Storage method for composition containing hydrophobically modified cellulose fibers

Abstract

The present invention relates to a refrigerated storage method for a composition containing modified cellulose fibers (component (A)) and a non-aqueous liquid (component (B)) that is a liquid at 25°C and 1 atm. According to the present invention, it is possible to provide a storage method for suppressing an increase in viscosity of a composition containing modified cellulose fibers over time.

Description

Method for storing a composition containing hydrophobically modified cellulose fibers

[0001] The present invention relates to a method for storing a composition containing hydrophobically modified cellulose fibers.

[0002] In recent years, attention has been drawn to the fact that adding fine cellulose fibers to materials such as resins can significantly improve various mechanical properties of the materials. For example, Patent Document 1 discloses an example of a non-aqueous coating composition containing an epoxy resin and a fine cellulose fiber composite.

[0003] JP 2019-119881 A

[0004] That is, the present invention relates to the following [1] to

[16] . [1] A method for refrigerating and storing a composition containing the following components (A) and (B): Component (A): hydrophobically modified cellulose fiber Component (B): non-aqueous liquid that is liquid at 25°C and 1 atmosphere [2] A method for storing a composition containing the following components (A) and (B) at 20°C or below: Component (A): hydrophobically modified cellulose fiber Component (B): non-aqueous liquid that is liquid at 25°C and 1 atmosphere [3] A method for refrigerating and storing a composition containing the following components (A) and (B) at 20°C or below: Component (A): hydrophobically modified cellulose fiber Component (B): non-aqueous liquid that is liquid at 25°C and 1 atmosphere [4] A method for refrigerating and storing a composition comprising the following components (A) and (B): Component (A): Hydrophobically modified cellulose fiber Component (B): Non-aqueous liquid that is liquid at 25°C and 1 atmosphere [5] A method for storing a composition comprising the following components (A) and (B) at 20°C or below: Component (A): Hydrophobically modified cellulose fiber Component (B): Non-aqueous liquid that is liquid at 25°C and 1 atmosphere [6] A method for refrigerating and storing a composition comprising the following components (A) and (B) at 20°C or below: Component (A): Hydrophobically modified cellulose fiber Component (B): Non-aqueous liquid that is liquid at 25°C and 1 atmosphere [7] The method according to any one of [1] to [6] above, wherein the content of component (A) in the composition is 0.1 parts by mass or more and 100 parts by mass or less per 100 parts by mass of component (B). [8] The method according to any one of [1] to [7] above, wherein the content of component (A) in the composition is 0.1% by mass or more and 50% by mass or less. [9] The method according to any one of [1] to [8] above, wherein the content of the glucose moiety of component (A) in the composition is 0.1 parts by mass or more and 100 parts by mass or less per 100 parts by mass of component (B).

[10] The method according to any one of [1] to [9] above, wherein the content of the glucose moiety of component (A) in the composition is 0.1% by mass or more and 20% by mass or less.

[11] The method according to any one of [1] to

[10] above, wherein component (A) has a modifying group via an ionic bond and / or a covalent bond.

[12] The method according to

[11] above, wherein the modifying group possessed by component (A) is bonded to glucose constituting cellulose via an ionic bond and / or an amide bond.

[13] The method according to

[11] or

[12] above, wherein the modifying group carried by component (A) is one or more types selected from the group consisting of (a) a hydrocarbon group and (b) a polymer group.

[14] The method according to any one of

[11] to

[13] above, wherein the modifying group carried by component (A) is a group derived from one or more modifying compounds selected from the group consisting of primary amines, secondary amines, tertiary amines, and quaternary ammonium compounds.

[15] The method according to any one of [1] to

[14] above, wherein component (B) contains a non-aqueous resin and / or an organic solvent.

[16] The method according to any one of [1] to

[15] above, wherein the viscosity of the composition at 25°C after storage is 1 mPa s or more and 100,000 mPa s or less. Detailed Description of the Invention

[0005] The present inventors have investigated the physical properties of compositions containing hydrophobically modified cellulose fibers and found that the viscosity of such compositions may increase over time. Since an increase in viscosity of the composition significantly impairs handling, such as reducing the coatability when applied to a paint, it is necessary to suppress the increase in viscosity of such compositions during storage.

[0006] Therefore, the present invention relates to providing a storage method that suppresses an increase in viscosity over time of a composition containing hydrophobically modified cellulose fibers.

[0007] According to the present invention, it is possible to provide a storage method that suppresses an increase in viscosity over time of a composition containing hydrophobically modified cellulose fibers.

[0008] [Composition] The composition to be stored in the present invention is a composition containing component (A) and component (B), and a composition obtained by blending component (A) and component (B). Component (A): Hydrophobically modified cellulose fiber Component (B): Non-aqueous liquid that is liquid at 25°C and 1 atmosphere

[0009] As a result of investigations by the present inventors, although the mechanism is unclear, it is speculated that when the above composition is stored under non-refrigerated conditions, for example, at 25° C., the hydrophobically modified cellulose fibers slowly aggregate, resulting in an increase in viscosity of the composition. Therefore, it is speculated that storing the above composition in a refrigerator can slow down the aggregation rate of the hydrophobically modified cellulose fibers.

[0010] In the present invention, the "change in viscosity of a composition" refers to the change in viscosity of a composition before and after storage when the composition to be evaluated is stored, for example, for one day to six months. Specifically, when the rate of change in viscosity of a composition calculated from the viscosity of the composition measured by the method described in the Examples using the following formula is within a range of -50% to 50%, the viscosity change of the composition is determined to be suppressed. Rate of change in viscosity of composition (%) = 100 × (viscosity of composition after storage - viscosity of composition before storage) ÷ viscosity of composition before storage. According to the storage method of the present invention, by mixing a polymerizable compound such as a non-aqueous resin with hydrophobically modified cellulose fibers having a specific structure, the rate of change in viscosity of the composition after three months of storage can be set to -50% to 50%. The rate of change in viscosity of the composition after three months of storage is preferably -50% or more, more preferably -30% or more, even more preferably -10% or more, and even more preferably -1% or more, from the viewpoint of allowing the composition to perform its intended function, such as applying the composition to form a coating film or dispersing unnecessary substances such as pigments in the composition. On the other hand, from the viewpoint of facilitating the handling of the composition, the rate of change in viscosity of the composition after storage for 3 months is preferably 50% or less, more preferably 30% or less, even more preferably 10% or less, and even more preferably 1% or less.

[0011] [Component (A): Hydrophobically Modified Cellulose Fibers] Component (A) is a hydrophobically modified cellulose fiber in which a functional group having a specific structure is bonded to the cellulose fiber. The surface of the cellulose fiber is covered with hydroxy groups, which makes it highly hydrophilic, and therefore it has poor affinity with hydrophobic media such as organic solvents and resins. However, by modifying the hydroxy groups or anionic groups (introduced as described below) of the cellulose fiber with a functional group having a specific structure, it is possible to impart affinity to hydrophobic media, and as a result, it is possible to prepare cellulose fibers having nanoscale fiber diameters that are stable in dispersion in hydrophobic media. In this specification, such functional groups having a specific structure are referred to as "modifying groups," and cellulose fibers in which the hydroxy groups or anionic groups have been modified with modifying groups are referred to as "hydrophobically modified cellulose fibers." The modifying groups are preferably bonded to some or all of the hydroxy groups or anionic groups of the cellulose fiber, and are preferably bonded to the group (-CH) at the C6 position of the glucose units constituting the cellulose fiber. ２ It is more preferred that the modified group (OH) is bonded to the carboxy group converted to a carboxy group. Component (A) is preferably a hydrophobically modified cellulose fiber in which a modifying group is bonded to the anionic group of an anion-modified cellulose fiber. Hydrophobically modified cellulose fibers and anion-modified cellulose fibers have a cellulose type I crystal structure due to the use of natural cellulose fibers as the raw material.

[0012] Type I cellulose refers to the crystalline form of natural cellulose, and the degree of crystallinity of type I cellulose refers to the proportion of crystalline regions in the total amount of cellulose.

[0013] The crystallinity of the hydrophobically modified cellulose fibers and anionically modified cellulose fibers of the present invention is preferably 10% or more, more preferably 15% or more, and even more preferably 20% or more, from the viewpoint of improving dispersibility. Furthermore, from the viewpoint of raw material availability, it is preferably 90% or less, more preferably 85% or less, even more preferably 80% or less, and even more preferably 75% or less. In this specification, the crystallinity of various cellulose fibers refers to the cellulose type I crystallinity calculated from the diffraction intensity value by X-ray diffraction, and can be measured according to the method described in the Examples below. Cellulose type I refers to the crystalline form of native cellulose, and cellulose type I crystallinity refers to the proportion of crystalline regions in the entire cellulose fiber. The presence or absence of a cellulose type I crystalline structure can be determined by the presence of a peak at 2θ = 22.6° in X-ray diffraction measurement.

[0014] The average fiber diameter of the anionically modified cellulose fiber is preferably 0.1 μm or more, more preferably 1 μm or more, even more preferably 10 μm or more, and even more preferably 30 μm or more, from the viewpoint of enhancing the mechanical strength of the resin composition by the hydrophobically modified cellulose fiber when a resin is blended therewith. From the same viewpoint, the average fiber diameter is preferably 100 μm or less, more preferably 70 μm or less, and even more preferably 50 μm or less. The average fiber diameter of various cellulose fibers, such as anionically modified cellulose fiber, can be measured by the method described in the examples.

[0015] The average fiber length of the anionically modified cellulose fibers is preferably 1 μm or more, more preferably 10 μm or more, and even more preferably 100 μm or more, from the viewpoint of enhancing the mechanical strength of the resin composition by the hydrophobically modified cellulose fibers. From the same viewpoint, the average fiber length is preferably 10,000 μm or less, more preferably 5,000 μm or less, even more preferably 1,000 μm or less, and even more preferably 500 μm or less. The average fiber length of various cellulose fibers, such as anionically modified cellulose fibers, can be measured by the method described in the examples.

[0016] From the viewpoint of enhancing the mechanical strength of the resin composition by the hydrophobically modified cellulose fibers, the average aspect ratio of the anionically modified cellulose fibers, i.e., the value of fiber length / fiber diameter, is preferably at least 1, more preferably at least 2, and even more preferably at least 3. From the same viewpoint, it is preferably at most 250, more preferably at most 200, even more preferably at most 100, even more preferably at most 50, and even more preferably at most 30. The average aspect ratios of various cellulose fibers, such as anionically modified cellulose fibers, can be measured by the method described in the examples.

[0017] From the viewpoint of stable introduction of modifying groups, the anionic group content of the anion-modified cellulose fiber is preferably 0.1 mmol / g or more, more preferably 0.4 mmol / g or more, and even more preferably 1.0 mmol / g or more. The upper limit is preferably 3.0 mmol / g or less, more preferably 2.0 mmol / g or less, and even more preferably 1.8 mmol / g or less. The anionic group content of the anion-modified cellulose fiber can be measured by the method described in the Examples.

[0018] Examples of anionic groups include carboxyl groups, sulfate groups, and phosphate groups, and examples of cationic groups include groups containing an onium group such as ammonium, phosphonium, or sulfonium. From the viewpoint of efficiency of introduction into cellulose fibers, anionic groups are preferred as ionic groups, and carboxyl groups are more preferred as anionic groups. Furthermore, the counter ion of the anionic group is preferably a proton.

[0019] The preferred ranges of the average fiber diameter, average fiber length, average aspect ratio and degree of crystallinity of cellulose of the hydrophobically modified cellulose fibers are the same as those of the anionically modified cellulose fibers.

[0020] From the viewpoint of enhancing dispersibility, the amount of modifying groups bonded to the hydrophobically modified cellulose fiber is preferably 0.01 mmol / g or more, more preferably 0.1 mmol / g or more, and even more preferably 0.2 mmol / g or more, and from the same viewpoint, it is preferably 3 mmol / g or less, more preferably 2 mmol / g or less, even more preferably 1 mmol / g or less, and even more preferably 0.5 mmol / g or less.

[0021] From the viewpoint of improving dispersibility, the introduction rate of the modifying group in the hydrophobically modified cellulose fiber is preferably 10 mol% or more, more preferably 30 mol% or more, and even more preferably 40 mol% or more, and from the same viewpoint, it is preferably 100 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less.

[0022] The bonded amount and introduction rate of the modifying group can be adjusted by the type and amount of the modifying group added, the reaction temperature, the reaction time, the type of solvent, etc. The bonded amount (mmol / g) and introduction rate (mol%) of the modifying group refer to the amount and rate of the modifying group introduced (bonded) to the anionic group in the hydrophobically modified cellulose fiber. For example, when the anionic group is a carboxy group, the bonded amount and introduction rate of the modifying group in the hydrophobically modified cellulose fiber are calculated by the method described in the Examples below.

[0023] From the viewpoint of improving the dispersibility of the hydrophobically modified cellulose fiber, the amount of glucose moieties in the hydrophobically modified cellulose fiber is preferably 0.1% by mass or more, more preferably 10% by mass or more, and even more preferably 30% by mass or more in the composition. On the other hand, from the viewpoint of handling during production, the amount of glucose moieties in the composition is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.

[0024] In this specification, the term "glucose portion" refers to the portion consisting of glucose units in various cellulose fibers, and in the case of unmodified cellulose fibers, it refers to the entire glucose unit, in the case of anionically modified cellulose fibers, it refers to the entire glucose unit including the anionic group bonded to the glucose unit, and in the case of hydrophobically modified cellulose fibers, it refers to the entire glucose unit excluding the modifying group bonded to the glucose unit. That is, in this specification, glucose units also include glucose units in which the hydroxymethyl group has been converted to a carboxy group.

[0025] [Method for Producing Hydrophobically Modified Cellulose Fibers] The method for producing hydrophobically modified cellulose fibers is not particularly limited, and they can be produced according to any known method as long as the modifying group can be introduced into the anionically modified cellulose fibers described above.

[0026] Examples of methods for producing hydrophobically modified cellulose fibers include a method including a step of introducing anionic groups into raw cellulose fibers to obtain anionically modified cellulose fibers, and a step of introducing modifying groups into the anionically modified cellulose fibers to obtain hydrophobically modified cellulose fibers.

[0027] From the viewpoint of environmental load, it is preferable to use natural cellulose fibers as the raw material. Examples of natural cellulose fibers include wood pulps such as softwood pulp and hardwood pulp, cotton pulps such as cotton linter and cotton lint, non-wood pulps such as straw pulp and bagasse pulp, and bacterial cellulose, and these may be used alone or in combination of two or more.

[0028] Examples of anionic groups to be introduced into the raw cellulose fibers include carboxy groups, (phosphite) groups, sulfonic acid groups, etc. Methods for introducing carboxy groups as anionic groups into cellulose fibers include, for example, a method of converting hydroxy groups of the cellulose fibers into carboxy groups by oxidation, and a method of reacting the hydroxy groups of the cellulose fibers with at least one selected from the group consisting of compounds having carboxy groups, acid anhydrides of compounds having carboxy groups, and derivatives thereof.

[0029] Examples of methods for oxidizing the hydroxy groups of cellulose fibers include those described in Japanese Patent Laid-Open No. 2015-143336 and Japanese Patent Laid-Open No. 2015-143337, which involve reacting raw cellulose fibers with an oxidizing agent such as sodium hypochlorite and a bromide such as sodium bromide using 2,2,6,6-tetramethyl-1-piperidine-N-oxyl (TEMPO) as a catalyst. By oxidizing cellulose fibers using TEMPO as a catalyst, anion-modified cellulose fibers (referred to as "TEMPO-oxidized cellulose fibers") can be obtained in which the hydroxymethyl group at the C6 position of the glucose in the cellulose fiber structural unit is selectively converted to a carboxy group.

[0030] Methods for introducing (phosphorous) groups as anionic groups into cellulose fibers include a method of mixing a powder or aqueous solution of (phosphorous) acid or a (phosphorous) derivative with dry or wet cellulose fibers, a method of adding an aqueous solution of (phosphorous) acid or a (phosphorous) derivative to a dispersion of cellulose fibers, etc. When these methods are employed, dehydration treatment, heat treatment, etc. are generally carried out after mixing or adding a powder or aqueous solution of (phosphorous) acid or a (phosphorous) derivative.

[0031] An example of a method for introducing phosphate groups as anionic groups into cellulose fibers is the method described in Japanese Patent No. 7196051, in which raw cellulose fibers are impregnated with a mixed aqueous solution of ammonium dihydrogen phosphate and urea to convert hydroxy groups of the cellulose fibers into phosphoric acid esters. An example of a method for introducing sulfonic acid groups as anionic groups into cellulose fibers is a method in which sulfuric acid is added to cellulose fibers and the fibers are heated.

[0032] The modifying group is introduced by a reaction between a compound for introducing the modifying group (referred to herein as a "modifying compound") and the anion-modified cellulose fiber. Thus, the hydrophobically modified cellulose fiber of component (A) has the modifying group via an ionic bond and / or a covalent bond. When the modifying group is bonded to a hydroxy group in the anion-modified cellulose fiber, the bond between the modifying group and the anion-modified cellulose fiber is a covalent bond, such as an ether bond, an ester bond, or a carbonate bond.

[0033] When the bonding site of the modifying group is an anionic group in the anion-modified cellulose fiber, the bonding mode between the modifying group and the anion-modified cellulose fiber is an ionic bond or a covalent bond. Here, when the bonding mode is an ionic bond, the modifying compound having a cationic group bonds to the anionic group via electrostatic interaction. Here, when the bonding mode is a covalent bond, the two are bonded via an ester bond, an amide bond, or the like. In particular, when the anionic group is a carboxy group, the bonding mode is via an ester bond, an amide bond, a carbonate bond, a urethane bond, or the like.

[0034] When the bonding site of the modifying group is an anionic group, the modifying group may be bonded to the cellulose fiber via an ionic bond, which can be achieved by a known method. For example, the method described in JP 2015-143336 A can be used, in which the modifying group and the anionic group are bonded via an ionic bond. When the anionic group is a carboxy group, the modifying group may be bonded to the cellulose fiber via a covalent bond, which can be achieved by a known method. For example, the method described in JP 2015-143337 A can be used, in which the modifying group and the anionic group are bonded via an amide bond, which is a type of covalent bond.

[0035] Therefore, in one embodiment where the bonding site of the modifying group is an anionic group, the modifying group possessed by the hydrophobically modified cellulose fiber of component (A) is bonded to the glucose constituting the cellulose via an ionic bond and / or an amide bond.

[0036] (Modifying Group) The modifying group may be one or more groups selected from the group consisting of (a) hydrocarbon groups and (b) polymer groups.

[0037] (a) Hydrocarbon Group Examples of the hydrocarbon group include monovalent hydrocarbon groups, such as chain saturated hydrocarbon groups, chain unsaturated hydrocarbon groups, cyclic saturated hydrocarbon groups, and (heterocyclic) aromatic hydrocarbon groups. The hydrocarbon group has 1 or more carbon atoms, preferably 3 or more, more preferably 8 or more, and even more preferably 10 or more, and preferably 30 or less, more preferably 22 or less, and even more preferably 18 or less. The hydrocarbon group may have a substituent, as described below, and a portion of the hydrocarbon group may be substituted with a hydrogen nitride group.

[0038] Specific examples of the chain saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a pentyl group, a tert-pentyl group, an isopentyl group, a hexyl group, an isohexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, a dodecyl group, a tridecyl group, a trioctyl group, a tetradecyl group, an octadecyl group, a docosyl group, and an octacosanyl group.

[0039] Specific examples of the chain unsaturated hydrocarbon group include an ethylene group, a propylene group, a butene group, an isobutene group, an isoprene group, a pentene group, a hexene group, a heptene group, an octene group, a nonene group, a decene group, a dodecene group, a tridecene group, a tetradecene group, and an octadecene group.

[0040] Specific examples of the cyclic saturated hydrocarbon group include a cyclopropane group, a cyclobutyl group, a cyclopentane group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cyclododecyl group, a cyclotridecyl group, a cyclotetradecyl group, and a cyclooctadecyl group.

[0041] The aromatic hydrocarbon group is, for example, selected from the group consisting of an aryl group and an aralkyl group.

[0042] Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, a triphenyl group, a terphenyl group, and groups in which these groups are substituted with the substituents described below.

[0043] Examples of aralkyl groups include benzyl, dibenzyl, trityl, phenethyl, phenylpropyl, phenylpentyl, phenylhexyl, phenylheptyl, and phenyloctyl groups, as well as groups in which the aromatic group of these groups is further substituted with a substituent.

[0044] (b) Polymer Group The polymer group is a functional group containing a polymer structure. From the viewpoint of improving dispersion stability, the molecular weight of the polymer group is preferably 100 or more, more preferably 200 or more, more preferably 300 or more, more preferably 400 or more, even more preferably 600 or more, even more preferably 1,000 or more, and even more preferably 1,500 or more. From the same viewpoint, the molecular weight is preferably 10,000 or less, more preferably 7,000 or less, even more preferably 5,000 or less, even more preferably 4,000 or less, even more preferably 3,500 or less, and even more preferably 2,500 or less.

[0045] From the viewpoint of improving dispersion stability, the polymer group is preferably a functional group having a repeating structure linked by a structure having an oxygen atom, more preferably a functional group having a repeating structure linked by an oxygen atom, such as a polyoxyalkylene structure (alkylene oxide chain) or a polysiloxane structure (silicone chain), more preferably a functional group having a polyoxyalkylene structure, and even more preferably an alkoxypolyoxyalkylene group.

[0046] (b-1) Polysiloxane structure (silicone chain) The polysiloxane structure (silicone chain) is a structure having a siloxane bond as the main chain, and may further include an alkylene group. The polysiloxane structure may have a substituent, which will be described later.

[0047] (b-2) Polyoxyalkylene Structure (Alkylene Oxide Chain) From the viewpoint of improving dispersion stability, the polyoxyalkylene structure (alkylene oxide chain) is preferably a (co)polymer structure of one or more oxyalkylenes selected from oxyalkylenes having from 2 to 8 carbon atoms, more preferably a (co)polymer structure of one or more oxyalkylenes selected from oxyalkylenes having from 2 to 4 carbon atoms, even more preferably a (co)polymer structure of one or two oxyalkylenes selected from ethylene oxide (EO) and propylene oxide (PO), and even more preferably a copolymer structure (also referred to as an (EO / PO) structure) in which ethylene oxide (EO) and propylene oxide (PO) are polymerized randomly or in a block form.

[0048] Examples of the polyoxyalkylene structure include those represented by the following formula:

[0049]

[0050] (In the formula, R １ is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or —CH ２ CH (CH ３ ) NH ２ represents a group. EO and PO are present randomly or in a block form, a represents the average number of moles of EO added and is 0 or a positive number, and b represents the average number of moles of PO added and is 0 or a positive number. However, a and b cannot be 0 at the same time.

[0051] R １ When R is a linear or branched alkyl group having from 1 to 6 carbon atoms, the alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, or a sec-propyl group. １ may be a hydrogen atom.

[0052] From the viewpoint of improving dispersion stability, a is preferably 0 or more, more preferably 1 or more, even more preferably 3 or more, even more preferably 6 or more, even more preferably 11 or more, even more preferably 15 or more, even more preferably 20 or more, even more preferably 25 or more, and even more preferably 30 or more. From the same viewpoint, a is preferably 100 or less, more preferably 70 or less, even more preferably 60 or less, even more preferably 50 or less, and even more preferably 40 or less.

[0053] From the viewpoint of improving dispersion stability, b is preferably 0 or more, more preferably 1 or more, even more preferably 3 or more, and still more preferably 5 or more. From the same viewpoint, b is preferably 50 or less, more preferably 40 or less, even more preferably 30 or less, even more preferably 25 or less, even more preferably 20 or less, even more preferably 15 or less, and still more preferably 10 or less.

[0054] In the above formula, a+b represents the average total number of moles of EO and PO added, and is preferably 4 or more, more preferably 6 or more, and more preferably 8 or more, and from the same viewpoint, is preferably 100 or less, and more preferably 70 or less.

[0055] Examples of the alkylene group having 1 to 3 carbon atoms include a methylene group, an ethylene group, and a propylene group.

[0056] The PO content (mol%) in the (EO / PO) chain can be calculated based on the above a and b, specifically, by b × 100 / (a + b). From the viewpoint of further improving dispersibility, the PO content is preferably 1 mol% or more, more preferably 5 mol% or more, even more preferably 7 mol% or more, and even more preferably 10 mol% or more. From the same viewpoint, it is preferably 100 mol% or less, more preferably 90 mol% or less, even more preferably 85 mol% or less, even more preferably 75 mol% or less, even more preferably 60 mol% or less, even more preferably 50 mol% or less, even more preferably 40 mol% or less, and even more preferably 30 mol% or less.

[0057] From the viewpoint of improving dispersion stability, the formula weight (molecular weight) of the polyoxyalkylene structure is preferably 100 or more, more preferably 200 or more, even more preferably 300 or more, even more preferably 500 or more, even more preferably 1,000 or more, and even more preferably 1,500 or more. From the same viewpoint, it is preferably 10,000 or less, more preferably 7,000 or less, even more preferably 5,000 or less, even more preferably 4,000 or less, even more preferably 3,500 or less, and even more preferably 2,500 or less.

[0058] (c) Further Substituents The modifying group may further have a substituent. Examples of the substituent include alkoxy groups having 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, and hexyloxy; methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, and sec-butoxycarbonyl. alkoxycarbonyl groups having 1 to 6 carbon atoms in the alkoxy group, such as a tert-butoxycarbonyl group, a pentyloxycarbonyl group, or an isopentyloxycarbonyl group; halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; acyl groups having 1 to 6 carbon atoms, such as an acetyl group or a propionyl group; aralkyl groups; aralkyloxy groups; alkylamino groups having 1 to 6 carbon atoms; dialkylamino groups having an alkyl group with 1 to 6 carbon atoms; and a hydroxy group.

[0059] (Modifying Compound) From the viewpoint of improving dispersion stability, the modifying compound may be a compound that has the above-mentioned modifying group and is capable of bonding to anion-modified cellulose fibers. The modifying group possessed by component (A) is a group derived from the modifying compound, which is generated by bonding the modifying compound to the anion-modified cellulose fibers. When TEMPO-oxidized cellulose fibers are used as the anion-modified cellulose fibers, the modifying compound is preferably a compound having a modifying group and a cationic group, more preferably a compound having a modifying group and an amino group or a quaternary ammonium group. From the viewpoint of improving dispersion stability, preferred examples of the modifying compound include amine compounds having a modifying group and at least one amino group in the molecule, more specifically amine compounds having a hydrocarbon group, amine compounds having a polysiloxane structure, and amine compounds having a polyoxyalkylene structure.

[0060] Such amine compounds may be any of primary amines, secondary amines, tertiary amines, and quaternary ammonium compounds. In this case, the modifying group possessed by component (A) is a group derived from one or more modifying compounds selected from the group consisting of primary amines, secondary amines, tertiary amines, and quaternary ammonium compounds. From the viewpoint of reactivity, preferred anion components of the quaternary ammonium compound include halogen ions such as chloride ions and bromide ions, hydrogen sulfate ions, perchlorate ions, tetrafluoroborate ions, hexafluorophosphate ions, trifluoromethanesulfonate ions, and hydroxy ions. In this specification, primary to tertiary amines include not only compounds in which one to three hydrogen atoms of ammonia are substituted with hydrocarbon groups, but also compounds in which one to three hydrogen atoms of ammonia are substituted with functional groups other than hydrocarbon groups. Furthermore, quaternary ammonium compounds include not only compounds in which four hydrogen atoms of an ammonium ion are substituted with hydrocarbon groups, but also compounds in which four hydrogen atoms of an ammonium ion are substituted with functional groups other than hydrocarbon groups.

[0061] (a) Amine Compound Having a Hydrocarbon Group Specific examples of the amine compound having a hydrocarbon group include primary to tertiary amines, such as ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, butylamine, dibutylamine, hexylamine, 2-ethylhexylamine, dihexylamine, trihexylamine, octylamine, dioctylamine, trioctylamine, dodecylamine, didodecylamine, stearylamine, distearylamine, monoethanolamine, diethanolamine, triethanolamine, oleylamine, aniline, octadecylamine, dimethylbehenylamine, benzylamine, dibenzylamine, tritylamine, naphthylamine, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, and 1-(3-aminopropyl)imidazole.

[0062] Examples of quaternary ammonium compounds include tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetraethylammonium chloride, tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), tetrabutylammonium chloride, lauryltrimethylammonium chloride, dilauryldimethyl chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, cetyltrimethylammonium chloride, and alkylbenzyldimethylammonium chloride.

[0063] The amine compound having a hydrocarbon group may be a commercially available product or may be prepared according to a known method.

[0064] The hydrocarbon compound having a cationic group may have a substituent. Specific examples of the substituent include those described above in "(c) Further Substituents."

[0065] (b-1) Amine compound having a polysiloxane structure Examples of such amine compounds include those having a structure in which an amino group is bonded to the backbone of a polysiloxane structure via an alkylene group or the like. In this specification, such amine compounds may be referred to as "amino-modified silicones." Commercially available amino-modified silicones can be used, or they can be prepared according to known methods. Only one type of amino-modified silicone may be used, or two or more types may be used.

[0066] As amino-modified silicones, from the viewpoint of performance, TSF4703 (kinematic viscosity: 1000, amino equivalent: 1600) and TSF4708 (kinematic viscosity: 1000, amino equivalent: 2800) manufactured by Momentive Performance Materials, SS-3551 (kinematic viscosity: 1000, amino equivalent: 1600), SF8457C (kinematic viscosity: 1200, amino equivalent: 1800), SF8417 (kinematic viscosity: 1200, amino equivalent: 1700), BY16-209 (kinematic viscosity: 500, amino equivalent: 1800) manufactured by Dow Corning Toray Silicone Co., Ltd., and B Preferred examples include Y16-892 (kinematic viscosity: 1500, amino equivalent: 2000), BY16-898 (kinematic viscosity: 2000, amino equivalent: 2900), FZ-3760 (kinematic viscosity: 220, amino equivalent: 1600), KF8002 (kinematic viscosity: 1100, amino equivalent: 1700), KF867 (kinematic viscosity: 1300, amino equivalent: 1700), KF-864 (kinematic viscosity: 1700, amino equivalent: 3800), BY16-213 (kinematic viscosity: 55, amino equivalent: 2700), and BY16-853U (kinematic viscosity: 14, amino equivalent: 450) manufactured by Shin-Etsu Chemical Co., Ltd. In parentheses, the kinematic viscosity is measured at 25°C (unit: mm ２ / s), and the unit of amino equivalent is g / mol.

[0067] (b-2) Amine compound having a polyoxyalkylene structure In the amine compound, the polyoxyalkylene structure and the nitrogen atom of the amine compound are preferably bonded directly or via a linking group. The linking group is preferably a hydrocarbon group, and includes an alkylene group having preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. As such an alkylene group, for example, an ethylene group or a propylene group is preferable.

[0068] Examples of the amine compound having a polyoxyalkylene structure include those represented by the following formula (i):

[0069]

[0070] In formula (i), R １ , a and b are R in the formula showing an example of the polyoxyalkylene structure. １ , a and b are the same. Amine compounds having a polyoxyalkylene structure are compounds for introducing modifying groups represented by the polyoxyalkylene structure, and can be prepared according to known methods. For example, desired amounts of ethylene oxide and propylene oxide may be added to a propylene glycol alkyl ether, followed by aminating the hydroxyl group terminal. If necessary, the alkyl ether can be cleaved with an acid to convert the terminal to a hydrogen atom. For these production methods, reference can be made to JP-A-3-181448, and details of such amine compounds are described, for example, in Japanese Patent No. 6,105,139.

[0071] As the amine compound having a polyoxyalkylene structure, for example, commercially available products can be suitably used. Specific examples of the amine compound having an EO chain or a PO chain and optionally having a hydrocarbon group include SUNBRIGHT MEPA-10H, SUNBRIGHT MEPA-20H, SUNBRIGHT MEPA-50H, SUNBRIGHT MEPA-10T, SUNBRIGHT MEPA-12T, SUNBRIGHT MEPA-20T, SUNBRIGHT MEPA-30T, and SUNBRIGHT MEPA-40T, manufactured by NOF Corporation.

[0072] Specific examples of the amine compound having an EO / PO chain and optionally having a hydrocarbon group include Jeffamine M-2070, Jeffamine M-2005, Jeffamine M-2095, Jeffamine M-1000, Jeffamine M-600, Surfoamine B200, Surfoamine L100, Surfoamine L200, Surfoamine L207, Surfoamine L300, Surfoamine B-100, XTJ-501, XTJ-506, XTJ-507, XTJ-508, M3000, Jeffamine ED-600, Jeffamine ED-900, Jeffamine ED-2003, Jeffamine D-230, Jeffamine D-400, Jeffamine D-2000, Jeffamine D-4000, XTJ-510, and Jeffamine M-2005, all manufactured by HUNTSMAN. T-3000, Jeffamine T-5000, XTJ-502, XTJ-509, XTJ-510, etc. These may be used alone or in combination of two or more.

[0073] After the introduction of the modifying group, post-treatment may be carried out as appropriate to remove unreacted compounds, etc. Examples of post-treatment methods that can be used include filtration, centrifugation, dialysis, etc.

[0074] (Micronization Treatment) By micronizing the raw cellulose fibers, anion-modified cellulose fibers, or hydrophobically modified cellulose fibers, it is possible to reduce the micrometer-scale cellulose fibers to nanometer-scale. Reducing the average fiber diameter to nanometer size is preferred because it improves dispersibility.

[0075] The average fiber diameter of the finely divided cellulose fibers, anion-modified cellulose fibers, or hydrophobically modified cellulose fibers (hereinafter referred to as "finished fibers") is preferably 0.1 nm or more from the viewpoint of enhancing the mechanical strength of the resin composition by the hydrophobically modified cellulose fibers. Also, the average fiber diameter of the finely divided fibers is preferably 100 nm or less from the viewpoint of enhancing the handleability of the composition by the hydrophobically modified cellulose fibers.

[0076] The average fiber length of the finely divided fibers is preferably 150 nm or more from the viewpoint of enhancing the mechanical strength of the resin composition by the hydrophobically modified cellulose fibers, and is preferably 1,000 nm or less from the viewpoint of enhancing the handleability of the composition by the hydrophobically modified cellulose fibers.

[0077] The average aspect ratio of the fine fibers is preferably 1 or more from the viewpoint of enhancing the mechanical strength of the resin composition by the hydrophobically modified cellulose fibers. Also, the average aspect ratio of the fine fibers is preferably 250 or less from the viewpoint of enhancing the handleability of the resin composition by the hydrophobically modified cellulose fibers.

[0078] The micronization treatment can be carried out by a known micronization treatment method. For example, to obtain micronized hydrophobically modified cellulose fibers having an average fiber diameter on the nanometer scale, a treatment method using a grinder such as a mass colloider or a treatment method using a high-pressure homogenizer in a medium may be carried out.

[0079] As the apparatus used in the micronization treatment, in addition to a high-pressure homogenizer, known dispersers are also suitably used. For example, a disintegrator, a beater, a low-pressure homogenizer, a grinder, a mass colloider, a cutter mill, a ball mill, a jet mill, a single-screw extruder, a twin-screw extruder, an ultrasonic agitator, a household juicer mixer, etc. can be used. In addition, the solids concentration of the hydrophobically modified cellulose fiber in the micronization treatment is preferably 50 mass% or less.

[0080] (Fiber Shortening Treatment) In the present invention, various cellulose fibers, i.e., raw cellulose fibers, anion-modified cellulose fibers, hydrophobically modified cellulose fibers, and finely divided hydrophobically modified cellulose fibers, may be subjected to a fiber shortening treatment. By performing such a fiber shortening treatment, the dispersibility of the finely divided hydrophobically modified cellulose fibers can be improved. The fiber shortening treatment can be performed by subjecting the target cellulose fibers to one or more treatment methods selected from the group consisting of (i) alkali treatment, (ii) acid treatment, and (iii) heat treatment, ultraviolet treatment, electron beam treatment, mechanical treatment, and enzyme treatment.

[0081] [Component (B)] Component (B) in the present invention is a non-aqueous liquid that is liquid at 25° C. and 1 atmosphere. The non-aqueous liquid is a liquid excluding water.

[0082] The relative dielectric constant at 25°C of a non-aqueous liquid that is liquid at 25°C and 1 atmosphere is preferably 50 or less, more preferably 20 or less, and even more preferably 10 or less. The relative dielectric constant can be measured using a dielectric constant meter (for example, BI-871 (manufactured by BROOKHAVEN INSTRUMENTS)) at a frequency of 10 kHz.

[0083] The non-aqueous liquid may be a non-aqueous resin or an organic solvent. The non-aqueous liquid may be used alone or in combination of two or more kinds.

[0084] Specific examples of non-aqueous resins include epoxy resins, urethane resins, acrylic resins, vinyl chloride resins, phenoxy resins, phenolic resins, urea resins, melamine resins, polyimide resins, silicone resins, unsaturated polyester resins, diallyl phthalate resins, and rubber-based resins. Among these, epoxy resins, urethane resins, and acrylic resins are preferred from the viewpoint of availability. When blending non-aqueous resins, they are blended as monomers and / or prepolymers.

[0085] Specific examples of organic solvents include alcohols such as methanol, ethanol, propanol, 2-methoxyethanol (methyl cellosolve), 2-ethoxyethanol (ethyl cellosolve), 1-methoxy-2-propanol (PGME), and terpineol; tetrahydrofuran (THF), diethyl ether, ethylene glycol, and propylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, and ethylene glycol monoethyl ether acetate (ethyl cellosolve). Examples of such solvents include esters such as diethylene glycol monomethyl ether acetate (diethylene glycol monomethyl ether acetate), diethylene glycol monomethyl ether acetate (carbitol acetate), and propylene glycol monomethyl ether acetate (PGMEA); saturated or unsaturated hydrocarbons; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride and chloroform; lower alkyl ethers; and polar solvents such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone (DMI), and dimethyl sulfoxide. These may be used alone or in combination of two or more.

[0086] [Curing Agent] The composition may contain a curing agent. Known curing agents can be selected and used depending on the type of non-aqueous resin used.

[0087] When the non-aqueous resin is an epoxy resin, curing agents include those used as curing agents for ordinary epoxy resins, compounds that undergo a stoichiometric reaction, such as aliphatic polyamines, aromatic polyamines, dicyandiamide, polycarboxylic acids, polycarboxylic acid hydrazides, acid anhydrides, polymercaptans, and polyphenols, and compounds that act catalytically, such as imidazole, Lewis acid complexes, and onium salts.When a compound that undergoes a stoichiometric reaction is used, curing accelerators such as various amines, imidazole, Lewis acid complexes, onium salts, and phosphines can be used.

[0088] When the non-water-soluble resin is a urethane resin, a curing agent that is generally used as a curing agent for urethane resin, specifically, an aromatic isocyanate, can be used.

[0089] The amount of the curing agent in the present invention is not particularly limited, and an appropriate amount may be used depending on the type of curing agent.

[0090] [Other Components] The composition may contain, as necessary, known components such as coloring matter such as pigments and dyes, polymerization initiators, plasticizers, stabilizers, lubricants, etc. The amounts of such components are not particularly limited, and appropriate amounts may be used as appropriate.

[0091] [Composition of Components in the Composition] The composition according to the present invention, which is subject to refrigerated storage, can be produced by mixing the above-mentioned components (A) and (B), and, if necessary, other components. Thus, the composition according to the present invention is a blend of the above-mentioned components (A) and (B), and, if necessary, other components.

[0092] From the viewpoint of enhancing the mechanical strength of the hydrophobically modified cellulose fibers, the content of component (A) in the composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 10% by mass or more. On the other hand, from the viewpoint of the handleability of the composition, the content of component (A) in the composition is also preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less.

[0093] From the viewpoint of enhancing the mechanical strength by the hydrophobically modified cellulose fibers, the content of component (A) in the composition is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 10 parts by mass or more, per 100 parts by mass of component (B). On the other hand, from the viewpoint of enhancing the handleability of the composition by the hydrophobically modified cellulose fibers, the content of component (A) in the composition is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 30 parts by mass or less, per 100 parts by mass of component (B).

[0094] The content of the glucose moiety of component (A) in the composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 5% by mass or more, from the viewpoint of enhancing the mechanical strength of the hydrophobically modified cellulose fiber, while it is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, from the viewpoint of improving the dispersibility of the hydrophobically modified cellulose fiber.

[0095] The content of the glucose moiety of component (A) in the composition is preferably 0.1 parts by mass or more, more preferably 5 parts by mass or more, and even more preferably 8 parts by mass or more, per 100 parts by mass of component (B), from the viewpoint of improving the dispersibility of the hydrophobically modified cellulose fiber; on the other hand, from the viewpoint of handleability during production, it is preferably 100 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less, per 100 parts by mass of component (B).

[0096] From the viewpoint of ease of handling of the composition, the content of component (B) in the composition is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 80% by mass or more. On the other hand, from the viewpoint of enhancing the mechanical strength by the hydrophobically modified cellulose fiber, the content of component (B) in the composition is preferably 95% by mass or less, more preferably 90% by mass or less.

[0097] The composition may contain water. From the viewpoint of the mechanical strength of the composition when cured, the water content is preferably as low as possible, and is preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.1% by mass or less.

[0098] [Storage Method of the Present Invention] The storage method of the present invention preferably includes a step of refrigerating and storing the target composition. From the viewpoint of suppressing changes in the viscosity of the composition over time, the refrigerated storage temperature is preferably 20°C or lower, more preferably 15°C or lower, and even more preferably 5°C or lower. On the other hand, the lower limit of the refrigerated storage temperature is preferably -80°C or higher, more preferably -30°C or higher, even more preferably -10°C or higher, and even more preferably -4°C or higher. Therefore, a preferred embodiment of the storage method of the present invention is a method in which the target composition is stored at 20°C or lower. The preferred range of the storage temperature is the same as the above-mentioned "refrigerated storage temperature". A more preferred embodiment of the storage method of the present invention is a method in which the target composition is refrigerated and stored at 20°C or lower. The preferred range of the refrigerated storage temperature is the same as the above-mentioned "refrigerated storage temperature".

[0099] According to the storage method of the present invention, the change in viscosity of the composition over time can be suppressed, and therefore the composition after storage can be handled in the same way as the composition before storage. That is, when assuming a situation in which the composition according to the present invention is used in fields such as paints, coating agents, adhesives, electrical insulating materials such as sealants and printed wiring boards, composite materials such as glass fiber-carbon fiber composite materials, and civil engineering and construction materials such as flooring materials, paving materials, and lining materials, i.e., fields in which the composition is applied to the surface of an object, the same coatability as the composition before storage can be ensured.

[0100] Therefore, from the viewpoint of the coatability of the composition, the viscosity of the composition at 25°C after storage is preferably 100,000 mPa s or less, more preferably 50,000 mPa s or less, and even more preferably 10,000 mPa s or less, and from the viewpoint of preventing dripping of the composition, the viscosity of the composition at 25°C after storage is preferably 1 mPa s or more, more preferably 10 mPa s or more, even more preferably 100 mPa s or more, and even more preferably 1,000 mPa s or more. The viscosity of the composition here can be measured according to the method described in the Examples below.

[0101] [Method for Suppressing Viscosity Change in Composition] As described above, according to the present invention, it is possible to suppress viscosity change in a composition containing the above-mentioned components (A) and (B). Therefore, one aspect of the present invention is a method for suppressing viscosity change in a composition containing the above-mentioned components (A) and (B).

[0102] In relation to the above-mentioned embodiment, the present invention further discloses the following method for storing a composition.

[0103] <1> A method for refrigerating and storing a composition containing the following components (A) and (B): Component (A): hydrophobically modified cellulose fiber; and Component (B): a non-aqueous liquid that is liquid at 25°C and 1 atmosphere.

[0104] <2> A method for storing a composition containing the following components (A) and (B) at 20°C or below: Component (A): hydrophobically modified cellulose fiber Component (B): non-aqueous liquid that is liquid at 25°C and 1 atmosphere. <3> A method for refrigerating and storing a composition containing the following components (A) and (B) at 20°C or below: Component (A): hydrophobically modified cellulose fiber Component (B): non-aqueous liquid that is liquid at 25°C and 1 atmosphere. <4> A method for refrigerating and storing a composition comprising the following components (A) and (B): Component (A): hydrophobically modified cellulose fiber Component (B): non-aqueous liquid that is liquid at 25°C and 1 atmosphere. <5> A method for storing a composition comprising the following components (A) and (B) at 20°C or below: Component (A): hydrophobically modified cellulose fiber Component (B): non-aqueous liquid that is liquid at 25°C and 1 atmosphere. <6> A method for refrigerating and storing a composition comprising the following components (A) and (B) at 20°C or below: Component (A): Hydrophobically modified cellulose fiber Component (B): Non-aqueous liquid that is liquid at 25°C and 1 atmosphere

[0105] <7> The method according to any one of <1> to <6>, wherein component (A) is a hydrophobically modified cellulose fiber formed by bonding a modifying group to an anionic group of an anionically modified cellulose fiber, and the hydrophobically modified cellulose fiber and the anionically modified cellulose fiber have a cellulose type I crystal structure due to the use of natural cellulose fibers as raw materials. <8> The method according to any one of <1> to <7>, wherein component (A) has a crystallinity of preferably 10% or more, more preferably 15% or more, even more preferably 20% or more, and preferably 90% or less, more preferably 85% or less, even more preferably 80% or less, and even more preferably 75% or less. <9> The method according to any one of <1> to <8>, wherein component (A) has an average fiber diameter of preferably 0.1 μm or more, more preferably 1 μm or more, even more preferably 10 μm or more, even more preferably 30 μm or more, and preferably 100 μm or less, more preferably 70 μm or less, and even more preferably 50 μm or less. <10> The method according to any one of the above <1> to <9>, wherein the average fiber length of component (A) is preferably 1 μm or more, more preferably 10 μm or more, even more preferably 100 μm or more, and preferably 10,000 μm or less, more preferably 5,000 μm or less, even more preferably 1,000 μm or less, and even more preferably 500 μm or less. <11> The method according to any one of the above <1> to <10>, wherein the average aspect ratio of component (A) is preferably 1 or more, more preferably 2 or more, even more preferably 3 or more, and preferably 250 or less, more preferably 200 or less, even more preferably 100 or less, even more preferably 50 or less, and even more preferably 30 or less. <12> The method according to any one of <1> to <11>, wherein the bonding amount of the modifying group in component (A) is preferably 0.01 mmol / g or more, more preferably 0.1 mmol / g or more, even more preferably 0.2 mmol / g or more, and is preferably 3 mmol / g or less, more preferably 2 mmol / g or less, even more preferably 1 mmol / g or less, even more preferably 0.5 mmol / g or less.<13> The method according to any one of <1> to <12> above, wherein the introduction rate of the modifying group in component (A) is preferably 10 mol% or more, more preferably 30 mol% or more, even more preferably 40 mol% or more, and preferably 100 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less. <14> The method according to any one of <1> to <13> above, wherein component (B) contains a non-aqueous resin and / or an organic solvent. <15> The method according to any one of <1> to <14> above, wherein component (B) has a relative dielectric constant at 25°C of preferably 50 or less, more preferably 20 or less, and even more preferably 10 or less. <16> The method according to any one of <1> to <15> above, wherein component (B) contains one or more resins selected from the group consisting of epoxy resins, urethane resins, and acrylic resins. <17> The method according to any one of <1> to <16> above, wherein the content of component (A) in the composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 10% by mass or more. <18> The method according to any one of <1> to <17> above, wherein the content of component (A) in the composition is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less. <19> The method according to any one of <1> to <18> above, wherein the content of component (B) in the composition is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 80% by mass or more. <20> The method according to any one of <1> to <19> above, wherein the content of component (B) in the composition is preferably 95% by mass or less, more preferably 90% by mass or less. <21> The method according to any one of the above <1> to <20>, wherein the content of component (A) in the composition is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 10 parts by mass or more, per 100 parts by mass of component (B). <22> The method according to any one of the above <1> to <21>, wherein the content of component (A) in the composition is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 30 parts by mass or less, per 100 parts by mass of component (B).<23> The method according to any one of <1> to <22> above, wherein the content of the glucose moiety of component (A) in the composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 5% by mass or more. <24> The method according to any one of <1> to <23> above, wherein the content of the glucose moiety of component (A) in the composition is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less. <25> The method according to any one of <1> to <24> above, wherein the content of the glucose moiety of component (A) in the composition is preferably 0.1 parts by mass or more, more preferably 5 parts by mass or more, and even more preferably 8 parts by mass or more, per 100 parts by mass of component (B). <26> The method according to any one of <1> to <25> above, wherein the content of the glucose moiety of component (A) in the composition is preferably 100 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less, per 100 parts by mass of component (B). <27> The method according to any one of <1> to <26> above, wherein component (A) has a modifying group via an ionic bond and / or a covalent bond. <28> The method according to any one of <1> to <27> above, wherein the modifying group possessed by component (A) is bonded to glucose constituting cellulose via an ionic bond and / or an amide bond. <29> The method according to any one of <1> to <28> above, wherein the modifying group possessed by component (A) is one or more selected from the group consisting of (a) a hydrocarbon group and (b) a polymer group. <30> The method according to any one of <1> to <29> above, wherein the modifying group possessed by component (A) is one or more selected from the group consisting of an amine compound having a hydrocarbon group, an amine compound having a polysiloxane structure, and an amine compound having a polyoxyalkylene structure. <31> The method according to any one of the above <1> to <30>, wherein the modifying group in component (A) is a group derived from one or more modifying compounds selected from the group consisting of primary amines, secondary amines, tertiary amines, and quaternary ammonium compounds.<32> The method according to any one of <1> to <31> above, wherein the viscosity of the composition at 25°C after storage is preferably 100,000 mPa s or less, more preferably 50,000 mPa s or less, and even more preferably 10,000 mPa s or less. <33> The method according to any one of <1> to <32> above, wherein the viscosity of the composition at 25°C after storage is preferably 1 mPa s or more, more preferably 10 mPa s or more, even more preferably 100 mPa s or more, and even more preferably 1,000 mPa s or more. <34> The method according to any one of <1> to <33> above, wherein the refrigerated storage temperature is 20°C or less, more preferably 15°C or less, and even more preferably 5°C or less. <35> The method according to any one of <1> to <34> above, wherein the refrigerated storage temperature is preferably −80° C. or higher, more preferably −30° C. or higher, even more preferably −10° C. or higher, and even more preferably −4° C. or higher. <36> A method for refrigerating and storing a composition containing the following components (A) and (B) at 20° C. or lower: Component (A): hydrophobically modified cellulose fibers obtained by bonding one or more modifying compounds selected from the group consisting of primary amines, secondary amines, tertiary amines, and quaternary ammonium compounds to anionic groups of anionically modified cellulose fibers. Component (B): a non-aqueous liquid that is liquid at 25° C. and 1 atmosphere and has a dielectric constant of 10 or lower at 25° C. <37> A method for refrigerating and storing a composition containing the following components (A) and (B) at 20° C. or lower. Component (A): Hydrophobically modified cellulose fibers obtained by bonding one or more modifying compounds selected from the group consisting of primary amines, secondary amines, tertiary amines, and quaternary ammonium compounds to anionic groups of anionically modified cellulose fibers. Component (B): One or more non-aqueous liquids selected from the group consisting of epoxy resins, urethane resins, and acrylic resins, which are liquid at 25°C and 1 atmosphere. <38> A method for refrigerating and storing a composition containing the following components (A) and (B) at 20°C or below, wherein the content of component (A) in the composition is 10 parts by mass or more and 30 parts by mass or less per 100 parts by mass of component (B).Component (A): Hydrophobically modified cellulose fibers in which one or more modifying compounds selected from the group consisting of primary amines, secondary amines, tertiary amines, and quaternary ammonium compounds are bonded to the anionic groups of the anion-modified cellulose fibers. Component (B): One or more non-aqueous liquids selected from the group consisting of epoxy resins, urethane resins, and acrylic resins, which are liquid at 25°C and 1 atmosphere.

[0106] The present invention will be specifically described below with reference to examples. Note that the following examples are merely illustrative of the present invention and are not intended to limit the present invention in any way. Note that "normal pressure" refers to a state in which no pressure or pressure is applied, and "normal temperature" refers to 25°C.

[0107] [Average Fiber Diameter and Average Fiber Length of Cellulose Fibers and (Shortened) Anion-Modified Cellulose Fibers] Deionized water was added to the cellulose fibers to be measured or a suspension containing the cellulose fibers to be measured to prepare a dispersion with a cellulose fiber content of 0.01% by mass. This dispersion was measured using a wet dispersion type image analysis particle size distribution analyzer (manufactured by JUSCO International, product name: IF-3200) under the following conditions: front lens: 2x; telecentric zoom lens: 1x; image resolution: 0.835 μm / pixel; syringe inner diameter: 6515 μm; spacer thickness: 500 μm; image recognition mode: ghost; threshold: 8; analytical sample volume: 1 mL; and sampling: 15%. The cellulose fibers were then approximated as a rectangle, and the length of the minor axis was defined as the fiber diameter and the length of the major axis was defined as the fiber length. Each value was measured for 100 cellulose fibers, and the average values ​​were calculated.

[0108] [Anionic Group Content of Anion-Modified Cellulose Fiber] 0.5 g of the cellulose fiber to be measured, with a dry mass of 0.5 g, was placed in a beaker and mixed with deionized water or a 2 / 1 (volume ratio) methanol / deionized water solvent to a total volume of 55 mL. 5 mL of 0.01 M aqueous sodium chloride solution was added to the mixture to prepare a dispersion. The dispersion was stirred until the cellulose fiber to be measured was sufficiently dispersed. 0.1 M hydrochloric acid was added to the dispersion to adjust the pH to 2.5-3. Using an automatic titrator (DKK-TOA Corporation, AUT-701), 0.05 M aqueous sodium hydroxide solution was added dropwise to the dispersion with a waiting time of 60 seconds, and the conductivity and pH were measured every minute. Measurements were continued until the pH reached approximately 11, and a conductivity curve was obtained. The sodium hydroxide titration amount was determined from this conductivity curve, and the anionic group content of the cellulose fiber to be measured was calculated using the following formula: Anionic group content (mmol / g) = [titration amount of aqueous sodium hydroxide solution (mL) × concentration of aqueous sodium hydroxide solution (0.05 M)] / [mass of cellulose fiber to be measured (0.5 g)]

[0109] [Amount of bonded modifying groups and introduction rate of modified groups in hydrophobically modified cellulose fibers] The amount of bonded modifying groups in hydrophobically modified cellulose fibers was determined by the following IR measurement method, and the amount of bonded modifying groups and introduction rate were calculated using the following formula. Specifically, the IR measurement involved measuring the infrared absorption spectrum of dried cellulose fibers to be measured by the ATR method using an infrared absorption spectrometer (IR) (Nicolet 6700, manufactured by Thermo Fisher Scientific), and the amount of bonded modifying groups and introduction rate were calculated using formula A. The following describes the case where the anionic group is a carboxy group, i.e., the case of oxidized cellulose fibers. The following "1720 cm －１ The "peak intensity of" is the peak intensity derived from carbonyl groups. In the case of anionic groups other than carboxy groups, the wave number value can be changed appropriately to calculate the bond amount and introduction rate of the modifying group. <Formula A> Bond amount of modifying group (mmol / g) = a × (b - c) ÷ b a: Carboxy group content of oxidized cellulose fiber (mmol / g) b: 1720 cm －１ c: Peak intensity of hydrophobically modified cellulose fiber at 1720 cm －１Equation B: Modification group introduction rate (mol%) = 100 x f / g, f: amount of modified group bonded (mmol / g), g: carboxyl group content of oxidized cellulose fiber (mmol / g).

[0110] [Content of Each Component] The content of each component other than water was calculated from the blended amount of each component. The glucose moiety content was calculated by assuming that all of the anion-modified cellulose fiber and the modifying compound blended during the preparation of the hydrophobically modified cellulose fiber were bonded, and the mass of the anion-modified cellulose fiber contained in the blended hydrophobically modified cellulose fiber was regarded as the mass of the glucose moiety. The water content in the dispersion or suspension was measured by Karl Fischer titration using a Mitsubishi Analytech CA-200. The solids concentration of each cellulose fiber was calculated by measuring the moisture concentration in the sample using an infrared moisture meter (Shimadzu Corporation, MOC-120H) and calculating the difference from 100% by mass. The moisture concentration was measured every 30 seconds for 1 g of sample at a constant temperature of 150°C, and the value displayed when the mass loss over 30 seconds reached 0.1% or less was used.

[0111] [Measurement of Electrical Conductivity of Filtrate] The electrical conductivity of the filtrate was measured using a compact electrical conductivity meter (LAQUAtwin EC-33B, manufactured by Horiba, Ltd.).

[0112] [Measurement of viscosity of composition] Using a rheometer (MCR-300, manufactured by Anton Paar) and a cone plate (CP25-2 / Ti), the viscosity was measured at 25°C and a shear rate of 100 s －１ The viscosity measured after 180 seconds under the above conditions was regarded as the viscosity of the composition. When the storage temperature was a temperature other than 25°C (for example, 4°C), the viscosity was measured by setting the temperature of the composition immediately before storage to 25°C, and the viscosity was measured by setting the temperature of the composition immediately after storage was completed to 25°C.

[0113] [Measurement of the Average Degree of Polymerization of Anion-Modified Cellulose Fiber] The average degree of polymerization of anion-modified cellulose fiber was measured as follows. (1) Preparation of Measurement Solution: 0.06 g (dry mass) of anion-modified cellulose fiber to be measured was precisely weighed and placed in a 50 mL beaker. Water was added to the solution to a solids concentration of 1% by mass. 0.006 g of sodium borohydride was added and stirred at room temperature for 2 hours. 18 g of acetone was then added. The solution was then centrifuged at 10°C, 10,000 G, and 1 minute using a high-speed refrigerated centrifuge (Koki Holdings Co., Ltd., CR21G III) to remove the supernatant. 18 g of ethanol was added to the residue, and the same process of centrifuging and removing the supernatant was repeated three times to obtain a precipitate washed with ethanol. The resulting precipitate was vacuum-dried at 40°C for 12 hours to obtain reduced pulp in which the aldehyde groups in the anion-modified cellulose fiber were reduced. 15 mL of deionized water and 15 mL of 1 M copper ethylenediamine solution were added to 0.06 g of the obtained reduced pulp, and the mixture was stirred at room temperature for 1 hour to obtain a measurement solution.

[0114] (2) Measurement of average degree of polymerization The measurement solution obtained in (1) above was placed in an Ubbelohde viscometer, and allowed to stand in a thermostatic bath (25±0.1)°C for 1 hour. The flow time of the solution (t (seconds)) was then measured against the flow time of a 0.5M copper ethylenediamine solution without cellulose (t ０ (sec)) and the intrinsic viscosity [η] (dL / g) was calculated using the following formula: [η] = [(t / t ０ -1) / c] / [1+0.28×(t / t ０ -1)] (c: cellulose concentration (g / dL)) From the obtained intrinsic viscosity [η], the average degree of polymerization (DP) of the anion-modified cellulose fiber was calculated using the following formula: ｖ ) was calculated. [η] = 0.094 × (162 × DP ｖ ) ０．６７

[0115] [Confirmation of Crystal Structure in Various Cellulose Fibers] The crystal structures of various celluloses, such as raw cellulose, anion-modified cellulose fiber, and hydrophobically modified cellulose fiber, were confirmed by measurement using a diffractometer (MiniFlex II, manufactured by Rigaku Corporation) under the following conditions. Measurement pellet preparation conditions: A pressure of 10 to 20 MPa was applied to the target cellulose using a tablet molding machine to form pellets with an area of ​​320 mm. ２ Smooth pellets measuring 1 mm x 1 mm thick were prepared. X-ray diffraction analysis conditions: step angle 0.01°, scan speed 10° / min, measurement range: diffraction angle 2θ = 5 to 40°, X-ray source: Cu / Kα-radiation, tube voltage: 15 kV, tube current: 30 mA. Peak splitting conditions: After removing background noise, the peaks were fitted with a Gaussian function so that the error between 2θ = 13 and 23° was within 5%. The crystalline structures of various celluloses were confirmed by measurements using the above-mentioned diffractometer under the above-mentioned conditions. The crystallinity of the cellulose type I crystal structure was calculated based on the following formula (A) using the area of ​​the X-ray diffraction peak obtained by the above-mentioned peak splitting: Cellulose type I crystallinity (%) = [I ｃｒ / (I ｃｒ +I ａｍ )]×100 (A) [wherein, I ｃｒ is the area of ​​the diffraction peak of the lattice plane (002 plane) (diffraction angle 2θ = 22-23°) in X-ray diffraction, I ａｍ indicates the area of ​​the diffraction peak of the amorphous portion (diffraction angle 2θ=18.5°).

[0116] [Anion-modified cellulose fiber] Anion-modified cellulose fiber 1 having the physical properties shown in Table 1 was used as the raw material for component (A).

[0117]

[0118] Such anion-modified cellulose fiber 1 can be prepared, for example, by carrying out the following TEMPO oxidation treatment and alkaline hydrolysis treatment.

[0119] [TEMPO Oxidation Treatment] 20 g of bleached coniferous kraft pulp fiber as the raw natural cellulose fiber and 1,980 g of deionized water were weighed into a 2-L PP beaker equipped with a mechanical stirrer and stirring blades and stirred for 30 minutes at 25°C and 100 rpm. Next, 0.26 g of 2,2,6,6-tetramethyl-1-piperidine-N-oxyl (TEMPO), 2.6 g of sodium bromide, and 70.0 g of a 10.5% by mass aqueous solution of sodium hypochlorite were added to the 20 g of pulp fiber in this order. Next, pH stat titration was performed using an automatic titrator, and 0.5 M aqueous sodium hydroxide solution was added dropwise to maintain the pH at 10.5. The reaction was carried out at 25°C for 120 minutes at a stirring speed of 100 rpm. Next, 0.01 M hydrochloric acid was added to the suspension while stirring to adjust the pH to 2. The solids are then separated by suction filtration. The solids are dispersed in deionized water and the filtrate is separated by suction filtration. This procedure is repeated until the conductivity of the filtrate reaches 200 μS / cm or less. The resulting solids are then dehydrated to obtain anion-modified cellulose fibers.

[0120] [Alkaline Hydrolysis Treatment] The suspension of anion-modified cellulose fibers (solid content: 14.5 g) obtained by the TEMPO oxidation treatment was diluted with 100 g of deionized water, and 0.14 g of 35% hydrogen peroxide solution (1 part by mass of hydrogen peroxide per 100 parts by mass of the solid content of the raw cellulose fibers) was added thereto. The pH was adjusted to 12 with 1 M aqueous sodium hydroxide solution. Subsequently, alkaline hydrolysis treatment was performed at 80°C for 2 hours (solid content concentration of the anion-modified cellulose fiber suspension: 4.3% by mass). After cooling the suspension to room temperature, 0.01 M hydrochloric acid was added to adjust the pH of the suspension to 2. The solid content of the suspension was filtered off by suction filtration. The solid content was dispersed in deionized water and the suction filtration was repeated until the conductivity of the filtrate reached 200 μS / cm or less. The resulting solid content was dehydrated to obtain anion-modified cellulose fibers 1.

[0121] [Preparation of Shortened Anion-Modified Cellulose Fiber] Anion-modified cellulose fiber 1 having the physical properties listed in Table 1 was subjected to a fiber shortening process to obtain short anion-modified cellulose fiber 1 having the physical properties listed in Table 2. Specifically, deionized water was added to 227 g of the cake of anion-modified cellulose fiber 1 (solid content: 75 g) until the solid content concentration changed from the value shown in Table 2 to 5% by mass. The resulting suspension was stirred at 95°C for the time listed in Table 2 to obtain an aqueous suspension of short anion-modified cellulose fiber. The resulting suspension was centrifuged using a high-speed refrigerated centrifuge (CR21G III, manufactured by Koki Holdings Co., Ltd.) at 25°C, 10,000 G, and for 1 minute to obtain short anion-modified cellulose fiber 1 listed in Table 2 as a precipitate.

[0122]

[0123] [Preparation of hydrophobically modified cellulose fiber and composition] [Hydrophobically modified cellulose fiber 1] 1-methoxy-2-propanol (PGME) and the above-mentioned shortened anion-modified cellulose fiber 1 were mixed to obtain a dispersion with a solids concentration of 10% by mass. 40.5 g of EOPO amine was added to 300 g of the obtained dispersion, and the mixture was stirred at 25°C for 1 hour to obtain a dispersion of hydrophobically modified cellulose fiber 1. The bonding mode of the modifying group in hydrophobically modified cellulose fiber 1 was ionic bonding. The introduction rate of the modifying group in hydrophobically modified cellulose fiber 1 and other information are shown in Table 3.

[0124]

[0125] To the entire dispersion of hydrophobically modified cellulose fiber 1 obtained, 300 g of the epoxy resin Celloxide 2021P was added, and the mixture was stirred at 25°C for 1 hour. The mixture was then dispersed five times at 150 MPa using a high-pressure homogenizer (Nanovaita L-ES, manufactured by Yoshida Kikai Kogyo Co., Ltd.). PGME was then removed from the dispersion using an evaporator, yielding a composition containing hydrophobically modified cellulose fiber 1 and a resin. This composition was used as the composition in Example 1 and Comparative Example 1.

[0126] [Hydrophobically modified cellulose fiber 1'] 1-methoxy-2-propanol (PGME) and the above-mentioned shortened anion-modified cellulose fiber 1 were mixed to obtain a dispersion with a solids concentration of 1% by mass. 4.5 g of EOPO amine was added to 300 g of the obtained dispersion, and the mixture was stirred at 25°C for 1 hour to obtain a dispersion of hydrophobically modified cellulose fiber 1'. The bonding mode of the modifying group in hydrophobically modified cellulose fiber 1' was ionic bonding. The introduction rate of the modifying group in hydrophobically modified cellulose fiber 1' and other information are shown in Table 3.

[0127] To the entire dispersion of hydrophobically modified cellulose fiber 1' obtained, 300 g of the epoxy resin Celloxide 2021P was added and stirred at 25°C for 1 hour. The mixture was then dispersed five times at 150 MPa using a high-pressure homogenizer (Yoshida Kikai Kogyo Co., Ltd., Nanovaita L-ES). PGME was then removed from the dispersion using an evaporator, yielding a composition containing hydrophobically modified cellulose fiber 1' and resin. This composition was used as the composition in Example 2. A composition containing hydrophobically modified cellulose fiber 1' and resin was also obtained in the same manner as in Example 2, except that the same amount of jER828 was used as the epoxy resin instead of Celloxide 2021P. This composition was used as the composition in Example 3.

[0128] [Hydrophobically modified cellulose fiber 2] A dispersion of hydrophobically modified cellulose fiber 2 was obtained in the same manner as for hydrophobically modified cellulose fiber 1', except that the same amount of anionically modified cellulose fiber 1 was used instead of shortened anionically modified cellulose fiber 1. The bonding mode of the modifying group in hydrophobically modified cellulose fiber 2 was an ionic bond. The introduction rate of the modifying group in hydrophobically modified cellulose fiber 2 and other information are shown in Table 3.

[0129] To the total amount of the obtained dispersion of hydrophobically modified cellulose fiber 2, 300 g of epoxy resin (Examples 4 to 6), 300 g of terpineol (Example 7 and Comparative Example 2), 300 g of methyl ethyl ketone (Example 8), or 600 g of epoxy resin (Example 10) was added and stirred at 25°C for 1 hour. After that, a dispersion treatment was carried out five times at 150 MPa using a high-pressure homogenizer (Yoshida Kikai Kogyo Co., Ltd., Nanovaita L-ES). Subsequently, PGME was distilled off from the dispersion using an evaporator, thereby obtaining compositions containing hydrophobically modified cellulose fiber 2 and component (B). Each composition was used as the composition in the corresponding Example and Comparative Example.

[0130] [Hydrophobically modified cellulose fiber 3] 1-methoxy-2-propanol (PGME) and the above-mentioned anion-modified cellulose fiber 1 were mixed to obtain a dispersion with a solids concentration of 1% by mass. 0.66 g of trioctylamine was added to 300 g of the obtained dispersion, and the mixture was stirred at 25°C for 1 hour to obtain a dispersion of hydrophobically modified cellulose fiber 3. The bonding mode of the modifying group in hydrophobically modified cellulose fiber 3 was ionic bonding. The introduction rate of the modifying group in hydrophobically modified cellulose fiber 3 and other information are shown in Table 3.

[0131] To the entire dispersion of hydrophobically modified cellulose fiber 3 obtained, 300 g of methyl ethyl ketone was further added, and the mixture was stirred at 25°C for 1 hour. The mixture was then dispersed five times at 150 MPa using a high-pressure homogenizer (Nanovaita L-ES, manufactured by Yoshida Kikai Kogyo Co., Ltd.). PGME was then removed from the dispersion using an evaporator, yielding a composition containing hydrophobically modified cellulose fiber 3 and component (B). This composition was used as the composition in Example 9.

[0132] Examples 1 to 10 and Comparative Examples 1 and 2 [Storage Test] The above compositions were placed in screw tubes No. 7 (manufactured by AS ONE Corporation), the caps were sealed, and the compositions were stored at the temperatures shown in Tables 4 to 6 for 3 months under normal pressure and light-shielded conditions.

[0133] Reference Example 1 [Storage Test] A sample consisting of only the epoxy resin Celloxide 2021P was placed in a screw tube No. 7 (manufactured by AS ONE Corporation), the cap was sealed, and the sample was stored at the temperature shown in Table 4 for 3 months under normal pressure and light-shielded conditions.

[0134] In the above examples, the following components were used without any special purification. EOPO amine Jeffamine M2070: manufactured by Huntsman Corporation Trioctylamine Trioctylamine manufactured by Tokyo Chemical Industry Co., Ltd. Epoxy resin Celloxide 2021P: manufactured by Daicel Corporation (This resin is an alicyclic epoxy resin and is a liquid at 25°C and 1 atmosphere.) jER828: manufactured by Mitsubishi Chemical Corporation (This resin is a bisphenol A epoxy resin and is a liquid at 25°C and 1 atmosphere.) Organic solvent Terpineol: manufactured by Tokyo Chemical Industry Co., Ltd. (This organic solvent is a liquid at 25°C and 1 atmosphere.) MEK (methyl ethyl ketone): manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. (This organic solvent is a liquid at 25°C and 1 atmosphere.)

[0135] The compositions and test results of the above examples are shown in Tables 4 to 6.

[0136]

[0137]

[0138]

[0139] *: The content (mass%) of glucose moieties in the hydrophobically modified cellulose fiber in the composition.

[0140] Reference Example 1 is a composition consisting of uncured epoxy resin monomers, and its viscosity remained almost constant even after storage at 25°C for three months. In contrast, when a composition containing hydrophobically modified cellulose fibers and epoxy resin monomers was stored under the same conditions, the viscosity was significantly higher than before storage (Comparative Example 1). On the other hand, when the storage temperature was 4°C, the viscosity remained almost unchanged compared to before storage (Example 1). This suggests that viscosity changes can be suppressed by refrigerating a composition containing hydrophobically modified cellulose fibers and a nonaqueous liquid that is liquid at 25°C and 1 atmosphere, such as epoxy resin monomers.

[0141] Examples 2 to 8 demonstrated that viscosity changes of compositions can be suppressed even when various nonaqueous liquids, such as epoxy resins with different structures, are used, or when alcohols or ketones are used instead of resins. Example 9 demonstrated that viscosity changes of compositions can be suppressed when the modifying group structure of the hydrophobically modified cellulose fiber is not only a polymer group such as an (EO / PO) structure, but also a hydrocarbon group such as a trioctyl group. Example 10 demonstrated that viscosity changes of compositions can be suppressed even when the amount of hydrophobically modified cellulose fiber is reduced. Examples 4 to 6 demonstrated that sufficient viscosity change suppression was achieved at storage temperatures ranging from -4 to 15°C. Furthermore, comparing Example 7 with Comparative Example 2, even when the composition has the same composition, when the storage temperature exceeds 20°C, as in Comparative Example 2, the viscosity change rate increases, and viscosity changes of the composition tend to become uncontrollable.

[0142] [Production Example of Anion-Modified Cellulose Fiber 2] Results similar to those of the above examples can be obtained by using anion-modified cellulose fiber 2 having phosphate groups introduced therein instead of anion-modified cellulose fiber 1 having carboxy groups introduced therein. Such anion-modified cellulose fiber 2 can be prepared by the following phosphorylation treatment.

[0143] [Phosphorylation Treatment] 100 parts by mass of solids of bleached softwood kraft pulp fiber as the raw natural cellulose fiber is impregnated with a mixed aqueous solution of ammonium dihydrogen phosphate and urea, and then compressed to obtain 56 parts by mass of ammonium dihydrogen phosphate and 150 parts by mass of urea, to obtain chemical-impregnated fiber. The chemical-impregnated fiber is dried in a dryer at 105°C to evaporate water. The evaporated fiber is heated for 4 minutes in a fan dryer set at 140°C. 10,000 parts by mass of deionized water is added to 100 parts by mass of the obtained fiber, and the fiber is dispersed by stirring, and the solids are then filtered off by suction filtration. 10,000 parts by mass of deionized water is added to 100 parts by mass of the solids in the filtered cake, and the fiber is dispersed by stirring, and the solids are then filtered off by suction filtration. To the resulting cake, 10,000 parts by mass of deionized water is added, and while stirring, a 1 N aqueous sodium hydroxide solution is added dropwise to obtain a slurry with a pH of 12 to 13. Next, while stirring, 0.01 M hydrochloric acid is added to the suspension to adjust the pH to 2. The solid content is then separated by suction filtration. The resulting cake is dispersed in deionized water, and the cake is separated by suction filtration. This operation is repeated until the conductivity of the filtrate reaches 200 μS / cm or less. The resulting solid content is subjected to a dehydration treatment to obtain anion-modified cellulose fiber 2.

[0144] The storage method of the present invention can suppress changes in viscosity over time of compositions containing hydrophobically modified cellulose fibers and non-aqueous liquids, and is therefore effective for storing various paints, coating agents, adhesives, sealing materials, electrical insulating materials such as printed wiring boards, composite materials such as glass fiber / carbon fiber composite materials, and civil engineering and construction materials such as flooring materials, paving materials, and lining materials, which contain hydrophobically modified cellulose fibers.

Claims

1. A method for storing a composition containing the following components (A) and (B) in a refrigerator: Component (A): Hydrophobically modified cellulose fiber; Component (B): A non-aqueous liquid that is liquid at 25°C and 1 atmosphere.

2. A method of storing a composition containing the following components (A) and (B) at 20°C or below: Component (A): Hydrophobically modified cellulose fiber Component (B): A non-aqueous liquid that is liquid at 25°C and 1 atmosphere.

3. A method of storing a composition containing the following components (A) and (B) in a refrigerator at 20°C or below: Component (A): Hydrophobically modified cellulose fiber Component (B): A non-aqueous liquid that is liquid at 25°C and 1 atmosphere.

4. A method for storing a composition containing the following components (A) and (B) in a refrigerator: Component (A): Hydrophobically modified cellulose fiber Component (B): A non-aqueous liquid that is liquid at 25°C and 1 atmosphere.

5. A method of storing a composition containing the following components (A) and (B) at 20°C or below: Component (A): Hydrophobically modified cellulose fiber Component (B): A non-aqueous liquid that is liquid at 25°C and 1 atmosphere.

6. A method of storing a composition containing the following components (A) and (B) in a refrigerator at 20°C or below: Component (A): Hydrophobically modified cellulose fiber Component (B): A non-aqueous liquid that is liquid at 25°C and 1 atmosphere.

7. The method according to any one of claims 1 to 6, wherein the content of component (A) in the composition is 0.1 parts by mass or more and 100 parts by mass or less per 100 parts by mass of component (B).

8. The method according to any one of claims 1 to 7, wherein the content of component (A) in the composition is 0.1% by mass or more and 50% by mass or less.

9. The method according to any one of claims 1 to 8, wherein the content of the glucose moiety of component (A) in the composition is 0.1 parts by mass or more and 100 parts by mass or less per 100 parts by mass of component (B).

10. The method according to any one of claims 1 to 9, wherein the content of the glucose moiety of component (A) in the composition is 0.1% by mass or more and 20% by mass or less.

11. The method according to any one of claims 1 to 10, wherein component (A) has a modifying group via an ionic and / or covalent bond.

12. The method according to claim 11, wherein the modifying group carried by component (A) is bonded to glucose constituting cellulose via an ionic bond and / or an amide bond.

13. The method according to claim 11 or 12, wherein the modifying group carried by component (A) is one or more types selected from the group consisting of (a) hydrocarbon groups and (b) polymer groups.

14. The method according to any one of claims 11 to 13, wherein the modifying group possessed by component (A) is a group derived from one or more modifying compounds selected from the group consisting of primary amines, secondary amines, tertiary amines, and quaternary ammonium compounds.

15. The method of any one of claims 1 to 14, wherein component (B) comprises a non-aqueous resin and / or an organic solvent.

16. The method according to any one of claims 1 to 15, wherein the viscosity of the composition at 25°C after storage is 1 mPa·s or more and 100,000 mPa·s or less.

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