.

When the range of the content of the lubricating oil in the cellulose-containing resin composition of the present embodiment is adjusted as described above, it is preferable from the viewpoint of improving wear characteristics during sliding and further improving stable slidability.

An apparatus for producing the resin composition of the present embodiment is not particularly limited, and a kneader in general use can be applied. Examples of the kneader include, but are not limited to, a single-screw or multi-screw kneading extruder, a roll, a Banbury mixer, and the like. Among them, a twin-screw extruder equipped with a decompression device and a side feeder facility is preferable.

The resin composition of the present invention can be provided in various forms. Specific examples thereof include resin pellets, sheets, fibers, plates, rods, and the like, but resin pellets are more preferable from the standpoint of ease of post-processing and ease of transportation. Preferable pellet shapes in this case include round, elliptical, and cylindrical shapes, which differ depending on the cutting method during extrusion. Pellets cut by a cutting method called underwater cutting are often round, and pellets cut by a cutting method called hot cutting are often round or elliptical, and are called strand cuts. 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 as a pellet diameter. In the case of cylindrical pellets, the preferable diameter is 1 mm or more and 3 mm or less, and the preferable length is 2 mm or more and 10 mm or less. From the viewpoint of operational stability during extrusion, the above diameter and length are preferably at least the lower limit, and from the viewpoint of biting into a molding machine in post-processing, they are preferably at most the upper limit.

Specific examples of the method for producing the resin composition include the following methods.
(1) Using a single-screw or twin-screw extruder, a mixture of a thermoplastic resin, cellulose nanofibers, a surface treatment agent, and an antioxidant is melt-kneaded, extruded into strands, cooled and solidified in a water bath, A method of obtaining a pellet-shaped compact.
(2) Using a single-screw or twin-screw extruder, a mixture of a thermoplastic resin, cellulose nanofibers, a surface treatment agent, and an antioxidant is melt-kneaded, extruded into a rod or cylinder, and cooled to form an extrudate. how to get
(3) Using a single-screw or twin-screw extruder, a mixture of a thermoplastic resin, cellulose nanofibers, a surface treatment agent, and an antioxidant is melt-kneaded, and extruded from a T-die to form a sheet or film-like molded body. how to get

Moreover, the following method is mentioned as a specific example of the melt-kneading method of the mixture of a thermoplastic resin, a cellulose nanofiber, a surface treating agent, and an antioxidant.
(1) A method of collectively melting and kneading a thermoplastic resin and a mixed powder of cellulose nanofibers, a surface treatment agent, and an antioxidant mixed at a desired ratio.
(2) After melt-kneading a thermoplastic resin and, if necessary, a surface treatment agent and an antioxidant, cellulose nanofiber powder mixed at a desired ratio, and if necessary, a surface treatment agent and an antioxidant are added, and A method of melt-kneading.
(3) After melt-kneading a thermoplastic resin, cellulose nanofibers mixed at a desired ratio, a surface treatment agent, an antioxidant mixed powder, and water, cellulose nanofibers and water mixed at a desired ratio, and a method of melting and kneading together after mixing a surface treatment agent if necessary.
(4) After melt-kneading the thermoplastic resin and, if necessary, the surface treatment agent, the thermoplastic resin, cellulose nanofibers, surface treatment agent, antioxidant mixed powder, and water mixed at a desired ratio are added. , and a method of further melt-kneading.
(5) A method in which the above (1) to (4) are separately added to the top and side at an arbitrary ratio using a single-screw or twin-screw extruder, and melt-kneaded.

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

The member of the present embodiment obtained from the cellulose-containing resin composition described above is preferably used in applications that require high paintability, sliding resistance, and little dimensional change due to heat after molding. be.

Applications of the member of the present embodiment are not limited to the following, but include, for example, 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, and shutters. , reels, shafts, joints, axles, bearings, guides, etc.; outsert-molded resin parts, insert-molded resin parts, chassis, trays, side plates, printers, and offices typified by copiers Parts for automation equipment; VTR (Video tape recorder), 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 , CD (Compact disk) [including CD-ROM (Read only memory), CD-R (Recordable), 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, and other optical disc drives; MFD (Multi-Function Display), MO (Magneto-Optical Disk), music, video or information equipment represented by navigation systems and mobile personal computers, parts for communication equipment represented by mobile phones and facsimiles; parts for electrical equipment; electronics Further, the molded product of the present embodiment can be used as parts for automobiles such as gasoline tanks, fuel pump modules, valves, fuel-related parts such as gasoline tank flanges; Door-related parts such as handles, window regulators, and speaker grills; seat belt peripheral parts such as seat belt slip rings and press buttons; parts such as combination switch parts, switches, and clips; and mechanical pencils. mechanical parts for inserting and removing the lead of mechanical pencils; sinks, drains, and drain plug opening/closing mechanism parts; vending machine opening/closing lock mechanisms, product discharge mechanism parts; cord stoppers, adjusters, and buttons for clothing watering nozzles, watering hose connection joints; stair handrails and construction articles as flooring supports; disposable cameras, toys, fasteners, chains, conveyors, buckles, sporting goods, vending machines, furniture, musical instruments, Industrial machine parts (e.g., electromagnetic equipment housing, roll materials, transport arms, medical equipment parts, etc.), general machine parts, automobile/railway/vehicle parts (e.g., outer panels, chassis, aerodynamic members, seats, transmission interiors, etc.) friction materials, etc.), ship parts (hulls, seats, etc.), aviation-related parts (fuselage, main wings, tail wings, rotor blades, fairings, cowls, doors, seats, interior materials, etc.), spacecraft, satellites Materials (motor cases, main wings, structures, antennas, etc.), electronic/electric parts (e.g., personal computer housings, mobile phone housings, OA equipment, AV equipment, telephones, facsimiles, home appliances, toys, etc.), construction and civil engineering Materials (e.g. rebar replacement materials, truss structures, suspension bridge cables, etc.), daily necessities, sports and leisure goods (e.g., golf club shafts, fishing rods, tennis and badminton rackets, etc.), housing members for wind power generation, etc. It can also be used as a material for containers and packaging members, for example, high-pressure containers filled with hydrogen gas and the like used in fuel cells.

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

≪Linear expansion coefficient≫
Since the resin composition of the present embodiment contains (A) cellulose nanofibers, it is possible to exhibit lower linear expansion than conventional molded articles. Specifically, the coefficient of linear expansion of the resin molding in the temperature range of 0° C. to 60° C. is preferably 60 ppm/K or less. The linear expansion coefficient is more preferably 50 ppm/K or less, still more preferably 45 ppm/K or less, and most preferably 35 ppm/K or less. Although the lower limit of the coefficient of linear expansion is not particularly limited, it is preferably 5 ppm/K, more preferably 10 ppm/K from the viewpoint of ease of production.

The present invention will be further described based on examples, but the present invention is not limited to these examples.

≪Raw material and evaluation method≫
The raw materials and evaluation methods used are described below.

≪(A) Cellulose nanofibers≫
(a-1) Cellulose A
After cutting the linter pulp, it is heated in hot water of 120° C. or higher for 3 hours using an autoclave, and the refined pulp from which the hemicellulose portion has been removed is pressed to a solid content of 1.5% by weight in pure water. After being highly short-fiberized and fibrillated by a beating treatment to obtain a defibrated cellulose, the fibrillated cellulose was fibrillated with a high-pressure homogenizer (operation pressure: 10 times at 85 MPa) at the same concentration. Here, in the beating treatment, a disc refiner is used, and after processing for 2.5 hours with a beating blade with a high cutting function (hereinafter referred to as a cutting blade), a beating blade with a high defibrating function (hereinafter referred to as a defibrating blade) is applied. Beating was further carried out for 2 hours using the cellulose A to obtain cellulose A.

(a-2) cellulose B
Cellulose E was prepared by the method described in [0108] Example 1 of WO2017/159823.

<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 "The Japanese Pharmacopoeia 14th Edition" (published by Hirokawa Shoten).

<Crystal form and crystallinity of cellulose component>
Using an X-ray diffractometer (manufactured by Rigaku Co., Ltd., multi-purpose X-ray diffractometer), a diffraction pattern was measured (at room temperature) by the powder method, and the degree of crystallinity was calculated by the Segal method. Also, the crystal form was measured from the obtained X-ray diffraction image.

<L/D of cellulose component>
A cellulose component is suspended in pure water 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 conditions: rotation speed 15,000 rpm x 5 minutes). The aqueous dispersion dispersed in is diluted with pure water to 0.1 to 0.5% by mass, cast on mica, and air-dried, obtained when measured with an atomic force microscope (AFM). The ratio (L/D) of the long diameter (L) and short diameter (D) of the particle image obtained was obtained, and the average value of 100 to 150 particles was calculated.

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

<<(B) Surface treatment agent>>
(b-1) 11 parts by mass of polypropylene oxide (Mn2000) and 0.6 parts by mass of KOH as a catalyst were placed in a 2-liter autoclave, and after nitrogen substitution, 100 parts by mass of polyethylene oxide (Mn9000) was added and heated at 160°C for 4 hours. introduced gradually over time. After completion of the reaction, the mixture was neutralized with 1.2 parts by mass of lactic acid to obtain b-1.
(b-2) 130 parts by mass of polypropylene oxide (Mn2000) and 0.6 parts by mass of KOH as a catalyst are placed in a 2 L autoclave, and after purging with nitrogen, 100 parts by mass of polyethylene oxide (Mn750) are added and heated at 160°C for 4 hours. introduced gradually over time. After completion of the reaction, the mixture was neutralized with 1.2 parts by mass of lactic acid to obtain b-2.
(b-3) 150 parts by mass of polypropylene oxide (Mn2100) and 0.6 parts by mass of KOH as a catalyst are placed in a 2 L autoclave, and after purging with nitrogen, 100 parts by mass of polyethylene oxide (Mn700) are added and heated at 160°C for 4 hours. introduced gradually over time. After completion of the reaction, the mixture was neutralized with 1.2 parts by mass of lactic acid to obtain b-3.

(b-4) In a 2 L autoclave, 160 parts by mass of polypropylene oxide (Mn2050) and 0.6 parts by mass of KOH as a catalyst are charged, nitrogen-substituted, and then 100 parts by mass of polyethylene oxide (Mn625) are added. introduced gradually over time. After completion of the reaction, the mixture was neutralized with 1.2 parts by mass of lactic acid to obtain b-4.
(b-5) 180 parts by mass of polypropylene oxide (Mn2000) and 0.6 parts by mass of KOH as a catalyst are placed in a 2 L autoclave, and after nitrogen substitution, 100 parts by mass of polyethylene oxide (Mn550) are added and heated at 160°C for 4 hours. introduced gradually over time. After completion of the reaction, the product was neutralized with 1.2 parts by mass of lactic acid to obtain b-5.
(b-6) 230 parts by mass of polypropylene oxide (Mn1950) and 0.6 parts by mass of KOH as a catalyst are placed in a 2 L autoclave, and after nitrogen substitution, 100 parts by mass of polyethylene oxide (Mn425) are added and heated at 160°C for 4 hours. introduced gradually over time. After completion of the reaction, neutralization was performed with 1.2 parts by mass of lactic acid to obtain b-6.

(b-7) In a 2 L autoclave, 250 parts by mass of polypropylene oxide (Mn1750) and 0.6 parts by mass of KOH as a catalyst are charged, nitrogen-substituted, 100 parts by mass of polyethylene oxide (Mn325) are added, and the mixture is heated at 160°C for 4 hours. introduced gradually over time. After completion of the reaction, neutralization was carried out with 1.2 parts by mass of lactic acid to obtain b-7.
(b-8) In a 2 L autoclave, 550 parts by mass of polypropylene oxide (Mn1870) and 0.6 parts by mass of KOH as a catalyst are charged, nitrogen-substituted, and then 100 parts by mass of polyethylene oxide (Mn165) are added. introduced gradually over time. After completion of the reaction, neutralization was carried out with 1.2 parts by mass of lactic acid to obtain b-8.
(b-9) In a 2 L autoclave, 700 parts by mass of polypropylene oxide (Mn1750) and 0.6 parts by mass of KOH as a catalyst are charged, nitrogen-substituted, and then 100 parts by mass of polyethylene oxide (Mn125) are added. introduced gradually over time. After completion of the reaction, neutralization was carried out with 1.2 parts by mass of lactic acid to obtain b-9.

(b-10) Polyethylene oxide (Mn31000) was used.
(b-11) Into a 2 L autoclave, 100 parts by mass of glycerin (Mn92) and 0.6 parts by mass of KOH as a catalyst are placed and substituted with nitrogen, and then 340 parts by mass of polyethylene oxide (Mn325) are successively added at 160° C. over 4 hours. introduced. After completion of the reaction, 680 parts by mass of polypropylene oxide (Mn650) was added and introduced successively at 160° C. over 4 hours. After completion of the reaction, the product was neutralized with 1.2 parts by mass of lactic acid to obtain b-11.
(b-12) Brownon RCW-20 manufactured by Aoki Oil Industry Co., Ltd. was used.

<(B) Measurement of molecular weight of surface treatment agent>
For each surface treatment agent, the molecular weight of 10,000 or more was measured by GPC, and the 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 are solid at room temperature were melted by heating to the melting point or above, then dissolved in water and measured.
Device name: HLC-8320GPC EcoSEC (manufactured by Tosoh Corporation)
Column: Shodex GPC KD-802 + KD-80 (manufactured by Showa Denko Co., Ltd.)
Eluent: 0.01M LiBr in DMF
Flow rate: 1.0 mL/min
Detector: RI
Measurement temperature: 50°C

[HPLC measurement]
Those that are solid at room temperature were melted by heating to the melting point or above, then dissolved in water and measured.
Apparatus name: HP-1260 (manufactured by Agilent Technologies Inc.)
Column: TSKgel ODS-80Ts (manufactured by Tosoh Corporation)
Mobile phase: Solvent gradient with water/acetonitrile 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

<Melting point of (B) surface treatment agent>
Those that are solid at room temperature were melted by heating above the melting point, sealed in an aluminum pan, and measured.
Device name: DSC8500 manufactured by PerkinElmer Co., Ltd. Measurement temperature: -60 to 100°C

<(B) Clouding point of surface treatment agent>
Those that are solid at room temperature were melted by heating above the melting point and then dissolved in water to obtain samples.
Apparatus 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
For those that did not show a cloud point by the above method, the temperature was raised after sealing in a glass container that can be visualized, and the point at which the precipitation aqueous solution became cloudy was visually observed to measure the cloud point.

«(C) Antioxidant»
The antioxidants listed in Table 3 were used. c-4 was first dissolved in hexane and then reprecipitated by adding acetone and used. Others were dissolved with acetone and used.

<<(D) Water-soluble organic solvent>>
Solvents listed in Table 4 were used. For the dielectric constant of d-2, the numbers described in Chemical Handbook Basic Edition, IP 770-777, Revised 5th Edition, edited by The Chemical Society of Japan, were used. Except for c-2, measurement was performed using a HEWLETT PACKARD Presion LCR meter HP4284A (liquid measurement electrode HP 16452A, solid measurement electrode HP 16451B).

«(E) Thermoplastic resin»
The thermoplastic resins listed in Table 5 were used.

<<Production-1 Cellulose nanofiber aqueous dispersion>>
(B) The surface treatment agent was poured into distilled water under an environment of 20° C., placed in a sealed container, and allowed to stand overnight for dissolution. Separately, (C) an antioxidant was dissolved in a soluble solvent.
The next day, after confirming that the solution was a uniform surface treatment agent solution, (C) the antioxidant solution was added. The resulting (B) surface treatment agent aqueous solution is added to a cellulose nanofiber slurry (solid content 10 to 20 wt%), and stirred for 30 minutes using a high-power general-purpose stirrer BLh3000 manufactured by Sintokagaku Co., Ltd. to obtain uniform cellulose. A nanofiber water-containing dispersion was obtained.

≪Production-2 Dry cellulose nanofibers≫
The cellulose nanofiber water-containing dispersion obtained in the previous production was dried under reduced pressure at 40° C. for 1 hour with stirring using ACM-5LVT manufactured by Kodaira Seisakusho Co., Ltd. to obtain uniform crumb-like masses. This was dried in a nitrogen atmosphere at 120° C. for 24 hours using an Inert Oven DN43HI manufactured by Yamato Scientific Co., Ltd. to obtain a dried cellulose nanofiber.

≪Manufacturing-3 resin composition≫
Using a twin-screw extruder (Toshiba Machine Co., Ltd. TEM-26SS extruder (L / D = 48, with vent), polyamide-based materials at 260 ° C., polypropylene-based materials at 190 ° C., polyoxymethylene-based materials The cylinder temperature is set to 200° C., (E) thermoplastic resin is supplied from the extruder main throat using a metering feeder, and the cellulose nanofiber water-containing dispersion or the cellulose nanofiber dry body is metered from the side of the extruder. The resin kneaded product is fed using a feeder and extruded into strands under the conditions of an extrusion rate of 15 kg/hour and a screw rotation speed of 250 rpm, quenched in a strand bath, and cut with a strand cutter to obtain a pellet-shaped resin composition. rice field.

<Resin composition odor>
1 kg of pellets immediately after the strand cutter was collected in a paper bag having a length of 50 cm and a width of 25 cm during the above <<manufacturing-3>>, and the odor was judged by five people. The judgment value was the average value of 5 people and was rounded off to the first decimal place.
Judgment criteria were as follows.
1: No odor was felt.
2: A slight odor was sensed.
3: A smell was sensed.
4: A strong odor was sensed.
5: The odor was sensed quite strongly.

≪Manufacturing-4 Molded body≫
Using an injection molding machine (EC-75NII, manufactured by Toshiba Machine Co., Ltd.), a multi-purpose test piece conforming to ISO294-3 was molded.
Polyamide-based materials: Conditions based on JIS K6920-2 Polypropylene-based materials: Conditions based on JIS K6921-2 Polyoxymethylene-based materials: Conditions based on JIS K7364-2 Raw resin (that is, thermoplastic resin alone) and resin composition For each of the products (that is, the cellulose-containing 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.

≪Molding Machine Retention≫
Separately from when molding a multi-purpose test piece conforming to ISO294-3 using the previous injection molding machine, an injection molding machine (EC-75NII, manufactured by Toshiba Machine Co., Ltd.) was used to increase the cylinder temperature to +20 ° C. (The standard temperature of each resin described above), the residence time is 30 minutes, the injection time is 35 seconds, and the cooling time is 15 seconds. got The mold temperature at this time was 70°C. This flat plate was molded, and the degree of yellowing of the molded piece was evaluated. Numerical values according to the degree of yellowing of the molded pieces are shown in the table. It was judged that the smaller the numerical value, the better the retention in the molding machine.
1: No discoloration was observed.
2: Slight yellowing is observed.
3: Slight yellowing is observed.
4: Yellowing is observed.
5: Yellowing is recognized even when viewed from a distance.

≪Moldability≫
Separately from when molding a multi-purpose test piece conforming to ISO294-3 using the previous injection molding machine, an injection molding machine (EC-75NII, manufactured by Toshiba Machine Co., Ltd.) was used to set the cylinder temperature to 250 ° C. A flat plate having a thickness of 2 mm, a length of 120 mm and a width of 80 mm was obtained by molding under the injection conditions of 35 seconds of injection time and 15 seconds of cooling time. The mold temperature at this time was 70°C. This flat plate was molded at 50 points, and the number of defective molding points was counted. Molding defects include silver streaks, sink marks, and poor appearance.
Numerical values according to the number of occurrences are listed in the table. It was judged that the smaller the numerical value, the better the moldability.
1: No molding defects were observed.
2: Defective molding was observed, but the score was 3 points or less.
3: Molding defects were more than 3 points and 5 points or less.
4: Molding defects were more than 5 points and 10 points or less.
5: Defective molding was more than 10 points.

≪Characteristic evaluation conditions/mechanical property measurement≫
<Cellulose nanofiber aqueous dispersion dilution test>
The cellulose nanofiber water-containing dispersion obtained in Production-1 was placed in a 20 ml Laboran screw vial manufactured by AS ONE Corporation, and diluted with distilled water to a cellulose concentration of 0.1% by mass. After stirring to obtain a uniform cellulose nanofiber water-containing dispersion, one drop was dropped on a slide glass, and a cover glass was placed on the drop. The cover glass was pressed, and the cellulose nanofiber aqueous dispersion protruding from the cover glass was removed using a Kimwipe manufactured by Nippon Paper Crecia Co., Ltd. The water-containing 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: Uniformly dispersed, no aggregation observed.
B: Dispersed, but some aggregation is observed.
C: Aggregation is confirmed.

<Dried cellulose nanofiber redispersion test-1>
The dried cellulose nanofibers obtained in Production-2 were placed in a 20 ml Labran screw vial manufactured by AS ONE Corporation, and diluted with hexafluoroisopropanol to a cellulose concentration of 1% by mass. After standing still for 24 hours, the mixture was stirred again to obtain a uniform cellulose nanofiber solution, and then visually inspected. It was determined that excellent re-solubility in an organic solvent means less aggregation of cellulose particles and excellent solubility in resins.
A: Uniformly dispersed.
B: Dispersed, but some aggregation is observed.
C: Aggregation is confirmed.

<Dried cellulose nanofiber redispersion test-2>
The dried cellulose nanofibers obtained in Production-2 were placed in a 20 ml Labran screw vial manufactured by AS ONE Corporation, and diluted with distilled water to a cellulose concentration of 1% by mass. After standing still for 24 hours, the mixture was stirred again to obtain a uniform cellulose nanofiber water-containing dispersion, and then visually inspected. It was determined that excellent re-solubility in distilled water means less aggregation of cellulose and excellent solubility in resin.
A: Uniformly dispersed.
B: Dispersed, but some aggregation is observed.
C: Aggregation is confirmed.

<Dried cellulose nanofiber heat resistance test>
The weight loss of the dried cellulose nanofibers obtained in Production-2 was measured in an air atmosphere at 170° C. for 60 minutes using PerkinElmer's 7 Series/UNIX (registered trademark) TGA7. It was judged that the smaller the amount of weight loss at this time, the smaller the amount of decomposition of the surface treatment agent and the better the heat resistance.

<Resin molding linear expansion coefficient>
From the central part of the multi-purpose test piece obtained in the above <<Manufacturing-4>>, a cubic sample of 4 mm in length, 4 mm in width, and 4 mm in length is cut out with a precision cut saw. and calculated the coefficient of expansion between 0°C and 60°C. It was evaluated that the lower the coefficient of linear expansion, the better the dispersibility of the cellulose nanofibers in the resin.

<Resin Mold Wear Resistance>
For the multi-purpose test piece obtained in the above <<Production-4>>, using a reciprocating friction and wear tester (AFT-15MS type manufactured by Toyo Seimitsu Co., Ltd.) and a SUS304 test piece (ball with a diameter of 5 mm) as a mating material, A sliding test was performed 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 wear amount (wear depth) of the sample after the sliding test was measured using a confocal microscope (OPTELICS (registered trademark) H1200, Lasertec Co., Ltd.). The abrasion depth was taken as the average value of the numerical values measured at n=4. The measurement points were at equal intervals of 12.5 mm from the edge of the wear scar. In addition, the lower the wear depth, the better the wear characteristics.

[Cellulose nanofiber aqueous dispersion Examples 1-1 to 1-42 and Comparative Examples 1-1 to 1-2]
Using the method described in Production-1, each component was used in the proportions described in Tables 6 to 8 to obtain each dispersion. The obtained dispersion was evaluated according to the evaluation method described above.

[Dried Cellulose Nanofiber Examples 2-1 to 2-42 and Comparative Examples 2-1 to 2-2]
Using the cellulose nanofiber aqueous dispersion obtained in the previous example (described in Tables 6 to 8), each cellulose nanofiber dry body (described in Tables 6 to 8) was obtained by the method described in Production-2. The obtained dried cellulose was evaluated according to the evaluation method described above.

[Resin Composition Examples 3-1 to 3-44 and Comparative Examples 3-1 to 3-5]
A resin composition (Table 9 ~ 14 description) was obtained. The obtained composition was molded by the method described in Manufacturing-5.

Examples and Comparative Examples listed in Tables 6 to 8 (Examples 1-1 to 1-42 and Comparative Examples 1-1 to 1-2, Examples 2-1 to 2-42 and Comparative Examples 2-1 to 2- For those not shown in Tables 9 to 14 of 2), ingredients other than (E) were used in the proportions shown in each table, and production was carried out by the methods described in Productions 1 and 2. Thereafter, a composition and a molded article were obtained by the methods described in Production-3 and -4.

Each molded article was evaluated according to the evaluation method described above.

By blending each component in an appropriate type and amount as described above, the aqueous dispersion of cellulose nanofibers and the dried cellulose nanofibers can be easily redispersed in water and an organic solvent, and It can be seen that it is excellent in dispersibility to. Moreover, it turns out that the cellulose nanofiber dry body is excellent in heat resistance.

It can be seen that the resin composition and resin molding are excellent in moldability, abrasion resistance in practical use, odor resistance, and moldability while providing excellent mechanical properties and thermal properties.

The cellulose nanofiber composition (for example, a water-containing dispersion) and the dried cellulose nanofibers according to the present invention can be dispersed in a system using water as a main medium by a simple method without aggregating the cellulose nanofibers, and can be heat-resistant. It has excellent dispersibility in water, organic solvents, and resins. In addition, since the cellulose nanofiber resin composition according to the present invention provides sufficient mechanical and thermal properties, abrasion resistance, excellent odor resistance, and excellent moldability, the resin composition has these properties. It is suitably applied to various required uses.

Claims (16)

(A) cellulose nanofibers, (B) a cellulose nanofiber surface treatment agent, and (C) an antioxidant, wherein the surface treatment agent is a nonionic interface having a hydrophilic segment and/or a hydrophobic segment A dried cellulose nanofiber composition, which is an active agent. (A) cellulose nanofibers, (B) a cellulose nanofiber surface treatment agent, and (C) an antioxidant, wherein the surface treatment agent is a hydrophilic segment that is a PEG block and/or a hydrophobic segment that is a PPG block A dried cellulose nanofiber composition having a sex segment. 3. The dry cellulose nanofiber composition according to claim 1 or 2, wherein (C) an antioxidant is contained in an amount of 0.01 to 100 parts by mass with respect to 100 parts by mass of the surface treatment agent (B). (B) The dried cellulose nanofiber composition according to any one of claims 1 to 3, wherein the surface treatment agent has a number average molecular weight of 200 to 30,000. (B) The dried cellulose nanofiber composition according to any one of claims 1 to 4, wherein the surface treatment agent has a cloud point of 10°C or higher. The dried cellulose nanofiber composition according to any one of claims 1 to 5, comprising 0.1 to 100 parts by mass of (B) a surface treatment agent with respect to 100 parts by mass of (A) cellulose nanofibers. (B) The dried cellulose nanofiber composition according to any one of claims 1 to 6, wherein the HLB value of the surface treatment agent is 0.1 or more and less than 12. (C) The antioxidant is selected from the group consisting of hindered phenol antioxidants, sulfur antioxidants, and phosphorus antioxidants, according to any one of claims 1 to 7. Dry cellulose nanofiber composition. (B) The cellulose nanos according to any one of claims 1 to 8, wherein the molecular structure of the surface treatment agent is one selected from an ABA-type triblock structure, tri-branched structure, and tetra-branched structure. A dry fiber composition. The dried cellulose nanofiber composition according to any one of claims 1 to 9, further comprising (D) a water-soluble organic solvent. (E) a thermoplastic resin, (A) cellulose nanofibers, (B) a surface treatment agent for cellulose nanofibers, and (C) an antioxidant, wherein the surface treatment agent comprises hydrophilic segments and/or hydrophobic A cellulose nanofiber resin composition that is a segmented nonionic surfactant, comprising (A) cellulose nanofibers, (B) a surface treatment agent for the cellulose nanofibers, and (C) an antioxidant. A cellulose nanofiber resin composition obtained by mixing a dried nanofiber composition and (E) a thermoplastic resin . (E) a thermoplastic resin, (A) cellulose nanofibers, (B) a surface treatment agent for cellulose nanofibers, and (C) an antioxidant, wherein the surface treatment agent is a PEG block hydrophilic segment and / Or a cellulose nanofiber resin composition having a hydrophobic segment that is a PPG block (excluding reactive surfactants) , comprising: (A) cellulose nanofibers; and (B) surface treatment of cellulose nanofibers A cellulose nanofiber resin composition obtained by mixing a dried cellulose nanofiber composition containing an agent and (C) an antioxidant, and (E) a thermoplastic resin. A method for producing a cellulose nanofiber resin composition,
The method includes mixing a dry cellulose nanofiber composition containing (A) cellulose nanofibers, (B) a cellulose nanofiber surface treatment agent, and (C) an antioxidant with (E) a thermoplastic resin. including
The method, wherein the surface treatment agent is a nonionic surfactant having a hydrophilic segment and/or a hydrophobic segment. A method for producing a cellulose nanofiber resin composition,
The method includes mixing a dry cellulose nanofiber composition containing (A) cellulose nanofibers, (B) a cellulose nanofiber surface treatment agent, and (C) an antioxidant with (E) a thermoplastic resin. including
The method, wherein the surface treatment agent has hydrophilic segments that are PEG blocks and/or hydrophobic segments that are PPG blocks. (E) The thermoplastic resin consists of 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. 15. A method according to claim 13 or 14, selected from the group. A method for manufacturing a resin molded body,
Producing a cellulose nanofiber resin composition by the method according to any one of claims 13 to 15, and molding the cellulose nanofiber resin composition,
A method, including