Thickener composition

Abstract

To provide a thickener composition of a non-aqueous solvent, which is inhibited from viscosity decrease even at a high temperature and is suitable for use at 50°C or higher.SOLUTION: A thickener composition comprises modified cellulose fiber and a non-aqueous solvent and is used at 50°C or higher, where the modified cellulose fiber is at least one selected from the group consisting of the following (1) and (2): (1) one formed by bonding a modifying group to cellulose fiber and having an I type crystal structure, where the modifying group includes one or more selected from the group consisting of (a) a hydrocarbon group, (b) a silicone chain, and (c) an alkylene oxide chain; and (2) an acid-type anion-modified cellulose fiber having an I type crystal structure.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a thickener composition, a viscosity control agent for a non-aqueous solvent, the use of the thickener composition, and a method for applying inorganic compounds. [Background technology]

[0002] In recent years, environmentally friendly technologies have been attracting attention, and against this technological background, materials using cellulose fibers, which are naturally occurring biomass, have been attracting attention. For example, Patent Document 1 discloses a fine cellulose fiber composite dispersion containing a fine cellulose fiber composite formed by bonding an amine to the anionic groups of an anion-modified cellulose fiber containing an anionic group via an ionic bond, a dispersant, and an organic liquid compound. Patent Document 2 also discloses a method for producing a gel composition, which includes the steps of dispersing cellulose having a cellulose type I crystal structure in water, converting the hydroxyl groups of the cellulose into substituents having carboxyl groups, substituting water, which is the dispersant for the cellulose, with an organic solvent, hydrophobizing the cellulose after the dispersant substitution, and nano-defibrating the hydrophobized cellulose to obtain a gel composition in which cellulose nanofibers are dispersed in an organic solvent, wherein the cellulose is hydrophobized by a neutralization reaction with a polyetheramine. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2019-119867 [Patent Document 2] Japanese Patent Application Laid-Open No. 2017-19896 Summary of the Invention [Problem to be solved by the invention]

[0004] Patent Document 1 describes the dispersibility of cellulose fibers in organic liquid compounds, and Patent Document 2 describes a method for producing a gel composition in which cellulose fibers are dispersed in an organic solvent, but these documents do not make any mention of changes in viscosity properties at high temperatures. The present invention relates to a thickener composition for a non-aqueous solvent, which is suitable for use at temperatures of 50°C or higher because the decrease in viscosity is suppressed even at high temperatures. [Means for solving the problem]

[0005] The present invention relates to the following [1] to [7]. [1] A thickener composition containing modified cellulose fiber and a non-aqueous solvent, which is used at 50°C or higher, A thickener composition, wherein the modified cellulose fiber is one or more types selected from the group consisting of the following (1) and (2): (1) A cellulose fiber having a type I crystal structure in which a modifying group is bonded to the cellulose fiber, the modifying group containing one or more groups selected from the group consisting of (a) a hydrocarbon group, (b) a silicone chain, and (c) an alkylene oxide chain. (2) Acid-type anion-modified cellulose fiber with I-type crystal structure [2] The thickener composition according to [1] above, which is for use in electronic materials, optical materials, or structural materials. [3] The thickener composition according to [1] or [2] above, further comprising an inorganic compound. [4] A viscosity control agent for a non-aqueous solvent, comprising one or more modified cellulose fibers selected from the group consisting of the following (1) and (2): (1) A cellulose fiber having a type I crystal structure in which a modifying group is bonded to the cellulose fiber, the modifying group containing one or more groups selected from the group consisting of (a) a hydrocarbon group, (b) a silicone chain, and (c) an alkylene oxide chain. (2) Acid-type anion-modified cellulose fiber with I-type crystal structure [5] The viscosity control agent according to [4], further comprising an inorganic compound. [6] Use of a thickener composition containing one or more modified cellulose fibers selected from the group consisting of the following (1) and (2) and a non-aqueous solvent at 50°C or higher: (1) A cellulose fiber having a type I crystal structure in which a modifying group is bonded to the cellulose fiber, the modifying group containing one or more groups selected from the group consisting of (a) a hydrocarbon group, (b) a silicone chain, and (c) an alkylene oxide chain. (2) Acid-type anion-modified cellulose fiber with I-type crystal structure [7] A method for applying an inorganic compound, comprising a step of heating a composition containing one or more modified cellulose fibers selected from the group consisting of (1) and (2) below, a non-aqueous solvent, and an inorganic compound to 100°C or higher to remove the non-aqueous solvent. (1) A cellulose fiber having a type I crystal structure in which a modifying group is bonded to the cellulose fiber, the modifying group containing one or more groups selected from the group consisting of (a) a hydrocarbon group, (b) a silicone chain, and (c) an alkylene oxide chain. (2) Acid-type anion-modified cellulose fiber with I-type crystal structure [Effects of the Invention]

[0006] The non-aqueous solvent thickener composition of the present invention has the effect of suppressing a decrease in viscosity even at high temperatures of 50°C or higher. [Brief explanation of the drawings]

[0007] [Figure 1] FIG. 1 is a rheometer chart of the thickener compositions of Example 1 and Comparative Example 1. [Figure 2] FIG. 2 is a rheometer chart of the thickener compositions in Examples 8 to 10. DETAILED DESCRIPTION OF THE INVENTION

[0008] Although the detailed mechanism of the thickener composition of the present invention is unknown, it is speculated that the cellulose fibers to which hydrophobic modifying groups have been introduced are uniformly dispersed in a non-aqueous solvent, forming a loose network structure, thereby exerting the effect of maintaining viscosity at high temperatures.

[0009] <Thickener composition> The thickener composition of the present invention contains modified cellulose fibers and a non-aqueous solvent, and is used at temperatures of 50°C or higher.

[0010] [Modified cellulose fiber] The modified cellulose fiber in the present invention is one or more types selected from the group consisting of the following (1) and (2).

[0011] (1) A cellulose fiber having a type I crystal structure in which a modifying group is bonded to the cellulose fiber, the modifying group containing one or more groups selected from the group consisting of (a) a hydrocarbon group, (b) a silicone chain, and (c) an alkylene oxide chain. (2) Acid-type anion-modified cellulose fibers with type I crystal structure. In this specification, when it is necessary to distinguish between the two, the modified cellulose fiber (1) will be referred to as "modified cellulose fiber (1)" and the modified cellulose fiber (2) will be referred to as "modified cellulose fiber (2)."

[0012] Modified cellulose fibers (1) The modified cellulose fiber (1) is a cellulose fiber to which a modifying group is bonded. From the viewpoint of ease of bonding of the modifying group, the cellulose fiber is preferably anion-modified cellulose fiber.

[0013] (anion-modified cellulose fiber) Anion-modified cellulose fibers are cellulose fibers having anionic groups, such as one or more groups selected from the group consisting of carboxyl groups, (phosphite) groups, and sulfonic acid groups, in the molecule. Introduction of anionic groups into cellulose fibers can be achieved by the methods described below. From the standpoints of availability and effectiveness, anion-modified cellulose fibers having carboxyl groups as anionic groups are preferred, and anion-modified cellulose fibers in which the group (—CHOH) at the C6 position of the glucose unit constituting the cellulose fiber has been selectively converted to a carboxyl group (referred to as “oxidized cellulose fibers”) are more preferred. The counter ion of the anionic group is preferably a proton.

[0014] The anionic group content in the anion-modified cellulose fiber is preferably 0.1 mmol / g or more, more preferably 0.4 mmol / g or more, even more preferably 0.6 mmol / g or more, even more preferably 0.7 mmol / g or more, and even more preferably 0.8 mmol / g or more, from the viewpoint of stable introduction of modifying groups. Furthermore, from the viewpoint of improving handleability, it is preferably 3 mmol / g or less, more preferably 2.5 mmol / g or less, even more preferably 2.3 mmol / g or less, even more preferably 2.1 mmol / g or less, even more preferably 2.0 mmol / g or less, and even more preferably 1.9 mmol / g or less. The term "anionic group content" refers to the total amount of anionic groups in the glucose constituting the cellulose fiber, and is specifically measured by the method described in the Examples below.

[0015] The preferred ranges of the average fiber diameter and average fiber length of the anion-modified cellulose fibers are preferably the same as those of the raw material cellulose fibers, although they depend on the order of the manufacturing steps.

[0016] The term "modifying groups bonded to anionic groups of anion-modified cellulose fibers" means that the modifying groups are bonded to anionic groups, preferably carboxy groups, possessed by the anion-modified cellulose fibers. The bond between the modifying groups and the anionic groups can be an ionic bond and / or a covalent bond. Examples of covalent bonds include amide bonds, ester bonds, and urethane bonds, with amide bonds being preferred.

[0017] (modifying group) The modifying groups include (a) hydrocarbon groups, (b) silicone chains, and (c) alkylene oxide chains. These modifying groups may be bonded (introduced) to cellulose fibers either alone or in combination.

[0018] (a) Hydrocarbon group The hydrocarbon group includes monovalent hydrocarbon groups, for example, chain saturated hydrocarbon groups, chain unsaturated hydrocarbon groups, cyclic saturated hydrocarbon groups, and aromatic hydrocarbon groups.

[0019] The number of carbon atoms in the hydrocarbon group is 1 or more, preferably 3 or more, more preferably 8 or more, and even more preferably 10 or more, from the viewpoint of improving the dispersibility of cellulose in non-aqueous solvents and suppressing a decrease in viscosity even at high temperatures of 50°C or higher (hereinafter simply referred to as high temperature), and from the same viewpoints, is preferably 30 or less, more preferably 22 or less, and even more preferably 20 or less. The hydrocarbon group may further have a substituent described below, and a portion of the hydrocarbon group may be substituted with a hydrogen nitride group.

[0020] The chain saturated hydrocarbon group is preferably one having 3 to 30 carbon atoms, and specific examples include 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 tetraethyl group, a tetrabutyl group, a tetrapropyl group, a tetradecyl group, an octadecyl group, a docosyl group, and an octacosanyl group.

[0021] The chain unsaturated hydrocarbon group is preferably one having 3 to 30 carbon atoms, and specific examples include a propenyl group, a butenyl group, an isobutenyl group, an isoprenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, and an octadecenyl group.

[0022] The cyclic saturated hydrocarbon group is preferably one having 3 to 20 carbon atoms, and specific examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl 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.

[0023] Examples of aromatic hydrocarbon groups include aryl groups and aralkyl groups. In the aryl group and aralkyl group, the aromatic ring itself may be substituted or unsubstituted. The heterocyclic aromatic hydrocarbon group includes an imidazole group.

[0024] The total number of carbon atoms in the aryl group is preferably 6 or more and 24 or less, and specific 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 a substituent.

[0025] The total number of carbon atoms in the aralkyl group is preferably 7 or more and 24 or less, and specific examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylpentyl group, a phenylhexyl group, a phenylheptyl group, a phenyloctyl group, and groups in which the aromatic group in these groups is substituted with a substituent. The total number of carbon atoms in the imidazole group is preferably 3 or more and 24 or less, and specific examples of the imidazole group include an imidazole group, a methylimidazole group, an ethylimidazole group, a propylimidazole group, a 2-phenylimidazole group, a benzimidazole group, and groups in which these groups are substituted with a substituent.

[0026] (b) Silicone chain The silicone chain is a monovalent group having a siloxane bond as the main chain, and may further include an alkylene group. The silicone chain may further include a substituent, as described below.

[0027] (c) alkylene oxide chain The alkylene oxide chain is a structure containing a (co)polymer of ethylene oxide (EO) or propylene oxide (PO), and is preferably one or more (co)polymer moieties selected from the group consisting of a structure containing a polymer of EO (EO polymerized moiety), a structure containing a polymer of PO (PO polymerized moiety), and a structure containing a copolymer in which EO and PO are polymerized randomly or in a block form ((EO / PO) copolymerized moiety). The alkylene oxide chain may further have a substituent described below.

[0028] Examples of the alkylene oxide chain include those represented by the following formula:

[0029] [ka]

[0030] (In the formula, R 1 represents a hydrogen atom, a hydrocarbon group having from 1 to 6 carbon atoms, or a -CH2CH(CH3)NH2 group. EO and PO are present randomly or in a block form, a is 0 or a positive number indicating the average number of moles of EO added, and b is 0 or a positive number indicating the average number of moles of PO added, except when both a and b are 0.

[0031] In the above formula, a represents the average number of moles of EO added, and from the viewpoints of availability and affinity with non-aqueous solvents, it is preferably 0 or more, more preferably 1 or more, and even more preferably 2 or more; from the same viewpoints, it is preferably 100 or less, more preferably 70 or less.

[0032] In the above formula, b represents the average number of moles of PO added, and from the viewpoint of affinity with non-aqueous solvents, it is preferably 0 or more, more preferably 1 or more, and even more preferably 3 or more, and from the viewpoint of availability, it is preferably 50 or less, more preferably 40 or less.

[0033] R in the above formula 1 Specific examples of the hydrocarbon group having 1 to 6 carbon atoms 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, and an isohexyl group.

[0034] The formula weight (molecular weight) of the alkylene oxide chain is preferably 500 or more, more preferably 1,000 or more, from the viewpoint of suppressing a decrease in viscosity even at high temperatures (e.g., 50°C or higher), and from the same viewpoint, is preferably 10,000 or less, more preferably 7,000 or less. The formula weight of the alkylene oxide chain can be determined by calculation from the average number of moles added when producing an amine compound having an alkylene oxide chain, which will be described later.

[0035] The PO content (mol %) in the (EO / PO) copolymerization portion is preferably 1 mol % or more, more preferably 5 mol % or more, from the viewpoint of suppressing a decrease in viscosity even at high temperatures, and from the same viewpoint, is preferably 100 mol % or less, more preferably 95 mol % or less, and even more preferably 90 mol % or less. The PO content in the (EO / PO) copolymerization portion can be determined by calculation from the average number of moles added when producing an amine compound having an alkylene oxide chain, which will be described later.

[0036] (d) Further Substituents The modifying group may further have a substituent, such as an alkoxy group having 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, an isopentyloxy group, or a hexyloxy group; a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, or a sec-butoxycarbonyl group; alkoxycarbonyl groups having 1 to 6 carbon atoms, 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.

[0037] [Method for producing modified cellulose fiber (1)] The modified cellulose fiber (1) can be produced, for example, by introducing anionic groups into raw cellulose fibers to produce anion-modified cellulose fibers (step 1), and then bonding modifying groups to the anionic groups of the anion-modified cellulose fibers (step 2).

[0038] (Process 1) Raw material: cellulose fiber As the cellulose fiber that is the raw material for the anion-modified cellulose fiber, natural cellulose is preferred from an environmental perspective, and examples thereof include wood pulp such as softwood pulp and hardwood pulp; cotton pulp such as cotton linter and cotton lint; non-wood pulp such as straw pulp and bagasse pulp; and bacterial cellulose, and these can be used alone or in combination of two or more.

[0039] The average fiber diameter of the raw cellulose fibers is not particularly limited, but from the viewpoints of handleability and cost, it is preferably 5 μm or more, more preferably 7 μm or more, and from the same viewpoints, it is preferably 500 μm or less, more preferably 300 μm or less. The average fiber diameter of the raw cellulose fibers is determined by the method described in the Examples below.

[0040] The average fiber length of the raw cellulose fibers is not particularly limited, but from the viewpoints of availability and cost, it is preferably 5 μm or more, more preferably 25 μm or more, and from the same viewpoints, it is preferably 5,000 μm or less, more preferably 3,000 μm or less. The average fiber length of the raw cellulose fibers can be measured according to the method described in the Examples below.

[0041] Processing method (1) When carboxyl groups are introduced as anionic groups into cellulose fibers Methods for introducing carboxy groups into cellulose fibers include, for example, a method of oxidizing the hydroxy groups of the cellulose fibers to convert them into carboxy groups, 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.

[0042] Examples of methods for oxidizing the hydroxy groups of cellulose fibers include those described in JP 2015-143336 and JP 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, the group at C6 of the glucose of the cellulose fiber structural unit is selectively converted to a carboxy group, thereby producing the oxidized cellulose fibers described above.

[0043] The compound having a carboxy group to be used for introducing a carboxy group into cellulose fibers is not particularly limited, but specific examples include halogenated acetic acids, such as chloroacetic acid.

[0044] The acid anhydrides of compounds having a carboxyl group and their derivatives to be used for introducing a carboxyl group into cellulose fibers are not particularly limited, and examples thereof include acid anhydrides of dicarboxylic acid compounds such as maleic anhydride, succinic anhydride, phthalic anhydride, and adipic anhydride, imidized products of acid anhydrides of compounds having a carboxyl group, and derivatives of acid anhydrides of compounds having a carboxyl group. These compounds may be substituted with a hydrophobic group.

[0045] (2) When sulfonic acid groups or (phosphorous) groups are introduced as anionic groups into cellulose fibers As a method for introducing sulfonic acid groups into cellulose fibers, a method of adding sulfuric acid to cellulose fibers and heating the fibers can be given.

[0046] Methods for introducing (phosphite) groups into cellulose fibers include mixing a powder or aqueous solution of (phosphite) phosphorous or a (phosphite) derivative with dry or wet cellulose fibers, or adding an aqueous solution of (phosphite) phosphorous or a (phosphite) derivative to a dispersion of cellulose fibers. When these methods are employed, dehydration treatment, heat treatment, etc. are generally carried out after mixing or adding a powder or aqueous solution of (phosphite) phosphorous or a (phosphite) derivative.

[0047] (Process 2) Introduction of modifying groups into the anionic groups of anion-modified cellulose fibers is achieved by reacting the anion-modified cellulose fibers with a compound for introducing modifying groups into the anionic groups (referred to as a "modifying compound"). Methods for introducing modifying groups include (1) JP 2015-143336 A when introducing via an ionic bond, and (2) JP 2015-143337 A when introducing via an amide bond. After completion of step 2, 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.

[0048] (1) Introduction via ionic bond When the modifying group is introduced via an ionic bond, the anion-modified cellulose fiber and the modifying compound are mixed, and an ionic bond is formed between the anionic group contained in the anion-modified cellulose fiber and the amino group of the modifying compound. Specifically, when oxidized cellulose fibers are used as the anion-modified cellulose fibers and a primary amine having the aforementioned modifying group is used as the modifying compound, the aforementioned modifying group can be introduced via an ionic bond to the carboxy group at the C6 position of the glucose constituting the cellulose fibers, as shown in the following formula (where C 6 is the carbon atom at the 6th position of the glucose that makes up the cellulose fiber, and R is a modifying group.

[0049] [ka]

[0050] Compound for modification The modifying compound used in this embodiment may be any compound capable of introducing a desired modifying group, and preferred examples include the above-mentioned amine compounds having a hydrocarbon group, an alkylene oxide chain, or a silicone chain, phosphonium compounds, and guanidino group-containing compounds.

[0051] Amine compounds The amine compound is, for example, an amine compound having the aforementioned hydrocarbon group, the aforementioned alkylene oxide chain, or the aforementioned silicone chain as a modifying group, and such hydrocarbon group or the like is introduced into the anion-modified cellulose fiber via an ionic bond to become the modifying group in the modified cellulose fiber.

[0052] The amine compound may be any of primary amines, secondary amines, tertiary amines, and quaternary ammonium compounds. From the viewpoint of reactivity, preferred anion components of the quaternary ammonium compounds include halogen ions such as chloride ions and bromide ions, hydrogen sulfate ions, perchlorate ions, tetrafluoroborate ions, hexafluorophosphate ions, trifluoromethanesulfonate ions, and hydroxy ions.

[0053] Amine compounds having hydrocarbon groups Specific examples of amine compounds 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, naphthylamine, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, and 1-(3-aminopropyl)imidazole. 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.

[0054] The amine compound having a hydrocarbon group may be a commercially available product or may be prepared according to a known method.

[0055] Amine compounds having alkylene oxide chains In the amine compound, the alkylene oxide chain 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. Preferred examples of such alkylene groups include ethylene and propylene groups.

[0056] Examples of the amine having an alkylene oxide chain include amines represented by the following formula (i):

[0057] [ka]

[0058] In formula (i), R 1 , a and b are R in the formula showing an example of the alkylene oxide chain. 1 , a and b.

[0059] Amine compounds having alkylene oxide chains can be prepared according to known methods. For example, desired amounts of ethylene oxide and propylene oxide can 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, see JP-A-3-181448, and details of such amine compounds are described, for example, in JP-A-6105139.

[0060] As the amine compound having an alkylene oxide chain, for example, commercially available products can be suitably used. Specific examples 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-900, Jeffamine ED-2003, Jeffamine D-2000, Jeffamine D-4000, XTJ-510, Jeffamine T-3000, and Jeffamine ED-2003, all manufactured by HUNTSMAN. Examples include T-5000, XTJ-502, XTJ-509, and XTJ-510, and 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. These may be used alone or in combination of two or more.

[0061] Amine compounds with silicone chains Examples of such amine compounds include those having a structure in which an amino group is bonded to a silicone chain skeleton via an alkylene group or the like. In this specification, such amine compounds may be referred to as "amino-modified silicones." The amino-modified silicones may be commercially available products or may be prepared according to known methods. Only one type of amino-modified silicone may be used, or two or more types may be used.

[0062] As amino-modified silicones, from the viewpoint of performance, the following products are recommended: 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), 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), all manufactured by Shin-Etsu Chemical Co., Ltd. Kinematic viscosity is measured at 25°C (unit: mm 2 / s), and the unit of amino equivalent is g / mol.

[0063] Guanidino group-containing compounds The guanidino group-containing compound is, for example, a guanidine compound having the aforementioned hydrocarbon group, alkylene oxide chain, or silicone chain as a modifying group, and such hydrocarbon group or the like is introduced into the anion-modified cellulose fiber via an ionic bond to become the modifying group in the modified cellulose fiber. Examples of the guanidino group-containing compound include diphenylguanidine, ditolylguanidine, 1,2,3-triphenylguanidine, aminoguanidine, and arginine.

[0064] Reaction conditions etc. The amount of modifying compound used is, from the standpoint of reactivity, preferably an amount such that the number of amino groups in the modifying compound is 0.01 mol or more, more preferably 0.1 mol or more, even more preferably 0.5 mol or more, even more preferably 0.7 mol or more, and even more preferably 1 mol or more per mol of carboxy groups in the oxidized cellulose fiber, and, from the standpoint of product purity, preferably an amount such that the number of amino groups is 50 mol or less, more preferably 20 mol or less, and even more preferably 10 mol or less. When the modifying compound has multiple amino groups, it is used so that the total number of moles of amino groups is the above-mentioned number of moles.

[0065] It is preferable to use a solvent when mixing. As the solvent, it is preferable to select a solvent in which the compound to be used dissolves, and examples thereof include methanol, ethanol, isopropanol (IPA), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N,N-dimethylacetamide, tetrahydrofuran (THF), acetone, methyl ethyl ketone (MEK), cyclohexanone, ethyl acetate, acetonitrile, dichloromethane, chloroform, toluene, acetic acid, 1-methoxy-2-propanol (PGME), water, etc., and these can be used alone or in combination of two or more.

[0066] The temperature during mixing is preferably 0°C or higher, more preferably 5°C or higher, and even more preferably 10°C or higher, from the viewpoint of the reactivity of the compound. Furthermore, from the viewpoint of suppressing discoloration of the modified cellulose fiber, it is preferably 50°C or lower, more preferably 40°C or lower, and even more preferably 30°C or lower. The mixing time can be appropriately set depending on the type of compound and solvent used, but from the viewpoint of the reactivity of the compound, it is preferably 0.01 hour or higher, more preferably 0.1 hour or higher, and from the viewpoint of productivity, it is preferably 48 hours or lower, more preferably 24 hours or lower.

[0067] (2) Introduction via an amide bond When the modifying group is introduced via an amide bond, the anion-modified cellulose fiber and the modifying compound are mixed in the presence of a known condensing agent, whereby an amide bond is formed between the anionic group contained in the anion-modified cellulose fiber and the amino group of the modifying compound.

[0068] Specifically, when oxidized cellulose fibers are used as the anion-modified cellulose fibers and a primary amine having the aforementioned modifying group is used as the modifying compound, the aforementioned modifying group can be introduced via an amide bond to the carboxy group at the C6 position of the glucose constituting the cellulose fibers, as shown in the following formula (wherein: C 6 is the carbon atom at the 6th position of the glucose that makes up the cellulose fiber, and R is a modifying group.

[0069] [ka]

[0070] Compound for modification The modifying compound used in this embodiment may be any compound capable of introducing a desired modifying group, and preferred examples include the above-mentioned amine compounds having a hydrocarbon group, an alkylene oxide chain, or a silicone chain.

[0071] Amine compounds The amine compound is, for example, an amine compound having the aforementioned hydrocarbon group, the aforementioned alkylene oxide chain, or the aforementioned silicone chain as a modifying group, and such hydrocarbon group or the like is introduced into the anion-modified cellulose fiber via an amide bond to become the modifying group in the modified cellulose fiber.

[0072] Examples of the amine compound include primary amines and secondary amines. Specific examples of the amine compound include primary amines and secondary amines among amine compounds having a hydrocarbon group, amine compounds having an alkylene oxide chain, and amine compounds having a silicone chain, which are exemplified in the above-mentioned "(1) Aspect of introduction via ionic bond."

[0073] Reaction conditions The amount of modifying compound used is, from the viewpoint of reactivity, preferably an amount such that the amount of amino groups in the modifying compound is 0.05 mol or more, more preferably 0.1 mol or more, even more preferably 0.2 mol or more, even more preferably 0.3 mol or more, and even more preferably 0.5 mol or more per mol of carboxy groups in the oxidized cellulose fiber, and, from the viewpoint of product purity, an amount such that the amount is 50 mol or less, more preferably 20 mol or less, and even more preferably 10 mol or less. When the modifying compound has multiple amino groups, it is used so that the total number of moles of amino groups is the above-mentioned number of moles.

[0074] The condensing agent is not particularly limited, but includes those described on page 116 of Synthetic Chemistry Series: Peptide Synthesis (Maruzensha) or those described in Tetrahedron, 57, 1551 (2001), such as 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (hereinafter sometimes referred to as "DMT-MM"). It is also possible to carry out the reaction by heat treatment alone without using a condensing agent.

[0075] A solvent may or may not be used in the amidation reaction. When a solvent is used, it is preferable to select a solvent that dissolves the compound to be used. Specific examples of the solvent include the solvents exemplified in the above-mentioned "(1) Mode of introduction via ionic bond."

[0076] The reaction time and reaction temperature in the amidation reaction can be appropriately selected depending on the type of compound and solvent used, etc., but from the viewpoint of the reaction rate, they are preferably 1 to 24 hours, more preferably 10 to 20 hours. From the viewpoint of reactivity, the reaction temperature is preferably 0°C or higher, more preferably 5°C or higher, and even more preferably 10°C or higher. From the viewpoint of product quality such as coloration, the reaction temperature is preferably 200°C or lower, more preferably 80°C or lower, and even more preferably 30°C or lower.

[0077] (Refining process) By micronizing the cellulose fibers at any stage of the production method of the modified cellulose fibers (for example, before step 1, before step 2, and after step 2), it is possible to micronize the cellulose fibers from the micrometer scale to the nanometer scale. Reducing the average fiber diameter to the nanometer size is preferable because it improves dispersibility in the resin.

[0078] The micronization treatment can be carried out by a known micronization treatment method. For example, to obtain modified cellulose fibers having an average fiber diameter of nanometer size, 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] Examples of the medium include alcohols having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, such as water, methanol, ethanol, propanol, and 1-methoxy-2-propanol (PGME); ketones having 3 to 6 carbon atoms, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ketones having 2 to 4 carbon atoms, such as ethyl acetate and butyl acetate; saturated or unsaturated hydrocarbons having 1 to 6 carbon atoms; aromatic hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as methylene chloride and chloroform; lower alkyl ethers having 2 to 5 carbon atoms; and polar solvents such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide, and dimethyl sulfoxide. These solvents can be used alone or in combination. The amount of the medium used should be an effective amount for dispersing the modified cellulose fibers. The amount used is preferably at least 1 times, more preferably at least 2 times, and preferably at most 500 times, more preferably at most 200 times the mass of the modified cellulose fibers.

[0080] 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 solid content of the modified cellulose fiber in the micronization treatment is preferably 50 mass% or less.

[0081] (Short fiber processing) At any stage in the production method of the modified cellulose fiber 1, the cellulose fiber may be further subjected to a fiber shortening treatment, i.e., a treatment to shorten the fiber length. The fiber shortening treatment can be achieved by subjecting the cellulose fiber to one or more treatment methods selected from the group consisting of alkali treatment, acid treatment, heat treatment, ultraviolet treatment, electron beam treatment, mechanical treatment, and enzyme treatment.

[0082] Modified cellulose fibers (2) The modified cellulose fiber (2) is an acid-type anion-modified cellulose fiber having a predetermined average fiber diameter. The acid-type anion-modified cellulose fiber is an "anion-modified cellulose fiber" in the description of the modified cellulose fiber (1) in which the counter ion of the anionic group is a proton, and is preferably an oxidized cellulose fiber in which the counter ion of the carboxyl group is a proton.

[0083] The preferred range of the anionic group content in the modified cellulose fiber (2) is the same as that in the "anion-modified cellulose fiber" in the description of the modified cellulose fiber (1). The modified cellulose fiber (2) can be produced by passing through step 1 in the "method for producing modified cellulose fiber (1)" and then the above-mentioned "microfibrillation step". At any stage in the process for producing the modified cellulose fibers (2), the cellulose fibers may be subjected to a fiber shortening treatment.

[0084] [Properties of modified cellulose fibers] The main properties of the modified cellulose fiber of the present invention are as follows:

[0085] (average fiber diameter, average fiber length) The modified cellulose fibers are preferably those that have been subjected to a micronization treatment to nanometer sizes. In this case, the average fiber diameter of the modified cellulose fibers is preferably 1 nm or more, more preferably 2 nm or more, from the viewpoints of handleability, availability, cost, and suppressing a decrease in viscosity even at high temperatures, and is preferably 300 nm or less, more preferably 200 nm or less, even more preferably 150 nm or less, and even more preferably 120 nm or less, from the viewpoints of handleability and solvent dispersibility. The average fiber diameter of the modified cellulose fibers that have been subjected to a micronization treatment can be determined by the method described in the Examples below.

[0086] The average fiber length of the modified cellulose fiber is preferably 100 nm or more, more preferably 200 nm or more, from the viewpoints of handleability, availability, cost, and suppressing a decrease in viscosity even at high temperatures, and is preferably 10,000 nm or less, even more preferably 5,000 nm or less, from the viewpoints of handleability and bringing the 80°C / 25°C viscosity ratio closer to 1. The average fiber length of the modified cellulose fiber can be determined by the method described in the examples below.

[0087] (average aspect ratio) In the present invention, the modified cellulose fiber may be one that has been subjected to a fiber shortening treatment. The average aspect ratio of the modified cellulose fiber is not particularly limited, but from the viewpoint of exerting its effect as a thickener, it is preferably 5 or more, more preferably 10 or more, and even more preferably 20 or more, while from the viewpoints of availability and handleability, it is preferably 300 or less, more preferably 200 or less, and even more preferably 100 or less. The average aspect ratio of the modified cellulose fiber is determined by the method described in the Examples below. By using modified cellulose fibers with a small average aspect ratio, the viscosity ratio at 80°C / 25°C can be brought closer to 1, improving handling properties.

[0088] (Amount of modified group bonded and introduction rate) The amount of modifying groups bonded to the modified cellulose fiber is preferably 0.01 mmol / g or more, more preferably 0.1 mmol / g or more, from the viewpoints of dispersibility and suppressing a decrease in viscosity even at high temperatures, and from the same viewpoint, is preferably 3.0 mmol / g or less, more preferably 2.5 mmol / g or less. When any two or more types of modifying groups are simultaneously introduced into the modified cellulose fiber, the amount of modifying groups bonded is preferably within the above range.

[0089] The introduction rate of the modifying group in the modified cellulose fiber is preferably 10 mol% or more, and the higher the better, from the viewpoints of dispersibility and suppressing a decrease in viscosity even at high temperatures, and is preferably 100 mol%. When any two or more types of modifying groups are simultaneously introduced as modifying groups, it is preferable that the total introduction rate be within the above range, provided that it does not exceed the upper limit of 100 mol%.

[0090] The bonded amount and introduction rate of the modifying group can be adjusted by the type and amount of the modifying compound 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 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 modified cellulose fiber are calculated by the method described in the Examples below.

[0091] (crystal structure) The modified cellulose fiber preferably has a cellulose type I crystal structure from the viewpoint of suppressing a decrease in viscosity even at high temperatures. The degree of crystallinity of the modified cellulose fiber is preferably 10% or more, more preferably 15% or more, and even more preferably 20% or more from the viewpoint of strength development of molded articles of the resin composition. Furthermore, from the viewpoint of raw material availability, the degree of crystallinity is preferably 90% or less, more preferably 85% or less, even more preferably 80% or less, and even more preferably 75% or less. Herein, the degree of crystallinity of the cellulose fiber 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 the cellulose type I crystal structure can be determined by the presence of a peak at 2θ = 22.6° in X-ray diffraction measurement.

[0092] The content of modified cellulose fiber in the composition of the present invention is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, in terms of cellulose (not including modifying groups) to impart thickening properties to the composition and suppress a decrease in viscosity even at high temperatures, while from the viewpoint of ease of handling the composition, it is preferably 50% by mass or less, more preferably 30% by mass or less, more preferably 20% by mass or less, more preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less. Hereinafter, the amount of modified cellulose fiber is expressed in terms of cellulose not including modifying groups.

[0093] [Non-aqueous solvent] From the viewpoint of using the thickener composition of the present invention at 50° C. or higher, the non-aqueous solvent preferably has a melting point of 100° C. or lower, more preferably 50° C. or lower, and even more preferably 20° C. or lower, and from the same viewpoint, the non-aqueous solvent preferably has a boiling point of 80° C. or higher, more preferably 100° C. or higher. The non-aqueous solvent is preferably liquid at the temperature at which it is used.

[0094] The non-aqueous solvent is preferably a hydrophobic solvent from the viewpoint of workability when used together with an inorganic compound, etc. The hydrophobic solvent preferably dissolves 100 g of water (at 20° C. and 1 atmosphere) in an amount of 100 g or less, more preferably 50 g or less, even more preferably 30 g or less, and still more preferably 10 g or less.

[0095] Specifically, alcohol-based solvents such as methanol, normal and isopropanol, t-butanol, 1-butanol, 1-hexanol, hexanal, and glycerin; ketone-based solvents such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, methyl hexyl ketone, diisobutyl ketone, diacetone alcohol, and isophorone; ether-based solvents such as diethyl ether, tetrahydrofuran (THF), and dioxane; methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, and polycarboxylic acid esters (e.g., phthalates, succinates, and adipates); Ester-based solvents such as fatty acid esters of aliphatic polyols such as glycerin; highly polar solvents such as N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), ethylene carbonate, N,N-dimethylacetamide (DMAc), and N-methylpyrrolidone; halogenated solvents such as methylene chloride, dichloromethane, chloroform, trichloroethylene, perchloroethylene, and chlorobenzene; non-aromatic hydrocarbon solvents such as hexane, petroleum ether, liquid paraffin, squalane, and squalene; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; and nitrile-based solvents such as acetonitrile.Glycol ether solvents such as t-butyl glycol, methyl diglycol, ethyl diglycol, butyl diglycol, 1-methoxy-2-propanol, methyl dipropylene glycol, 3-methoxybutanol, 3-methyl-3-methoxybutanol, (mono-, di-, tri-, poly)ethylene glycol methyl ether, ethylene glycol monophenyl ether, (mono-, di-, tri-, poly)ethylene glycol dimethyl (ethyl) ether, (mono-, di-, tri-, poly)ethylene glycol monobutyl ether, polyethylene glycol, methoxypolyethylene glycol, polyoxyethylene bisphenol A, polyoxypropylene bisphenol A, etc. (Glycol ether solvents include the following glycol ether (ester) solvents: butyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether ... Glycol ether ester solvents such as butyl ether acetate, methoxybutyl acetate, methyl methoxybutyl acetate, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether propionate, and dimethyl carbonate; polymerizable compounds, such as epoxy prepolymers (e.g., bisphenol type, novolac type, biphenyl type, biphenyl aralkyl type, aryl alkylene type, tetraphenylolethane type, naphthalene type, anthracene type, phenoxy type, dicyclopentadiene type, norbornene type, adamantane type, fluorene type, and glycidyl methacrylate copolymers); isocyanates (e.g., aromatic isocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, and aliphatic isocyanates such as hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, and tetramethylxylylene diisocyanate);Acrylic prepolymers (e.g., methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, nonanediol diacrylate, phenoxyethyl acrylate, (meth)acrylates of bisphenol A-alkylene oxide adducts, epoxy (meth)acrylates (bisphenol A type epoxy (meth)acrylate, novolac type epoxy (meth)acrylate, etc.); polyester (meth)acrylates (e.g., aliphatic polyester type ( (meth)acrylates, aromatic polyester-type (meth)acrylates, etc.); urethane (meth)acrylates (polyester-type urethane (meth)acrylates, polyether-type urethane (meth)acrylates, etc.); silicone (meth)acrylates, cyanoacrylate mono(meth)acrylates, etc., and oligomers of these polymerizable compounds; fatty acids such as oleic acid, palmitic acid, stearic acid, etc.; animal and vegetable oils such as olive oil, jojoba oil, and castor oil; silicone oil, fluorine-based inert liquids, process oils, etc. In this specification, non-aromatic hydrocarbon solvents and aromatic hydrocarbon solvents are collectively referred to as hydrocarbon solvents.

[0096] The non-aqueous solvent preferably contains a hydrocarbon solvent or a glycol ether solvent. Among these, when the modifying group is (a) a hydrocarbon group or (b) a silicone chain, hydrocarbon solvents, silicone oil, or glycol ether solvents (including glycol ether ester solvents) are preferred. When the modifying group is (c) an alkylene oxide chain, hydrocarbon solvents, alcohol solvents, ether solvents, ester solvents, glycol ether solvents (including glycol ether ester solvents), fatty acids, animal or vegetable oils, silicone oil, fluorine-based inert liquids, process oil, etc. are preferred. When the modifying group is (c) an alkylene oxide chain, hydrocarbon solvents or glycol ether solvents (including glycol ether ester solvents) are more preferred, and glycol ether solvents (including glycol ether ester solvents) are even more preferred. In the case of acid-type anion-modified cellulose fibers, a highly polar solvent is preferred.

[0097] The content of the non-aqueous solvent in the composition of the present invention depends on the presence or absence of inorganic compounds, but is generally preferably 15% by mass or more, more preferably 20% by mass or more, preferably 50% by mass or more, more preferably 75% by mass or more, even more preferably 85% by mass or more, and is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, preferably 15% by mass or more and 99.5% by mass or less, more preferably 20% by mass or more and 99% by mass or less. If necessary, part or all of the non-aqueous solvent may be removed from the composition of the present invention. Therefore, the composition of the present invention may be in the form of a solution or dispersion, or may be in the form of a dried powder.

[0098] Furthermore, in the composition of the present invention, the content of modified cellulose fiber (excluding modifying groups, etc.) is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and even more preferably 0.1 parts by mass or more, per 100 parts by mass of non-aqueous solvent, from the viewpoint of suppressing a decrease in viscosity even at high temperatures; and from the same viewpoint, it is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less, and is preferably 0.01 parts by mass or more and 20 parts by mass or less, more preferably 0.05 parts by mass or more and 10 parts by mass or less, and even more preferably 0.1 parts by mass or more and 5 parts by mass or less, per 100 parts by mass of non-aqueous solvent.

[0099] The water content in the composition of the present invention is preferably 20% by mass or less, more preferably 10% by mass or less, preferably 5% by mass or less, more preferably 1% by mass or less, and even more preferably 0.1% by mass or less, and may be substantially 0% by mass. The water content includes the amount of water carried over from the non-aqueous solvent.

[0100] [Inorganic compounds] Within the scope of not impairing the effects of the present invention, the composition of the present invention may contain inorganic compounds exemplified by metal oxides such as titanium oxide, zinc oxide, aluminum oxide, and zirconium oxide; metal powders such as gold, silver, copper, iron, tin, lead, zinc, and aluminum; inorganic salts such as calcium carbonate, aluminum hydroxide, and ammonium bromide; and inorganic solids such as ceramics, zeolite, carbon black, fullerene, carbon nanotubes, carbon fibers, graphene, silicon carbide, boron nitride, aluminum nitride, silica, talc, and clay. There are no particular limitations on the shape of the inorganic compound, but from the viewpoint of ease of handling, powder, granules, fibers, flakes, pellets, lumps, and paste are preferred.

[0101] The content of the inorganic compound in the composition of the present invention varies depending on the application and is not particularly limited, but from the viewpoint of dispersion stability of the inorganic compound at high temperatures of 50°C or higher and from the viewpoint of manifesting the effect of adding the inorganic compound, it is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, even more preferably 1 part by mass or more, even more preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, even more preferably 10 parts by mass or more, and even more preferably 100 parts by mass or more, per 100 parts by mass of modified cellulose fiber; on the other hand, from the viewpoint of manifesting the effects of the present invention, it is preferably 1,000,000 parts by mass or less, more preferably 500,000 parts by mass or less, even more preferably 300,000 parts by mass or less, even more preferably 100,000 parts by mass or less, even more preferably 50,000 parts by mass or less, even more preferably 30,000 parts by mass or less, and even more preferably 10,000 parts by mass or less. Therefore, in the composition of the present invention, the mass ratio of inorganic compound to modified cellulose fiber is preferably 0.1 / 100 or more and 10,000 / 1 or less, more preferably 1 / 100 or more and 1,000 / 1 or less, even more preferably 1 / 10 or more and 300 / 1 or less, and even more preferably 1 / 1 or more and 100 / 1 or less, from the viewpoint of dispersing the inorganic compound in a non-aqueous solvent.

[0102] Furthermore, the content of the inorganic compound 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, and on the other hand, is preferably 99% by mass or less, more preferably 95% by mass or less, more preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less. In the composition, the mass ratio of inorganic compound to non-aqueous solvent is preferably 1 / 100 or more, more preferably 1 / 10 or more, and even more preferably 1 / 1 or more, from the viewpoint of dispersing the inorganic compound in the non-aqueous solvent, and is preferably 500 / 1 or less, more preferably 300 / 1 or less, and even more preferably 100 / 1 or less, from the viewpoint of dispersion stability in the non-aqueous solvent at 50°C or higher.

[0103] [Other ingredients] The composition of the present invention may contain other components, such as plasticizers, nucleating agents, fillers (inorganic fillers, organic fillers), hydrolysis inhibitors, flame retardants, antioxidants, lubricants such as hydrocarbon waxes and anionic surfactants, UV absorbers, antistatic agents, antifogging agents, light stabilizers, pigments, mildew inhibitors, antibacterial agents, foaming agents, surfactants; starches, polysaccharides such as alginic acid; natural proteins such as gelatin, glue, and casein; tannins; fragrances; flow control agents; leveling agents; conductive agents; UV dispersants; and deodorizers, as long as the components do not impair the effects of the present invention. Furthermore, other polymeric materials and other compositions may also be added as long as the effects of the present invention are not impaired. These other components may be the inorganic compounds described above.

[0104] [Method for producing thickener composition] The thickener composition of the present invention can be produced, for example, by mixing the modified cellulose fiber with the non-aqueous solvent and the like. For example, the above-mentioned components can be kneaded using a known kneader such as an internal kneader, a single-screw or twin-screw extruder, a roll mill, or an open-roll kneader, or can be sheared by a solvent casting method or by shearing with a shearing device such as a high-shear processing machine.

[0105] Properties of the Thickener Composition Generally, the viscosity of a liquid substance tends to decrease as the temperature increases, but the composition of the present invention is characterized by a smaller tendency. Specifically, the value of [viscosity at 80°C] / [viscosity at 25°C] (viscosity ratio at 80°C / 25°C) of the composition of the present invention is preferably 0.6 or more, more preferably 0.7 or more, even more preferably 0.8 or more, and even more preferably 0.9 or more, from the viewpoint of suppressing viscosity decrease even at high temperatures, and is preferably 5 or less, more preferably 3 or less, even more preferably 2 or less, and even more preferably 1.5 or less, from the viewpoint of reducing temperature dependency. Furthermore, the [viscosity at 80°C] / [viscosity at 25°C] of the composition of the present invention is preferably 0.6 or more, more preferably 0.7 or more, even more preferably 0.8 or more, and even more preferably 0.9 or more, from the viewpoint of reducing temperature dependency. 120 Viscosity at ℃ / Viscosity at 25℃ ( 120 From the viewpoint of suppressing a decrease in viscosity even at high temperatures, the viscosity ratio (viscosity at 25°C / at 25°C) is preferably 0.6 or more, more preferably 0.7 or more, even more preferably 0.8 or more, and even more preferably 0.9 or more, and from the viewpoint of reducing temperature dependency, it is preferably 5 or less, more preferably 3 or less, even more preferably 2 or less, and even more preferably 1.5 or less.

[0106] The viscosity (mPa·s) of the composition of the present invention at 25°C is -1 On the other hand, from the viewpoint of workability when used as a thickener composition, it is preferably 500,000 or less, more preferably 300,000 or less, even more preferably 200,000 or less, even more preferably 100,000 or less, and even more preferably 30,000 or less, from the viewpoint of workability when used as a thickener composition, provided that

[0107] The viscosity (mPa·s) of the composition of the present invention at 80°C is -1 On the other hand, from the viewpoint of workability when used as a thickener composition, it is preferably 500,000 or less, more preferably 300,000 or less, even more preferably 200,000 or less, even more preferably 100,000 or less, and even more preferably 30,000 or less, from the viewpoint of workability when used as a thickener composition, provided that

[0108] The composition of the present invention 120 Viscosity (mPa·s) at a shear rate of 1.0 s -1 On the other hand, from the viewpoint of workability when used as a thickener composition, it is preferably 500,000 or less, more preferably 300,000 or less, even more preferably 200,000 or less, even more preferably 100,000 or less, and even more preferably 30,000 or less, from the viewpoint of workability when used as a thickener composition, provided that The thickener composition of the present invention has the above-described fluidity, and thus can improve workability.

[0109] The viscosity in this specification can be measured using a rheometer by the method described in the Examples below.

[0110] [Uses of the thickener composition] The thickener composition of the present invention can be used in various products without any particular restrictions. Specific examples of products to which the thickener composition of the present invention can be applied include foods and beverages, cosmetics, quasi-drugs, pharmaceuticals, daily necessities, feed, miscellaneous goods, agricultural chemicals, and chemical industrial products. More specifically, in fields such as home appliance parts, electronic materials (electronics), packaging containers, aerospace, civil engineering and construction, automobiles, and vehicle-mounted products, examples include resin molding materials, electrical insulating materials, paints, inks, coating agents, adhesives, repair materials, pressure-sensitive adhesives, lubricants, sealants, heat insulating materials, sound-absorbing materials, artificial leather materials, electronic materials, semiconductor materials, tires, automobile parts, and fiber composite materials. Among these, preferred are those for electronic materials, optical materials, and structural materials.

[0111] The amount of thickener composition to be blended into these products is not particularly limited, but is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and even more preferably 0.1 parts by mass or more, per 100 parts by mass of the product (or the total amount of each component constituting the product), while being preferably 1000 parts by mass or less, more preferably 800 parts by mass or less, and even more preferably 500 parts by mass or less.

[0112] <Use of Thickener Composition> The thickener composition of the present invention contains the modified cellulose fiber and a non-aqueous solvent, and is intended to be used at 50° C. or higher, preferably 60° C. or higher, and more preferably 80° C. or higher. From the viewpoint of thickening effect, the upper limit of the usable temperature is preferably 300° C., more preferably 280° C., even more preferably 250° C., and even more preferably 200° C. The thickener composition of the present invention is preferably used in a temperature range of 50°C or more, more preferably 100°C or more, and preferably 250°C or less, so as to maintain its thickening properties. Here, a temperature range of 50°C or more means, for example, 50°C to 100°C (a temperature range of 50°C), 40°C to 150°C (a temperature range of 110°C), or 70°C to 200°C (a temperature range of 130°C).

[0113] In this specification, use of a thickener composition at a specified temperature (or temperature range) means adding the thickener composition at a specified temperature (or temperature range) to an object to be thickened, or adding the thickener composition to an object to be thickened and then adjusting the temperature to the specified temperature (or temperature range). The thickener composition of the present invention is used at temperatures above 50°C, and therefore some or all of the non-aqueous solvent may volatilize, but it can be used without any problems. Depending on the application, the viscosity may be maintained at a certain temperature, and then further heating may be performed to completely evaporate the solvent component and solidify the composition. Even in such a case, the thickener composition of the present invention can be suitably used. When using the thickener composition, it is preferable that the thickener composition further contains the inorganic compound described above. Specific examples of applications over a temperature range of 50°C or more include lubricants and grease oils. Specific examples of applications in which the solvent is used over a temperature range of 50° C. or more and consequently removes non-aqueous solvents include paints and inks.

[0114] <Viscosity control agent for non-aqueous solvents> The viscosity control agent of the present invention contains the modified cellulose fiber. The viscosity control agent of the present invention is for use in non-aqueous solvents, and by applying the viscosity control agent to a non-aqueous solvent, it is possible to control the viscosity of the non-aqueous solvent, for example, to suppress viscosity reduction at high temperatures of 50°C or higher. As described above, the viscosity control agent of the present invention is preferably used at 50°C or higher, preferably 60°C or higher, more preferably 80°C or higher, while it is preferably used at 300°C or lower, more preferably 280°C, even more preferably 200°C or lower, and even more preferably 150°C or lower. Examples of non-aqueous solvents include those described above.

[0115] In the viscosity control agent of the present invention, the content of the modified cellulose fiber (not including modifying groups, etc.) relative to 100 parts by mass of the non-aqueous solvent is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and even more preferably 0.1 parts by mass or more, from the viewpoint of controlling the viscosity of the non-aqueous solvent, and from the same viewpoint, it is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less. That is, the content of the modified cellulose fiber (not including modifying groups, etc.) relative to 100 parts by mass of the non-aqueous solvent is preferably 0.01 parts by mass or more and 20 parts by mass or less, more preferably 0.05 parts by mass or more and 10 parts by mass or less, and even more preferably 0.1 parts by mass or more and 5 parts by mass or less.

[0116] [Inorganic compounds] The viscosity control agent of the present invention may contain an inorganic compound that can be used in the thickener composition described above, as long as the effect of the present invention is not impaired. The shape of the inorganic compound is not particularly limited, but from the viewpoint of handleability, powder, granules, fibers, flakes, pellets, lumps, and paste are preferred.

[0117] In the viscosity control agent of the present invention, the amount of the inorganic compound relative to the modified cellulose fiber is as described above in the thickener composition, and the preferred range is the same. The viscosity control agent of the present invention can control the viscosity of a non-aqueous solvent to preferred values ​​at 25°C, 80°C, and 120°C, the viscosity ratio at 80°C / 25°C, and the viscosity ratio at 120°C / 25°C, as described in the properties of the thickener composition above.

[0118] <Inorganic compound coating method> The present invention provides a method for applying an inorganic compound, which comprises a step of heating a composition containing modified cellulose fibers, which are one or more types selected from the group consisting of (1) and (2) below, a non-aqueous solvent, and an inorganic compound to 100°C or higher to remove the non-aqueous solvent. (1) A cellulose fiber having a type I crystal structure in which a modifying group is bonded to the cellulose fiber, the modifying group containing one or more groups selected from the group consisting of (a) a hydrocarbon group, (b) a silicone chain, and (c) an alkylene oxide chain. (2) Acid-type anion-modified cellulose fiber with I-type crystal structure The non-aqueous solvent and the inorganic compound are as described above.

[0119] The heating temperature depends on the non-aqueous solvent used, but is preferably 150° C. or higher, more preferably 200° C. or higher. It is preferable to remove the non-aqueous solvent almost completely. The composition can be applied while suppressing the diffusion of inorganic compounds, because the decrease in viscosity is suppressed even at high temperatures of 50°C or higher. Examples of surfaces to which the composition can be applied include metal surfaces, plastic surfaces, and paper, and the composition can be used, for example, in paints and inks. The preferred compounds, preferred contents, and preferred content ratios of each component of the composition in the application method are as described above for the composition. [Example]

[0120] 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 scope of the present invention. Note that "normal pressure" refers to 101.3 kPa, and "normal temperature" refers to 25°C.

[0121] [Average fiber diameter, average fiber length and average aspect ratio of finely divided anion-modified cellulose fibers and modified cellulose fibers] When the measurement target is a finely divided anion-modified cellulose fiber, water is added. Alternatively, when the measurement target is a modified cellulose fiber, the same solvent as used in preparing the thickener composition is added to prepare a dispersion with a content of 0.0005% by mass. When the solvent is squalane or TGME, IPA is used. The dispersion is dropped onto mica and dried to form an observation sample. The fiber height (height difference between the fiber-containing and non-containing areas) of the cellulose fibers in the observation sample is measured using an atomic force microscope (AFM) (Digital Instruments, Nanoscope II Tapping mode AFM; Nanosensors, Point Probe (NCH) probe). At this time, 100 or more cellulose fibers are extracted from a microscopic image in which the cellulose fibers can be seen, and the average fiber diameter is calculated from their fiber height. The average fiber length is calculated from the distance in the fiber direction. The average aspect ratio is calculated by dividing the average fiber length by the average fiber diameter. The height analyzed in the AFM image can be considered the fiber diameter.

[0122] In Example 10 only, it was difficult to confirm the presence of modified cellulose fibers using the AFM. Therefore, in Example 10 only, the obtained thickener composition was diluted with IPA to 0.02% by mass, ultrasonically treated for 5 minutes, and one drop of the solution was dropped onto mica. After air drying, the sample was gold sputtered using an MSP-1S (manufactured by Vacuum Devices Co., Ltd.) and observed using an electron microscope VE-8800 (manufactured by KEYENCE Corporation) under measurement conditions of an accelerating voltage of 5 kV and a spot diameter of 8, and the average fiber diameter, average fiber length, and average aspect ratio of the modified cellulose fiber were determined in the same manner as above.

[0123] [Average fiber diameter and average fiber length of raw cellulose fibers and anion-modified cellulose fibers] Deionized water is added to the cellulose fibers to be measured to prepare a dispersion containing 0.01% by mass of cellulose. The dispersion is measured using a wet dispersion 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, analysis sample volume: 1 mL, and sampling: 15%. At least 100 cellulose fibers are measured, and the average ISO fiber diameter and average ISO fiber length are calculated as the average fiber diameter and average fiber length, respectively.

[0124] [Anionic Group Content of Anion-Modified Cellulose Fibers and Modified Cellulose Fibers] A dry mass of 0.5 g of the cellulose fiber to be measured is placed in a beaker and mixed with deionized water or a 2:1 (volume ratio) methanol / water mixture to a total volume of 55 mL. 5 mL of 0.01 M aqueous sodium chloride solution is then added to prepare a dispersion. The dispersion is stirred until the cellulose fiber to be measured is fully dispersed. 0.1 M hydrochloric acid is added to the dispersion to adjust the pH to 2.5-3. Using an automatic titrator (manufactured by DKK-TOA Corporation, product name "AUT-701"), 0.05 M aqueous sodium hydroxide solution is added dropwise to the dispersion with a waiting time of 60 seconds, and the conductivity and pH values ​​are measured every minute. Measurements are continued until the pH reaches approximately 11, and a conductivity curve is obtained. The sodium hydroxide titration amount is determined from this conductivity curve, and the anionic group content of the cellulose fiber to be measured is calculated using the following formula: Anionic group content (mmol / g) = [Titer 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)]

[0125] [Aldehyde group content of oxidized cellulose fiber] The carboxy group content of the oxidized cellulose fiber to be measured is measured by the above-mentioned method for measuring the anionic group content. Separately, 100 g of the aqueous dispersion of oxidized cellulose fiber to be measured (solids content: 1.0% by mass), 100 g of acetate buffer (pH 4.8), 0.33 g of 2-methyl-2-butene, and 0.45 g of sodium chlorite were added to a beaker and stirred at 25°C for 16 hours to oxidize any remaining aldehyde groups in the oxidized cellulose fiber. After the reaction was completed, the cellulose fiber was washed with deionized water to obtain cellulose fiber with the aldehyde groups oxidized. The carboxy group content of the dried product obtained after freeze-drying was measured using the above-mentioned method for measuring anionic group content, and the "carboxy group content of the oxidized oxidized cellulose fiber" was calculated. Next, the aldehyde group content of the oxidized cellulose fiber to be measured was calculated using Equation 1.

[0126] Aldehyde group content (mmol / g) = (carboxyl group content of oxidized cellulose fiber after oxidation treatment) - (carboxyl group content of oxidized cellulose fiber to be measured) Equation 1

[0127] [Solid content in gel or dispersion] Measurements are made using a halogen moisture meter (Shimadzu Corporation; product name "MOC-120H"). Measurements are made every 30 seconds for 1 g of sample at a constant temperature of 150°C, and the value when the mass loss is 0.1% or less of the initial sample weight is taken as the solid content. Note that if it is difficult to analyze the solid concentration using the above analytical method due to the use of a high-boiling organic solvent, a known alternative method such as the phenol-sulfuric acid method may be used.

[0128] [Amount of modified group bonded and introduction rate of modified cellulose fiber] The amount of modified group bonded is determined by the following IR measurement method, and the bonded amount and introduction rate are calculated using the following formula. Specifically, the IR measurement involves measuring the infrared absorption spectrum of dried modified cellulose fiber by the ATR method using an infrared absorption spectrometer (IR) (Nicolet 6700, manufactured by Thermo Fisher Scientific), and the bonded amount and introduction rate of the modified group are calculated using formulas A and B. The following describes the case where the anionic group is a carboxy group, i.e., the case of oxidized cellulose fiber. The following "1720 cm" -1The "peak intensity" is the peak intensity derived from the carbonyl group. In the case of an anionic group other than a carboxy group, the value of the wave number may be appropriately changed to calculate the bond amount and introduction rate of the modifying group.

[0129] <Formula A-1 (Ionic bond)> Amount of modified group bound (mmol / g) = a × (bc) ÷ b a: Carboxylic group content of oxidized cellulose fiber (mmol / g) b: 1720 cm of oxidized cellulose fiber -1 Peak intensity of c: 1720 cm of modified cellulose fiber -1 Peak intensity of <Formula A-2 (in the case of an amide bond)> Amount of modified group bonded (mmol / g) = de d: Carboxylic group content of oxidized cellulose fiber (mmol / g) e: Carboxylic group content of modified cellulose fiber (mmol / g) <Formula B> Modification group introduction rate (mol%) = 100 × f / g f: Amount of modified group bound (mmol / g) g: Carboxylic group content of oxidized cellulose fiber (mmol / g)

[0130] [Confirmation of crystalline structure in modified cellulose fibers] The crystalline structure of the modified cellulose fiber is confirmed by measurement under the following conditions using an X-ray diffractometer (MiniFlexII, manufactured by Rigaku Corporation). The measurement conditions were as follows: X-ray source: Cu / Kα-radiation, tube voltage: 30 kV, tube current: 15 mA, measurement range: diffraction angle 2θ = 5 to 45°, X-ray scan speed: 10° / min. The measurement sample was a cellulose fiber to be measured, with an area of ​​320 mm. 2 The cellulose is compressed into a pellet with a thickness of 1 mm. The degree of crystallinity of the cellulose type I crystal structure is calculated from the obtained X-ray diffraction intensity using the following formula C.

[0131] <Formula C> Cellulose type I crystallinity (%) = [(I 22.6 -I 18.5 ) / I 22.6 ] x 100 [In the formula, I 22.6 is the diffraction intensity of the lattice plane (002 plane) (diffraction angle 2θ = 22.6°) in X-ray diffraction, I 18.5 indicates the diffraction intensity of the amorphous part (diffraction angle 2θ = 18.5°).

[0132] On the other hand, if the crystallinity obtained by the above formula C is 35% or less, in order to improve calculation accuracy, it is preferable to calculate based on the following formula D, in accordance with the description on pages 199-200 of the "Wood Science Experiment Manual" (edited by the Japan Wood Research Society; published in April 2000). Therefore, when the crystallinity obtained by the above formula C is 35% or less, the value calculated based on the following formula D can be used as the crystallinity.

[0133] <Formula D> Cellulose type I crystallinity (%) = [A c / (A c +A a )] × 100 [In the ceremony, A c is the sum of the peak areas of the lattice planes (002 plane) (diffraction angle 2θ = 22.6°), (011 plane) (diffraction angle 2θ = 15.1°), and (0-11 plane) (diffraction angle 2θ = 16.2°) in X-ray diffraction, A a indicates the peak area of ​​the amorphous portion (diffraction angle 2θ = 18.5°), and each peak area is determined by fitting the obtained X-ray diffraction chart with a Gaussian function.

[0134] [Cellulose fiber (equivalent amount) in modified cellulose fiber] The cellulose amount (equivalent amount) in a modified cellulose fiber is the amount of cellulose in the modified cellulose fiber excluding the modifying group. In the modified cellulose fiber of the present invention, the formula weight of the modifying group may be considerably larger (for example, than the molecular weight of glucose). Therefore, in this specification, when it is appropriate to explain the difference in formula weight of the modifying group without considering the difference, the amount of cellulose constituting the modified cellulose fiber (equivalent amount) is expressed rather than the amount of modified cellulose fiber. The cellulose fiber (equivalent amount) in the modified cellulose fiber is measured by the following method.

[0135] (1) When one type of "modifying compound" is added The amount of cellulose fiber (equivalent amount) is calculated by the following formula E. <Formula E> Amount of cellulose fiber (equivalent amount) (g) = mass of modified cellulose fiber (g) / [1 + molecular weight of modifying compound (g / mol) × bonding amount of modifying group (mmol / g) × 0.001] (2) When two or more types of "modifying compounds" are added The amount of cellulose fiber (equivalent amount) is calculated taking into consideration the molar ratio of each compound (that is, the molar ratio when the total molar amount of the compounds added is taken as 1).

[0136] [Preparation of anion-modified cellulose fibers 1] Preparation Example 1 Bleached coniferous kraft pulp (manufactured by Westfraser, product name: Hinton) was used as the raw material natural cellulose fiber. Commercially available TEMPO (manufactured by Aldrich, free radical, 98% by mass) was used. Commercially available sodium hypochlorite, sodium bromide, and sodium hydroxide were used.

[0137] First, 10 g of the bleached kraft pulp fiber and 990 g of deionized water were weighed into a 2 L polypropylene beaker equipped with a mechanical stirrer and impeller and stirred at 25°C and 100 rpm for 30 minutes. Next, 0.13 g of TEMPO, 1.3 g of sodium bromide, and 35.5 g of a 10.5 wt% sodium hypochlorite aqueous solution were added to the 10 g of pulp fiber, in that order. Using a pH-stat titration system with an automatic titrator (manufactured by DKK-TOA Corporation, product name: AUT-701), 0.5 M aqueous sodium hydroxide was added dropwise to maintain the pH at 10.5. The reaction was carried out at a stirring speed of 100 rpm for 120 minutes at 25°C, after which the addition of the aqueous sodium hydroxide solution was stopped, yielding a suspension of anion-modified cellulose fibers (i.e., oxidized cellulose fibers) in which the anionic group was a carboxy group.

[0138] The resulting suspension of anion-modified cellulose fibers was adjusted to pH 2 with 0.01 M hydrochloric acid, and the cellulose fibers were thoroughly washed with deionized water until the filtrate reached a conductivity of 200 μs / cm or less, as measured using a compact electrical conductivity meter (HORIBA, Ltd., LAQUAtwin EC-33B). The resulting anion-modified cellulose fibers had a carboxyl group content of 1.50 mmol / g and an aldehyde group content of 0.23 mmol / g.

[0139] Preparation Example 2 (Production of finely divided anion-modified cellulose fibers) Deionized water was added to the anion-modified cellulose fibers finally obtained in Preparation Example 1 to prepare 100 g of a suspension (solid content 2.0% by mass). A 0.5 M aqueous sodium hydroxide solution was added to the suspension to adjust the pH to 8, and deionized water was added to make a total of 200 g. This suspension was subjected to a micronization treatment three times at 150 MPa using a high-pressure homogenizer (manufactured by Yoshida Kikai Co., Ltd., trade name: Nanovaita L-ES) to obtain a micronized anion-modified cellulose fiber dispersion (solid content 1.0% by mass). The counter ions of the carboxy groups in this micronized anion-modified cellulose fiber were sodium ions.

[0140] Preparation Example 3 (Production of finely divided anion-modified cellulose fibers subjected to reduction treatment of aldehyde groups) 182 g of the finely divided anion-modified cellulose fiber dispersion (solid content 1.0% by mass) obtained in Preparation Example 2 was weighed out and mixed with deionized water to a total weight of 400 g. 1.2 mL of 0.1 M aqueous sodium hydroxide and 120 mg of sodium borohydride were added and stirred at 25°C for 4 hours. Next, 9 mL of 1 M hydrochloric acid was added to carry out protonation. After the reaction was completed, the mixture was filtered, and the resulting cake was washed six times with deionized water to remove salts and hydrochloric acid, yielding a finely divided anion-modified cellulose fiber dispersion (solid content 0.9% by mass) in which the aldehyde groups had been reduced. The resulting cellulose fibers had a carboxyl group content of 1.50 mmol / g and an aldehyde group content of 0.02 mmol / g. The carboxyl groups in this finely divided anion-modified cellulose fiber were in the free acid form (COOH), and are abbreviated as "TCNF (acid form)." The average fiber diameter of this finely divided anion-modified cellulose fiber was 3.3 nm, and the average fiber length was 600 nm.

[0141] [Preparation of anion-modified cellulose fibers 2] Preparation Example 4 Ten grams of bleached softwood kraft pulp (Hinton, manufactured by West Fraser) was thoroughly stirred with 990 g of ion-exchanged water. To the 10 g of pulp, 0.13 g of TEMPO (Aldrich, free radical, 98% by mass), 1.3 g of sodium bromide, and 27 g of a 10.5% by mass aqueous solution of sodium hypochlorite (10.5% by mass aqueous solution) were added, in this order. Using a pH-stat titration system with an automatic titrator (DKK-TOA Corporation, AUT-701), 0.5 M aqueous sodium hydroxide was added dropwise to maintain the pH at 10.5. The reaction was stirred at 200 rpm for 120 minutes (20°C), after which the addition of sodium hydroxide was stopped, yielding a suspension of anion-modified cellulose fibers (i.e., oxidized cellulose fibers) in which the anionic groups were carboxy groups.

[0142] The resulting suspension of anion-modified cellulose fibers was adjusted to pH 2 with 0.01 M hydrochloric acid. The anion-modified cellulose fibers were then thoroughly washed with ion-exchanged water until the filtrate reached a conductivity of 200 μs / cm or less, as measured using a compact electrical conductivity meter (HORIBA, Ltd., LAQUAtwin EC-33B). The fibers were then dehydrated to yield a cake of anion-modified cellulose fibers. The resulting anion-modified cellulose fibers had an average fiber length of 594 μm, an average fiber diameter of 2.7 μm, an aspect ratio of 220, and a carboxyl group content of 1.5 mmol / g. These anion-modified cellulose fibers were TCNF (acid type).

[0143] [Preparation of anionically modified cellulose fibers 3] Preparation Example 5 (Preparation of Short Anion-Modified Cellulose Fiber) 1.8 g (bone-dry mass) of the anion-modified cellulose fiber obtained in Preparation Example 4 was charged, and ion-exchanged water was added until the mass of the contents reached 36 g. The mixture was then stirred at 95°C for 3 hours to obtain an aqueous suspension of shortened anion-modified cellulose fiber. The resulting anion-modified cellulose fiber had an average fiber length of 210 μm, an average fiber diameter of 3.3 μm, an aspect ratio of 64, and a carboxy group content of 1.5 mmol / g. This anion-modified cellulose fiber was TCNF (acid type).

[0144] [Preparation of anion-modified cellulose fibers 4] Preparation Example 6 Eight grams of bleached softwood kraft pulp (Hinton, manufactured by West Fraser) was thoroughly stirred with 760 g of ion-exchanged water. To the 8 g of pulp, 0.09 g of TEMPO (Aldrich, free radical, 98% by mass), 1.0 g of sodium bromide, and 21 g of a 5.0% by mass aqueous sodium hypochlorite solution (3.8 mmol / g per gram of pulp) were added in this order. Using a pH-stat titration system with an automatic titrator (DKK-TOA Corporation, AUT-701), 0.5 M aqueous sodium hydroxide was added dropwise to maintain the pH at 10.5. The reaction was stirred at 200 rpm for 120 minutes (20°C), after which the addition of sodium hydroxide was stopped, yielding a suspension of anion-modified cellulose fibers (i.e., oxidized cellulose fibers) in which the anionic groups were carboxyl groups.

[0145] The resulting suspension of anion-modified cellulose fibers was adjusted to pH 2 with 0.01 M hydrochloric acid, and the anion-modified cellulose fibers were thoroughly washed with ion-exchanged water until the conductivity of the filtrate measured using a compact electrical conductivity meter (HORIBA, Ltd., LAQUAtwin EC-33B) was 200 μs / cm or less. The fibers were then dehydrated to obtain cake-like anion-modified cellulose fibers. The carboxyl group content of the resulting anion-modified cellulose fibers was 1.3 mmol / g. These anion-modified cellulose fibers were TCNF (acid type).

[0146] [Preparation of Thickener Composition] Example 1 (However, Examples 1 to 10 are reference examples.) The micronized anion-modified cellulose fiber dispersion obtained in Preparation Example 3 was washed three times with isopropyl alcohol (IPA) and then three times with squalane to perform solvent substitution. 66.7 g of the resulting gel (0.9% solids by mass) and 1.53 g of amino-modified silicone (equivalent to 1 equivalent of the carboxyl groups of the anion-modified cellulose fiber) were placed in a beaker and mixed, and squalane was added to make a total of 120 g. This mixture was stirred at room temperature for 5 minutes with a mechanical stirrer and then subjected to 10 passes at 150 MPa in a high-pressure homogenizer (Yoshida Kikai Co., Ltd., trade name: Nanovaita L-ES) to obtain a squalane dispersion of modified cellulose fiber in which the amino-modified silicone was linked to the anion-modified cellulose fiber via ionic bonds. This dispersion was used as a thickener composition.

[0147] Example 2 A toluene dispersion of modified cellulose fibers was obtained in the same manner as in Example 1, except that IPA was replaced with acetone, squalane with toluene, and amino-modified silicone with monoamine EOPOamine. This dispersion was used as a thickener composition.

[0148] Example 3 The anion-modified cellulose fiber dispersion obtained in Preparation Example 4 was washed three times with 1-methoxy-2-propanol (PGME) to perform solvent substitution. 7.0 g of the resulting gel (solid content 14.6% by mass) and 3.1 g of EOPO amine (equivalent to 1 equivalent of the carboxyl groups of the anion-modified cellulose fiber) were placed in a beaker and mixed, and 33.0 g of PGME was added to make a total of 43 g. This solution was stirred at room temperature for 1 hour using a mechanical stirrer and then subjected to five passes at 150 MPa using a high-pressure homogenizer (Yoshida Kikai Co., Ltd., trade name: Nanovaita L-ES) to obtain a 1-methoxy-2-propanol dispersion of modified cellulose fiber in which EOPO amine was linked to the anion-modified cellulose fiber via ionic bonds. This dispersion was used as a thickener composition.

[0149] Example 4 Methyl ethyl ketone (MEK) was used instead of PGME in Example 3, and the mixture was washed three times to perform solvent substitution. 5.3 g of the resulting gel (solid content: 3.77% by mass) and 0.086 g of oleylamine (equivalent to 1 equivalent of the carboxyl groups of the anion-modified cellulose fibers) were placed in a beaker and mixed. 20.0 g of MEK and 40.0 g of squalane were then added to make a total of 65 g. This solution was stirred at room temperature for 1 hour using a mechanical stirrer and then subjected to five passes at 150 MPa using a high-pressure homogenizer (Yoshida Kikai Co., Ltd., trade name: Nanovaita L-ES). The resulting dispersion was dried under reduced pressure at 80°C to remove solvents other than squalane, yielding a squalane dispersion of modified cellulose fibers in which oleylamine was linked to anion-modified cellulose fibers via ionic bonds. This dispersion was used as a thickener composition.

[0150] Example 5 A DMF dispersion of anion-modified cellulose fibers was obtained in the same manner as in Example 3, except that DMF was used instead of PGME in Example 3 and no modifying compound was used. This dispersion was used as a thickener composition.

[0151] Example 6 The anion-modified cellulose fiber dispersion obtained in Preparation Example 5 was washed three times with triethylene glycol monobutyl ether (manufactured by Tokyo Chemical Industry Co., Ltd., abbreviated as "TGME") to perform solvent substitution. 11.2 g of the resulting gel (solid content 13.4% by mass) and 2.0 g of a 25% by mass aqueous solution of tetrabutylammonium hydroxide (corresponding to 1 equivalent of the carboxyl groups of the anion-modified cellulose fiber) were mixed in a beaker, and 16.8 g of triethylene glycol monobutyl ether was added to make a total of 30 g. This solution was stirred at room temperature for 1 hour with a mechanical stirrer and then subjected to five passes at 150 MPa in a high-pressure homogenizer (Yoshida Kikai Co., Ltd., trade name: Nanovaita L-ES) to obtain a triethylene glycol monobutyl ether dispersion of modified cellulose fiber in which tetrabutylammonium was linked to the anion-modified cellulose fiber via ionic bonds. This dispersion was used as a thickener composition.

[0152] Example 7 The modifying compound used in Example 6 was changed to 1.0 g of a 25% by mass aqueous solution of tetrabutylammonium hydroxide (corresponding to 0.5 equivalents relative to the carboxy groups of the anion-modified cellulose fiber) and 2.0 g of EOPO amine (corresponding to 0.5 equivalents relative to the carboxy groups of the anion-modified cellulose fiber), and the same procedure as in Example 6 was repeated to obtain a triethylene glycol monobutyl ether dispersion of modified cellulose fiber in which tetrabutylammonium and EOPO amine were linked to the anion-modified cellulose fiber via ionic bonds. This dispersion was used as a thickener composition.

[0153] Example 8 A TGME dispersion of modified cellulose fibers in which EOPO amine was linked to anion-modified cellulose fibers via ionic bonds was obtained by performing the same procedure as in Example 7, except that the modifying compound used in Example 7 was changed to EOPO amine (corresponding to 1 equivalent relative to the carboxyl groups of the anion-modified cellulose fibers). This dispersion was used as a thickening composition.

[0154] Example 9 A TGME dispersion of modified cellulose fiber was obtained in the same manner as in Example 3, except that the solvent used in Example 3 was changed from PGME to TGME. This dispersion was used as a thickening composition. The concentration of modified cellulose fiber in the thickening composition (i.e., solid content) was the value shown in Table 1-1.

[0155] Example 10 1.38 g (solids content 18.5% by mass) of the cake-like anion-modified cellulose fiber obtained in Preparation Example 6 was placed in a beaker, and 50 g of ion-exchanged water and 0.66 g of EOPO amine (equivalent to 1 equivalent of the carboxyl groups of the anion-modified cellulose fiber) were added and mixed to a total of 52 g. This solution was stirred at room temperature for 1 hour using a mechanical stirrer and then subjected to one pass at 100 MPa using a high-pressure homogenizer (Yoshida Kikai Co., Ltd., trade name: Nanovaita L-ES). 50 g of TGME was then added, stirred, and subjected to another pass at 100 MPa. The dispersion was dried under reduced pressure at 80°C to remove solvents other than TGME, yielding a TGME dispersion of modified cellulose fiber in which EOPO amine was linked to anion-modified cellulose fiber via ionic bonds. This dispersion was used as a thickener composition.

[0156] The modifying compounds used in the above examples are as follows: Amino-modified silicone (BY16-209, manufactured by Toray Dow Corning Co., Ltd.) EOPO amine (Jeffamine M2070, manufactured by Huntsman, USA, PO / EO (molar ratio) = 10 / 31) Oleylamine (Fujifilm Wako Pure Chemical Industries, Ltd.) 25% by mass tetrabutylammonium hydroxide solution (Fujifilm Wako Pure Chemical Industries, Ltd.) Amino-modified silicone provides silicone chains as modifying groups to cellulose fibers, EOPO amine provides alkylene oxide chains (EO / PO copolymers) as modifying groups, and oleylamine and tetrabutylammonium hydroxide provide hydrocarbon groups as modifying groups.

[0157] [Preparation of low molecular weight thickener composition] Comparative Example 1 A thickener, 0.05 g (0.5% by mass) of lithium 12-hydroxystearate (manufactured by Katsuta Chemical Industry Co., Ltd.) was added to a vial container in an amount of 10 g of squalane, and the thickener was dissolved by heating and stirring in a block heater heated to 205° C. The mixture was allowed to cool to room temperature, yielding a low-molecular-weight thickener composition of Comparative Example 1.

[0158] Comparative Example 2 To a vial, 1.0 g (5% by mass) of fatty acid amide S (manufactured by Kao Corporation) was added as a thickener relative to 20 g of TGME, and the thickener was dissolved by heating and stirring in a block heater heated to 90°C. The mixture was allowed to cool to room temperature, yielding a low-molecular-weight thickening composition of Comparative Example 2.

[0159] Comparative Example 3 A 2% by weight aqueous dispersion of unmodified cellulose fiber (Sugino Machine Co., Ltd., BiNFi-s, WFo-10002 (average fiber diameter 10-50 nm)) was washed once with 1-methoxy-2-propanol (PGME) and then three times with methyl ethyl ketone (MEK) for solvent substitution. The resulting mixture (3.3 g, solids content 4.6% by weight), 5 g of PGME, and 30 g of MEK were added to a beaker, and 40.0 g of squalane was added for a total of 78 g. The solution was stirred for 1 hour with a mechanical stirrer and then subjected to five passes at 150 MPa in a high-pressure homogenizer (Yoshida Machine Co., Ltd., trade name: NanoVaita L-ES) to obtain an unmodified cellulose fiber dispersion.

[0160] The PGME / MEK was removed from the dispersion using an evaporator (80°C, 2 hours), yielding a squalane dispersion containing unmodified cellulose fibers. During the PGME / MEK removal process, the unmodified cellulose fibers aggregated and separated into a liquid and aggregates. Therefore, evaluations such as viscosity measurement were not possible.

[0161] Comparative Example 4 Solvent substitution was performed in the same manner as in Comparative Example 3, except that DMF was used instead of PGME / MEK. 7.6 g of the resulting mixture (solid content 2.7% by mass) was added to a beaker, and 40.0 g of DMF was added to make a total of 48 g. This solution was stirred with a mechanical stirrer for 1 hour, and then subjected to five passes at 150 MPa in a high-pressure homogenizer (Yoshida Kikai Co., Ltd., trade name: Nanovaita L-ES) to obtain a DMF dispersion of unmodified cellulose fibers. While the viscosity of this dispersion could be measured at 25°C, it separated into liquid and aggregates at 80°C, making viscosity measurement impossible.

[0162] Comparative Example 5 20 g of the cake-like anion-modified cellulose fiber (solids content 26.1% by mass) after dehydration obtained in Preparation Example 4 was thoroughly stirred with 250 g of ion-exchanged water, and then aqueous sodium hydroxide solution was added until the pH of the filtrate measured with a compact pH meter (LAQUATWIN-PH-11B, manufactured by Horiba, Ltd.) reached 7.0, yielding anion-modified cellulose fiber in which the carboxyl group terminals were Na-substituted. The resulting aqueous dispersion of Na-substituted anion-modified cellulose fiber was washed three times with DMF to perform solvent substitution.

[0163] 5.0 g of the resulting composition (solid content 3.0% by mass) was added to a beaker, and 25.0 g of DMF was added to make a total of 30 g. This solution was stirred with a mechanical stirrer for 1 hour, and then processed five times at 150 MPa with a high-pressure homogenizer (Yoshida Kikai Co., Ltd., trade name: Nanovaita L-ES) to obtain a DMF dispersion of Na-type anion-modified cellulose fibers. While the viscosity of this dispersion could be measured at 25°C, it separated into liquid and aggregates at 80°C, making viscosity measurement impossible.

[0164] Rheometer Evaluation of Thickener Compositions The viscosity of the thickener composition was evaluated by measuring the viscosity using a rheometer (Physica MCR300, manufactured by Anton Paar). The measurement jig used was a cone-type jig CP50-1 (rotation axis compliance was 4.5 × 10 -7m / N), and the measurement conditions were shear rate of 0.001 to 1000 s -1 , 2nd time 1000~0.001s -1 , 3rd time 0.001~1000s -1 The measurements were carried out under the conditions of 1.0 s at each temperature for the third measurement from the viewpoint of viscosity stability. -1 The viscosity at these times was compared. As a reference example, the viscosity of each non-aqueous solvent itself was also measured in the same manner.

[0165] The compositions and results of each example are shown in Tables 1-1, 1-2, 2-1 and 2-2.

[0166] [Table 1-1]

[0167] [Table 1-2]

[0168] [Table 2-1]

[0169] [Table 2-2]

[0170] [Rheometer chart of thickening composition] Rheometer charts for the thickener compositions of Example 1, Comparative Example 1, and Examples 8 to 10 are shown in Figures 1 and 2. The rheometer charts in Figures 1 and 2 were obtained using the above-mentioned rheometer and measuring jig under the measurement conditions shown in Table 3.

[0171] [Table 3]

[0172] Example 11 2.5 g of the TGME dispersion prepared in Example 8 and 10 g of inorganic powder were added to a vial and stirred with a spatula for 2 minutes. Then, the mixture was stirred at 2200 rpm for 10 minutes using a WATER THINKY MIXER (ARE-310, manufactured by THINKY CORPORATION). Then, the mixture was stirred with a spatula to prepare an inorganic powder-containing paste. Using a micropipette, 10 μL of the prepared inorganic powder-containing paste was dropped onto a glass slide (25°C). The slide was placed on a hot plate heated to 120°C or 200°C and heated for 1 minute. The diameter of the inorganic powder in each paste was then measured using an optical microscope, and the area ratio of the inorganic powder-containing paste before and after heating was evaluated. Note that when measured at 200°C, TGME had been almost completely removed by volatilization. The results are shown in Table 4.

[0173] Comparative Example 6 10 g of inorganic powder was added to 2.5 g of the TGME dispersion (fatty acid amide S) prepared in Comparative Example 2 in a vial. The thickener was then dissolved by heating and stirring for 5 minutes in a block heater heated to 90°C. The mixture was then allowed to cool and stirred with a spatula to obtain an inorganic powder-containing paste. The same evaluations as in Example 11 were then carried out. The results are shown in Table 4.

[0174] Reference example 6 An inorganic powder-containing paste was prepared in the same manner as in Example 11, except that the TGME dispersion liquid used in Example 11 was changed to TGME. Thereafter, the same evaluations as in Example 11 were carried out. The results are shown in Table 4.

[0175] The inorganic powders used in the above examples are as follows: Cu powder (Mitsui Mining & Smelting Co., Ltd., product number: wet copper powder 1100Y, average particle size 1.1 μm)

[0176] [Table 4]

[0177] Tables 1 and 2 show that in Examples 1 to 4 and 8 to 10, the decrease in viscosity at 80°C is suppressed compared to the viscosity at 25°C. Figures 1 and 2 show that the compositions of the examples of the present application exhibit a stable thickening effect over a wide temperature range compared to the compositions of the comparative examples. The same effect was confirmed when the modified cellulose fibers were shortened (Examples 5 to 7). These results demonstrate that the thickener composition of the present invention can be used at temperatures exceeding 50°C. From Table 4, it was found that Example 11 containing an inorganic compound does not decrease in viscosity even at high temperatures due to the high-temperature viscosity increasing property of the non-aqueous solvent, that is, the inorganic compound does not spread. These results show that the composition of the present invention is useful for applications involving processing at 50° C. or higher, such as compositions for electronic materials, optical materials, or structural materials. [Industrial Applicability]

[0178] The thickener composition of the present invention can be used in fields such as home appliance parts, electronic materials (electronics), packaging materials, aerospace, civil engineering and construction, automobiles, and in-vehicle applications.

Claims

1. A thickener composition containing modified cellulose fiber, a non-aqueous solvent, and a metal powder, which is used at 50°C or higher, A thickener composition, wherein the modified cellulose fiber is one or more types selected from the group consisting of the following (1) and (2): (1) A cellulose fiber having a type I crystal structure in which a modifying group is bonded to the cellulose fiber, the modifying group containing one or more groups selected from the group consisting of (a) a hydrocarbon group, (b) a silicone chain, and (c) an alkylene oxide chain. (2) Acid-type anion-modified cellulose fiber having I-type crystal structure

2. 2. The thickener composition of claim 1, having a viscosity ratio at 80°C / 25°C of 0.6 or greater.

3. The thickener composition according to claim 1 or 2, wherein the cellulose fiber in (1) is an anion-modified cellulose fiber.

4. 4. The thickener composition according to claim 3, wherein the modifying group is bonded to the anionic group of the anionically modified cellulose fiber via an ionic bond and / or a covalent bond.

5. The thickener composition according to any one of claims 1 to 4, wherein the alkylene oxide chain is one or more (co)polymer moieties selected from the group consisting of an ethylene oxide (EO) polymerization moiety, a propylene oxide (PO) polymerization moiety, and an (EO / PO) copolymerization moiety.

6. The thickener composition according to any one of claims 1 to 5, wherein the non-aqueous solvent contains a hydrocarbon solvent or a glycol ether solvent.

7. The thickener composition according to any one of claims 1 to 6, wherein the modifying group in the modified cellulose fiber contains (c) an alkylene oxide chain, and the non-aqueous solvent contains a glycol ether solvent.

8. The thickener composition according to any one of claims 1 to 7, wherein the average fiber diameter of the modified cellulose fiber is 1 nm or more and 300 nm or less.

9. The thickener composition according to any one of claims 1 to 8, which is used for electronic materials, optical materials, or structural materials.

10. A method for applying an inorganic compound, comprising the step of heating a composition containing one or more modified cellulose fibers selected from the group consisting of (1) and (2) below, a non-aqueous solvent, and an inorganic compound to 100°C or higher to remove the non-aqueous solvent, wherein the inorganic compound is a metal powder. (1) A cellulose fiber having a type I crystal structure in which a modifying group is bonded to the cellulose fiber, the modifying group containing one or more groups selected from the group consisting of (a) a hydrocarbon group, (b) a silicone chain, and (c) an alkylene oxide chain. (2) Acid-type anion-modified cellulose fiber having I-type crystal structure

11. A composition comprising modified cellulose fibers, a non-aqueous solvent, and a metal powder, The composition, wherein the modified cellulose fiber is one or more types selected from the group consisting of (1) and (2) below: (1) A cellulose fiber having a type I crystal structure in which a modifying group is bonded to the cellulose fiber, the modifying group containing one or more groups selected from the group consisting of (a) a hydrocarbon group, (b) a silicone chain, and (c) an alkylene oxide chain. (2) Acid-type anion-modified cellulose fiber having I-type crystal structure

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