WO2021230191A1 - Thickener composition - Google Patents

Abstract

The present invention pertains to a thickener composition that contains modified cellulose fibers and a nonaqueous solvent and is used at a temperature of 50℃ or higher, wherein the modified cellulose fibers are at least one type of modified cellulose fiber selected from the group consisting of (1) and (2) mentioned hereafter. (1) Modified cellulose fibers having a type I crystal structure obtained as a result of a modifying group being bonded to cellulose fiber, wherein the modifying group includes one or more substances selected from the group consisting of (a) hydrocarbon groups, (b) silicone chains, and (c) alkylene oxide chains; (2) acid-type anionic modified cellulose fibers having a type I crystal structure. The thickener composition, containing a nonaqueous solvent, according to the present invention is such that a decrease in viscosity can be suppressed even at high temperatures of 50℃ or higher.

Description

Thickener composition

The present invention relates to a thickener composition, a viscosity control agent for a non-aqueous solvent, a thickener composition, and a method for applying an inorganic compound.

In recent years, technologies that have less impact on the environment have come into the limelight, and under such technological background, materials using cellulose fibers, which are biomass that exists in large quantities in nature, are attracting attention.
For example, Patent Document 1 includes a fine cellulose fiber composite in which an amine is bonded to an anionic group of an anionic modified cellulose fiber containing an anionic group via an ionic bond, a dispersant, and an organic liquid compound. , A fine cellulose fiber composite dispersion is disclosed.
Further, Patent Document 2 describes a step of dispersing cellulose having a cellulose type I crystal structure in water and then converting a hydroxyl group of the cellulose into a substituent having a carboxyl group, and water as a dispersion medium of the cellulose. A gel-like composition in which the cellulose nanofibers are dispersed in an organic solvent by nano-defibrating the cellulose after the hydrophobicization, the step of replacing the cellulose with an organic solvent, and the step of making the cellulose after the dispersion medium substitution hydrophobic. In the method for producing a gel-like composition comprising the step of obtaining the above-mentioned, a method for producing a gel-like composition is disclosed, wherein the hydrophobicity of the cellulose is carried out by a neutralization reaction with a polyether amine.

Patent Document 1 describes the dispersibility of cellulose fibers in an organic liquid compound, and Patent Document 2 describes a method for producing a gel-like composition in which cellulose fibers are dispersed in an organic solvent. However, these documents do not describe any change in viscosity physical properties at high temperatures.

Japanese Unexamined Patent Publication No. 2019-119867 Japanese Unexamined Patent Publication No. 2017-1996

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

FIG. 1 is a rheometer chart of the thickener composition in Example 1 and Comparative Example 1. FIG. 2 is a rheometer chart of the thickener composition in Examples 8-10.

Detailed description of the invention

The present invention relates to a non-aqueous solvent thickener composition suitable for use at 50 ° C. or higher because the decrease in viscosity is suppressed even at high temperatures.

The non-aqueous solvent thickener composition of the present invention can suppress a decrease in viscosity even at a high temperature of 50 ° C. or higher.

Although the detailed mechanism of the thickener composition of the present invention is unknown, the cellulose fibers into which the hydrophobic modifying group has been introduced are uniformly dispersed in a non-aqueous solvent to form a loose network structure. It is presumed that the viscosity maintaining effect at high temperature is exhibited.

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

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

(1) It has an I-type crystal structure in which a modifying group is bonded to a cellulose fiber, and the modifying group is (a) a hydrocarbon group, (b) a silicone chain, and (c) an alkylene oxide chain. Those containing one or more selected from the group consisting of.
(2) An acid-type anion-modified cellulose fiber having an I-type crystal structure.
In the present specification, when it is necessary to explain separately, the modified cellulose fiber of (1) is referred to as "modified cellulose fiber (1)", and the modified cellulose fiber of (2) is "modified". Quality Cellulose Fiber (2) ”.

-Modified cellulose fiber (1)
The modified cellulose fiber (1) is formed by binding a modifying group to the cellulose fiber. As the cellulose fiber, an anion-modified cellulose fiber is preferable from the viewpoint of easiness of binding of a modifying group.

(Anion-modified cellulose fiber)
The anion-modified cellulose fiber is a cellulose fiber having one or more groups selected from the group consisting of an anionic group, for example, a carboxy group, a (sub) phosphate group and a sulfonic acid group in the molecule. The introduction of anionic groups into cellulose fibers can be achieved by the method described below. From the viewpoint of availability and effect, anion-modified cellulose fiber having a carboxy group as an anionic group is preferable, and the group at the C6 position (-CH ₂ OH) of the glucose unit constituting the cellulose fiber is selectively converted into a carboxy group. The anion-modified cellulose fiber (referred to as "oxidized cellulose fiber") is more preferable. The ion (counter ion) paired with the anionic group is preferably a proton.

The content of anionic groups in the anion-modified cellulose fiber is preferably 0.1 mmol / g or more, more preferably 0.4 mmol / g or more, still more preferably 0.6 mmol / g or more, from the viewpoint of stable introduction of modifying groups. , More preferably 0.7 mmol / g or more, still more preferably 0.8 mmol / g or more. Further, from the viewpoint of improving handleability, it is preferably 3 mmol / g or less, more preferably 2.5 mmol / g or less, still more preferably 2.3 mmol / g or less, still more preferably 2.1 mmol / g or less, still more preferably. It is 2.0 mmol / g or less, more preferably 1.9 mmol / g or less. The "anionic group content" means the total amount of anionic groups in glucose constituting the cellulose fiber, and is specifically measured by the method described in Examples described later.

The preferable range of the average fiber diameter and the average fiber length of the anion-modified cellulose fiber depends on the order of the manufacturing process, but is preferably the same as that of the raw material cellulose fiber.

The binding of the modifying group to the anionic group of the anion-modified cellulose fiber means that the modifying group is bound to the anionic group, preferably the carboxy group of the anion-modified cellulose fiber. Examples of the bonding mode between the modifying group and the anionic group include an ionic bond and / or a covalent bond. Examples of the covalent bond include an amide bond, an ester bond, and a urethane bond, and an amide bond is preferable.

(Modifying group)
Examples of the modifying group include (a) a hydrocarbon group, (b) a silicone chain, and (c) an alkylene oxide chain. These modifying groups may be bonded (introduced) to the cellulose fiber by one type alone or in combination of two or more types.

(a) Hydrocarbon groups Examples of the hydrocarbon groups include monovalent hydrocarbon groups, for example, chain-type saturated hydrocarbon groups, chain-type unsaturated hydrocarbon groups, cyclic-type saturated hydrocarbon groups, and aromatic hydrocarbon groups. Can be mentioned.

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

The chain saturated hydrocarbon group preferably has 3 or more carbon atoms and 30 or less carbon atoms, and specific examples thereof include a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, and a pentyl group. Group, tert-pentyl group, isopentyl group, hexyl group, isohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetraethyl group, tetrabutyl group, tetrapropyl group, tetradecyl Examples thereof include a group, an octadecyl group, a docosyl group, an octacosanyl group and the like.

The chain unsaturated hydrocarbon group preferably has 3 or more and 30 or less carbon atoms, and specific examples thereof include a propenyl group, a butenyl group, an isobutenyl group, an isoprenyl group, a pentenyl group, a hexenyl group, a heptenyl group, and an octenyl group. Examples thereof include a group, a nonenyl group, a decenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group and an octadecenyl group.

The cyclic saturated hydrocarbon group preferably has 3 or more and 20 or less carbon atoms, and specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclononyl group. , Cyclodecyl group, cyclododecyl group, cyclotridecyl group, cyclotetradecyl group, cyclooctadecyl group and the like.

Examples of the aromatic hydrocarbon group include an aryl group and an aralkyl group. As the aryl group and the aralkyl group, the aromatic ring itself may be substituted or unsubstituted.
Examples of the heterocyclic aromatic hydrocarbon group include an imidazole group.

The total number of carbon atoms of the aryl group is preferably 6 or more and 24 or less, and specific examples of the aryl group include, for example, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, a triphenyl group and a terphenyl group. , And groups in which these groups are substituted with substituents.

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

(b) Silicone chain The silicone chain is a monovalent group having a siloxane bond as a main chain, and may be further accompanied by an alkylene group. The silicone chain may further have a substituent described later.

(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 a structure containing a polymer of EO (EO polymerization). Part), a structure containing a polymer of PO (PO polymerization part), and a structure containing a copolymer in which EO and PO are polymerized randomly or in a block shape ((EO / PO) copolymer part). One or more (co) polymerized portions to be selected. The alkylene oxide chain may further have a substituent described later.

As the alkylene oxide chain, for example, the following formula:

(In the formula, R ¹ represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or -CH ₂ CH (CH ₃ ) NH ₂ groups. EO and PO exist in a random or block form, and a is. 0 or a positive number indicating the average number of added moles of EO, b is 0 or a positive number indicating the average number of added moles of PO, except when both a and b are 0). There is a monovalent group.

In the above formula, a indicates the average number of moles of EO added, and is preferably 0 or more, more preferably 1 or more, still more preferably 2 or more from the viewpoint of availability and affinity with a non-aqueous solvent, and the same viewpoint. Therefore, it is preferably 100 or less, more preferably 70 or less.

In the above formula, b indicates the average number of moles of PO added, and is preferably 0 or more, more preferably 1 or more, still more preferably 3 or more from the viewpoint of affinity with a non-aqueous solvent, and from the viewpoint of availability. It is preferably 50 or less, more preferably 40 or less.

Specific examples of the above hydrocarbon group having 1 to 6 carbon atoms of R ¹ in the formula is a methyl group, an ethyl group, a propyl group, an isopropyl group, butyl group, sec- butyl group, tert- butyl group, an isobutyl group, Examples thereof include a pentyl group, a tert-pentyl group, an isopentyl group, a hexyl group and an isohexyl group.

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 a high temperature (for example, 50 ° C. or higher), and is preferable from the same viewpoint. Is 10,000 or less, more preferably 7,000 or less. The formula amount of the alkylene oxide chain can be calculated from the average number of moles added when producing the amine compound having the alkylene oxide chain described later.

The PO content (mol%) in the (EO / PO) copolymer is preferably 1 mol% or more, more preferably 5 mol% or more, and is similar from the viewpoint of suppressing the decrease in viscosity even at high temperatures. From the viewpoint, it is preferably 100 mol% or less, more preferably 95 mol% or less, still more preferably 90 mol% or less. The content of PO in the (EO / PO) copolymer can be calculated from the average number of moles added when producing an amine compound having an alkylene oxide chain, which will be described later.

(d) Further substituents The modifying group may further have a substituent. Examples of the substituent include 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, a hexyloxy group and the like. An alkoxy group having 1 to 6 carbon atoms; a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, a pentyloxycarbonyl group. An alkoxy-carbonyl group having 1 to 6 carbon atoms in an alkoxy group such as a group and an isopentyloxycarbonyl group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; and a carbon number 1 such as an acetyl group and a propionyl group. Examples thereof include an acyl group of up to 6; an aralkyl group; an aralkyloxy group; an alkylamino group having 1 to 6 carbon atoms; a dialkylamino group having 1 to 6 carbon atoms of the alkyl group; a hydroxy group.

[Manufacturing method of modified cellulose fiber (1)]
In the modified cellulose fiber (1), for example, an anionic group is introduced into the raw material cellulose fiber to produce an anion-modified cellulose fiber (step 1), and then a modifying group is bonded to the anionic group of the anion-modified cellulose fiber. It can be manufactured by making it (step 2).

(Step 1)
Cellulose fiber as a raw material As the cellulosic fiber which is a raw material of anion-modified cellulose fiber, natural cellulose is preferable from the environmental point of view. For example, wood pulp such as coniferous pulp and broadleaf pulp; cotton pulp such as cotton linter and cotton lint. Non-wood pulp such as straw pulp and bagus pulp; bacterial cellulose and the like can be mentioned, and one of these can be used alone or in combination of two or more.

The average fiber diameter of the raw material cellulose fiber is not particularly limited, but is preferably 5 μm or more, more preferably 7 μm or more from the viewpoint of handleability and cost, and preferably 500 μm or less, more preferably 300 μm or less from the same viewpoint. Is. The average fiber diameter of the raw material cellulose fiber is obtained by the method described in Examples described later.

The average fiber length of the raw material cellulose fiber is not particularly limited, but is preferably 5 μm or more, more preferably 25 μm or more, and preferably 5,000 μm or less, from the viewpoint of availability and cost. It is preferably 3,000 μm or less. The average fiber length of the raw material cellulose fiber can be measured according to the method described in Examples described later.

Processing method
(1) When introducing a carboxy group as an anionic group into a cellulose fiber As a method for introducing a carboxy group into a cellulose fiber, for example, a method of oxidizing a hydroxy group of a cellulose fiber to convert it into a carboxy group, or a method of converting a hydroxy group of a cellulose fiber into a carboxy group. Examples of the group include a method of reacting at least one selected from the group consisting of a compound having a carboxy group, an acid anhydride of the compound having a carboxy group and a derivative thereof.

As a method for oxidizing the hydroxy group of the cellulose fiber, for example, 2,2,6,6-tetramethyl-1-piperidin-N described in JP-A-2015-143336 or JP-A-2015-143337. -Examples include a method in which an oxidizing agent such as sodium hypochlorite and a bromide such as sodium bromide are reacted with the raw material cellulose fiber using oxyl (TEMPO) as a catalyst. By oxidizing the cellulose fiber using TEMPO as a catalyst, the group at the C6 position of glucose, which is a constituent unit of the cellulose fiber, is selectively converted into a carboxy group, and the above-mentioned oxidized cellulose fiber can be obtained.

The compound having a carboxy group for use in introducing a carboxy group into a cellulose fiber is not particularly limited, and specific examples thereof include acetic acid halide. Examples of the halogenated acetic acid include chloroacetic acid and the like.

The acid anhydrides of the compounds having a carboxy group and their derivatives for use in introducing the carboxy group into the cellulose fiber are not particularly limited, but are not particularly limited, such as maleic anhydride, succinic anhydride, phthalic anhydride and adipic acid anhydride. Examples thereof include an acid anhydride of a dicarboxylic acid compound, an imide product of an acid anhydride of a compound having a carboxy group, and a derivative of an acid anhydride of a compound having a carboxyl group. These compounds may be substituted with hydrophobic groups.

(2) When introducing a sulfonic acid group or a (sub) phosphoric acid group as an anionic group into a cellulose fiber As a method for introducing a sulfonic acid group into a cellulose fiber, a method of adding sulfuric acid to the cellulose fiber and heating it can be mentioned. Be done.

As a method for introducing a (sub) phosphoric acid group into a cellulose fiber, a method of mixing a powder or an aqueous solution of (sub) phosphoric acid or a (sub) phosphoric acid derivative with a dry or wet state cellulose fiber, or a method of mixing a cellulose fiber. Examples thereof include a method of adding an aqueous solution of (sub) phosphoric acid or a (sub) phosphoric acid derivative to the dispersion liquid of. When these methods are adopted, in general, dehydration treatment, heat treatment and the like are performed after mixing or adding powder or aqueous solution of (sub) phosphorous acid or (sub) phosphorous acid derivative.

(Step 2)
The introduction of the modifying group into the anionic group of the anionic modified cellulose fiber is achieved by reacting the compound for introducing the modifying group into the anionic group (referred to as "modifying compound") with the anionic modified cellulose fiber. Will be done. As a method for introducing a modifying group, (1) Japanese Patent Application Laid-Open No. 2015-143336 can be referred to when introducing via an ionic bond, and (2) when introducing via an amide bond, Japanese Patent Application Laid-Open No. 2015-143336 can be referred to. 2015-143337 can be referred to.
After the completion of step 2, post-treatment may be appropriately performed in order to remove unreacted compounds and the like. As the post-treatment method, for example, filtration, centrifugation, dialysis and the like can be used.

(1) Mode of introduction via ionic bond When introducing a modifying group via an ionic bond, the anion-modified cellulose fiber and the modifying compound may be mixed, whereby the anion contained in the anion-modified cellulose fiber may be mixed. An ionic bond is formed between the sex group and the amino group of the modifying compound.
Specifically, when the oxidized cellulose fiber is used as the anion-modified cellulose fiber and the primary amine having the above-mentioned modifying group is used as the modifying compound, glucose constituting the cellulose fiber is as shown in the following formula. the C6 position carboxy group of, via ionic bonds, in can be introduced modifying group of the above (formula, C ⁶ is a carbon atom of 6 position of the glucose constituting the cellulose fibers, R represents a modifying group It is.).

Modification Compound The modifying compound used in this embodiment may be any compound capable of introducing a desired modifying group, preferably an amine compound having the above-mentioned hydrocarbon group, alkylene oxide chain, or silicone chain, phosphonium. Examples thereof include compounds and compounds containing a guanidino group.

Amine compound The amine compound is, for example, an amine compound having the above-mentioned hydrocarbon group, the above-mentioned alkylene oxide chain, or the above-mentioned silicone chain as a modifying group, and the hydrocarbon group or the like is an anion-modified cellulose fiber via an ionic bond. Introduced into a modifying group in a modified cellulose fiber.

The amine compound may be any of a primary amine, a secondary amine, a tertiary amine and a quaternary ammonium compound. As the anion component of the quaternary ammonium compound, from the viewpoint of reactivity, halogen ions such as chlorine ion and bromine ion, hydrogen sulfate ion, perchlorate ion, tetrafluoroborate ion and hexafluorophosphate ion are preferable. , Trifluoromethanesulfonate ion, hydroxy ion and the like.

Amine compounds having a hydrocarbon group Specific examples of amine compounds having a hydrocarbon group include ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, butylamine, dibutylamine and hexyl as primary to tertiary amines. Amine, 2-ethylhexylamine, dihexylamine, trihexylamine, octylamine, dioctylamine, trioctylamine, dodecylamine, diddecylamine, 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, 1 -(3-Aminopropyl) imidazole and the like can be mentioned. Examples of the quaternary ammonium compound include tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetraethylammonium chloride, tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), and tetra. Examples thereof include butylammonium chloride, lauryltrimethylammonium chloride, dilauryldimethylchloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, cetyltrimethylammonium chloride, and alkylbenzyldimethylammonium chloride.

The amine compound having a hydrocarbon group can be prepared by using a commercially available product or by a known method.

Amine compound having an alkylene oxide chain In an amine compound, the alkylene oxide chain and the nitrogen atom of the amine compound are preferably bonded directly or via a linking group. As the linking group, a hydrocarbon group is preferable, and an alkylene group having a carbon number of preferably 1 or more and 6 or less, more preferably 1 or more and 3 or less can be mentioned. As such an alkylene group, for example, an ethylene group and a propylene group are preferable.

Examples of the amine having an alkylene oxide chain include the following formula (i):

Examples thereof include the compounds indicated by. R ^1, a and b in the formula (i) is the same as R ^1, a and b in the formula of an example of the aforementioned alkylene oxide chain.

The amine compound having an alkylene oxide chain can be prepared according to a known method. For example, ethylene oxide and propylene oxide may be added in a desired amount to the propylene glycol alkyl ether, and then the hydroxy group terminal may be aminated. If necessary, the alkyl ether can be cleaved with an acid to form a hydrogen atom at the end. For these production methods, Japanese Patent Application Laid-Open No. 3-181448 can be referred to, and details of such amine compounds are described in, for example, Japanese Patent No. 6105139.

As the amine compound having an alkylene oxide chain, for example, a commercially available product can be preferably used, and specific examples thereof include Jeffamine M-2070, Jeffamine M-2005, Jeffamine M-2095, and Jeffamine M-1000 manufactured by HUNTSMAN. 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, Jeffamine T-5000, XTJ-502, XTJ-509, XTJ-510, etc., and SUNBRIGHT MEPA-manufactured by NOF CORPORATION. 10H, SUNBRIGHT MEPA-20H, SUNBRIGHT MEPA-50H, SUNBRIGHT MEPA-10T, SUNBRIGHT MEPA-12T, SUNBRIGHT MEPA-20T, SUNBRIGHT MEPA-30T, SUNBRIGHT MEPA-40T and the like. These may be used alone or in combination of two or more.

Amine Compounds with Silicone Chains Examples of such amine compounds include those having a structure in which an amino group is bonded to the skeleton of a silicone chain via an alkylene group or the like. As used herein, such amine compounds may be referred to as "amino-modified silicones". The amino-modified silicone can be prepared by using a commercially available product or by a known method. Only one kind of amino-modified silicone may be used, or two or more kinds may be used.

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

Guanidine group-containing compound The guanidine group-containing compound is, for example, a guanidine compound having the above-mentioned hydrocarbon group, the above-mentioned alkylene oxide chain, or the above-mentioned silicone chain as a modifying group, and such a hydrocarbon group or the like is mediated by an ionic bond. It is introduced into anion-modified cellulose fibers and becomes a modifying group in modified cellulose fibers. Examples of the guanidine group-containing compound include diphenylguanidine, ditrilguanidine, 1,2,3-triphenylguanidine, aminoguanidine, and arginine.

Reaction conditions, etc. From the viewpoint of reactivity, the amount of the modifying compound used is preferably such that the amino group in the modifying compound is 0.01 mol or more, more preferably 0.01 mol or more, with respect to 1 mol of the carboxy group of the oxidized cellulose fiber. The amount is 0.1 mol or more, more preferably 0.5 mol or more, further preferably 0.7 mol or more, still more preferably 1 mol or more, and preferably 50 mol from the viewpoint of product purity. The amount is as follows, more preferably 20 mol or less, still more preferably 10 mol or less. When the modifying compound has a plurality of amino groups, it is used so that the total number of moles of the amino groups is the above-mentioned number of moles.

It is preferable to use a solvent for mixing. As the solvent, it is preferable to select a solvent in which the compound to be used is dissolved, and for example, methanol, ethanol, isopropanol (IPA), N, N-dimethylformamide (DMF), dimethylsulfonate (DMSO), N, N-dimethylacetamide. , Tetrahydrofuran (THF), acetone, methylethylketone (MEK), cyclohexanone, ethyl acetate, acetonitrile, dichloromethane, chloroform, toluene, acetic acid, 1-methoxy-2-propanol (PGME), water and the like. It can be used alone or in combination of two or more.

The temperature at the time of mixing is preferably 0 ° C. or higher, more preferably 5 ° C. or higher, still more preferably 10 ° C. or higher, from the viewpoint of compound reactivity. Further, from the viewpoint of suppressing coloration of the modified cellulose fiber, the temperature is preferably 50 ° C. or lower, more preferably 40 ° C. or lower, and further preferably 30 ° C. or lower. The mixing time can be appropriately set depending on the type of the compound and the solvent used, but from the viewpoint of the reactivity of the compound, it is preferably 0.01 hours or more, more preferably 0.1 hours or more, and the productivity. From the viewpoint of the above, it is preferably 48 hours or less, more preferably 24 hours or less.

(2) Mode of introduction via amide bond When introducing a modifying group via an amide bond, the anion-modified cellulose fiber and the modifying compound may be mixed in the presence of a known condensing agent, whereby the modifying compound may be mixed. , An amide bond is formed between the anionic group contained in the anion-modified cellulose fiber and the amino group of the modifying compound.

Specifically, when the oxidized cellulose fiber is used as the anion-modified cellulose fiber and the primary amine having the above-mentioned modifying group is used as the modifying compound, the cellulose fiber is constituted as shown in the following formula. the C6 position carboxy group of glucose, via an amide bond, in can be introduced modifying group of the above (formula, C ⁶ is a carbon atom of 6 position of the glucose constituting the cellulose fibers, R represents modified It is the basis.).

Modification Compound The modifying compound used in this embodiment may be any compound capable of introducing a desired modifying group, and preferably includes the above-mentioned amine compounds having a hydrocarbon group, an alkylene oxide chain, or a silicone chain. Be done.

Amine compound The amine compound is, for example, an amine compound having the above-mentioned hydrocarbon group, the above-mentioned alkylene oxide chain, or the above-mentioned silicone chain as a modifying group, and the hydrocarbon group or the like is an anion-modified cellulose fiber via an amide bond. Introduced into, it becomes a modifying group in modified cellulose fibers.

Examples of the amine compound include primary amines and secondary amines. Specific examples of the amine compound include an amine compound having a hydrocarbon group, an amine compound having an alkylene oxide chain, and an amine compound having a silicone chain, which are exemplified in the above-mentioned "(1) Aspects of introduction via an ion bond". Of these, primary amines and secondary amines are mentioned.

Reaction conditions From the viewpoint of reactivity, the amount of the modifying compound used is such that the amino group in the modifying compound is preferably 0.05 mol or more, more preferably 0.1 mol or more, with respect to 1 mol of the carboxy group of the oxidized cellulose fiber. The amount is more preferably 0.2 mol or more, further preferably 0.3 mol or more, still more preferably 0.5 mol or more, and from the viewpoint of product purity, preferably 50 mol or less, more preferably 20 mol or less. The amount is, more preferably 10 mol or less. When the modifying compound has a plurality of amino groups, it is used so that the total number of moles of the amino groups is the above-mentioned number of moles.

The condensing agent is not particularly limited, and examples thereof include the condensing agent described in Synthetic Chemistry Series Peptide Synthesis (Maruzen Co., Ltd.) P116 or Tetrahedron, 57, 1551 (2001), and examples thereof include 4- (4,6-). Examples thereof include dimethoxy-1,3,5-triazine-2-yl) -4-methylmorpholinium chloride (hereinafter, may be referred to as "DMT-MM") and the like. It is also possible to carry out the reaction only by heat treatment without using a condensing agent.

The solvent may or may not be used in the amidation reaction. When a solvent is used, it is preferable to select a solvent in which the compound to be used dissolves, and specific examples of the solvent include the solvent exemplified in the above-mentioned "(1) Aspects of introduction via an ionic bond".

The reaction time and reaction temperature in the amidation reaction can be appropriately selected depending on the type of compound and solvent used, but are preferably 1 to 24 hours, more preferably 10 to 20 hours from the viewpoint of the reaction rate. be. The reaction temperature is preferably 0 ° C. or higher, more preferably 5 ° C. or higher, still more preferably 10 ° C. or higher, from the viewpoint of reactivity. Further, from the viewpoint of product quality such as coloring, it is preferably 200 ° C. or lower, more preferably 80 ° C. or lower, and further preferably 30 ° C. or lower.

(Miniaturization process)
By refining the cellulose fibers at any stage of the method for producing the modified cellulose fibers (for example, before step 1, before step 2 and after step 2), the cellulose fibers on the micrometer scale can be made into nanometer scale. Can be made finer. It is preferable to reduce the average fiber diameter to the nanometer size because the dispersibility in the resin is improved.

A known miniaturization treatment method can be adopted for the miniaturization treatment. For example, in the case of obtaining a modified cellulose fiber 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 or the like in a medium may be carried out.

Examples of the medium include water, methanol, ethanol, propanol, 1-methoxy-2-propanol (PGME) and other alcohols having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms; acetone, methyl ethyl ketone, methyl isobutyl ketone and the like. Ketones with 3 to 6 carbon atoms; Ketones with 2 to 4 carbon atoms such as ethyl acetate and butyl acetate; Saturated or unsaturated hydrocarbons with 1 to 6 carbon atoms; Aromatic hydrocarbons such as benzene and toluene; Methylene chloride , Hydrocarbons such as chloroform; lower alkyl ethers having 2 to 5 carbon atoms; polar solvents such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide, dimethylsulfoxide and the like are exemplified. These can be used alone or in admixture of two or more. The amount of the medium used may be an effective amount capable of dispersing the modified cellulose fiber, and is preferably 1 mass times or more, more preferably 2 mass times or more, preferably 500 mass times or less, based on the modified cellulose fiber. It is more preferable to use 200% by mass or less.

As a device used in the miniaturization process, a known disperser is preferably used in addition to the high-pressure homogenizer. For example, a breaker, a beater, a low-pressure homogenizer, a grinder, a mascot, a cutter mill, a ball mill, a jet mill, a short-screw extruder, a twin-screw extruder, an ultrasonic stirrer, a household juicer mixer and the like can be used. The solid content of the modified cellulose fiber in the miniaturization treatment is preferably 50% by mass or less.

(Shortened fiber treatment)
At any stage of the method for producing the modified cellulose fiber (1), a treatment for shortening the cellulose fiber, that is, a treatment for shortening the fiber length may be further carried out. The shortening fiber treatment is achieved by carrying out 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 on the target cellulose fiber. Can be done.

-Modified cellulose fiber (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 the "anion-modified cellulose fiber" described in the modified cellulose fiber (1) in which the counter ion of the anionic group is a proton, and is preferably an oxidized cellulose fiber. Therefore, the counter ion of the carboxy group is a proton.

The preferred range of the anionic group content in the modified cellulose fiber (2) is the same as that in the "anionic modified cellulose fiber" in the description of the modified cellulose fiber (1).
The modified cellulose fiber (2) can be produced by going through step 1 in the "method for producing the modified cellulose fiber (1)" and then the above-mentioned "miniaturization step".
At any stage of the method for producing the modified cellulose fiber (2), the cellulose fiber may be shortened.

[Properties of modified cellulose fiber]
The main properties of the modified cellulose fiber in the present invention are as follows.

(Average fiber diameter, average fiber length)
The modified cellulose fiber is preferably one that has been subjected to a miniaturization treatment so as to have a nanometer size. The average fiber diameter of the modified cellulose fiber in this case is preferably 1 nm or more, more preferably 2 nm or more, and is easy to handle and is easy to obtain, cost, and suppresses a decrease in viscosity even at high temperatures. From the viewpoint of solvent dispersibility, it is preferably 300 nm or less, more preferably 200 nm or less, still more preferably 150 nm or less, still more preferably 120 nm or less. The average fiber diameter of the modified cellulose fiber that has undergone the micronization treatment is determined by the method described in Examples described later.

The average fiber length of the modified cellulose fiber is preferably 100 nm or more, more preferably 200 nm or more, and the handleability and 80 ° C./ From the viewpoint of bringing the viscosity ratio at 25 ° C. closer to 1, it is preferably 10,000 nm or less, more preferably 5000 nm or less. The average fiber length of the modified cellulose fiber is determined by the method described in Examples described later.

(Average aspect ratio)
In the present invention, the modified cellulose fiber may be a short fiber-treated one. The average aspect ratio of the modified cellulose fiber is not particularly limited, but is preferably 5 or more, more preferably 10 or more, still more preferably 20 or more, while availability, from the viewpoint of exhibiting the effect as a thickener. And from the viewpoint of handleability, it is preferably 300 or less, more preferably 200 or less, still more preferably 100 or less. The average aspect ratio of the modified cellulose fiber is determined by the method described in Examples described later.
By using the modified cellulose fiber having a small average aspect ratio, the viscosity ratio of 80 ° C./25 ° C. can be brought close to 1, and the handleability can be improved.

(Amount of binding of modifying group and introduction rate)
The amount of the modifying group bonded to the modified cellulose fiber is preferably 0.01 mmol / g or more, more preferably 0.1 mmol / g or more, and is similar from the viewpoint of suppressing the decrease in viscosity even at high temperature and dispersibility. From the viewpoint, it is preferably 3.0 mmol / g or less, more preferably 2.5 mmol / g or less. When any two or more kinds of modifying groups are simultaneously introduced into the modified cellulose fiber as modifying groups, the amount of the modifying group bonded is preferably within the above range.

The introduction rate of the modifying group in the modified cellulose fiber is preferably 10 mol% or more, preferably higher, preferably 100 mol%, from the viewpoint of dispersibility and suppressing the decrease in viscosity even at high temperature. When any two or more kinds of modifying groups are introduced at the same time as the modifying group, it is preferable that the total introduction rate is within the above range within the range not exceeding the upper limit of 100 mol%.

The binding amount and introduction rate of the modifying group can be adjusted according to the type and addition amount of the modifying compound, reaction temperature, reaction time, type of solvent and the like. The binding amount (mmol / g) and introduction rate (mol%) of the modifying group are the amount and ratio of the modifying group introduced (bonded) to the anionic group in the modified cellulose fiber. The binding amount and introduction rate of the modifying group in the modified cellulose fiber are calculated by the method described in Examples described later, for example, when the anionic group is a carboxy group.

(Crystal structure)
The modified cellulose fiber preferably has a cellulose I-type crystal structure from the viewpoint of suppressing a decrease in viscosity even at a high temperature, and the crystallinity of the modified cellulose fiber is determined from the viewpoint of developing the strength of the molded product of the resin composition. It is preferably 10% or more, more preferably 15% or more, still more preferably 20% or more. Further, from the viewpoint of raw material availability, it is preferably 90% or less, more preferably 85% or less, still more preferably 80% or less, still more preferably 75% or less. In the present specification, the crystallinity of the cellulose fiber is the cellulose I-type crystallinity calculated from the diffraction intensity value by the X-ray diffraction method, and can be measured according to the method described in Examples described later. The cellulose type I is the crystal form of natural cellulose, and the cellulose type I crystallization degree means the ratio of the amount of the crystal region to the whole cellulose fiber. The presence or absence of the cellulose I-type crystal structure can be determined by the peak at 2θ = 22.6 ° in the X-ray diffraction measurement.

The content of the modified cellulose fiber in the composition of the present invention is preferably in terms of cellulose (not including modifying groups) from the viewpoint of imparting viscosity to the composition and suppressing a decrease in viscosity even at high temperatures. It is 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and on the other hand, from the viewpoint of handling the composition, it is preferably 50% by mass or less, more preferably 30% by mass or more. It is mass% or less, more preferably 20% by mass or less, more preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less. Hereinafter, the amount of the modified cellulose fiber is a cellulose equivalent value containing no modifying group.

[Non-aqueous solvent]
The non-aqueous solvent has a melting point of preferably 100 ° C. or lower, more preferably 50 ° C. or lower, still more preferably 20 ° C. or lower, from the viewpoint of using the thickener composition of the present invention at 50 ° C. or higher. From the same viewpoint, the boiling point is preferably 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.

The non-aqueous solvent is preferably a hydrophobic solvent from the viewpoint of workability such as being used together with an inorganic compound. The hydrophobic solvent has a dissolved amount (20 ° C., 1 atm) of 100 g of water, preferably 100 g or less, more preferably 50 g or less, still more preferably 30 g or less, still more preferably 10 g or less.

Specifically, alcohol-based solvents such as methanol, normal and isopropanol, t-butanol, 1-butanol, 1-hexanol, hexanal, and glycerin; to acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, and methyl. Ketone solvents such as xylketone, diisobutylketone, diacetone alcohol, isophorone; ether solvents such as diethyl ether, tetrahydrofuran (THF), dioxane; methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, polyvalent carboxylic acid esters (eg) , Phtalic acid ester, succinic acid ester, adipic acid ester, etc.), ester solvent such as fatty acid ester of aliphatic polyol such as glycerin; N, N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), ethylene carbonate, N, Highly polar solvents such as N-dimethylacetamide (DMAc) and N-methylpyrrolidone; halogen-based solvents such as methylene chloride, dichloromethane, chloroform, trichloroethylene, perchloroethylene and chlorbenzene; hexane, petroleum ether, liquid paraffin, squalane, squalane Non-aromatic hydrocarbon solvents such as; aromatic hydrocarbon solvents such as benzene, toluene, xylene; nitrile solvents such as acetonitrile; t-butyl glycol, methyl diglycol, ethyl diglycol, butyl diglycol, 1- Methoxy-2-propanol, methyldipropylene glycol, 3-methoxybutanol, 3-methyl-3-methoxybutanol, (mono, di, tri, poly) ethylene glycol methyl ether, ethylene glycol monophenyl ether, (mono, di, poly) Glycol ether solvent such as 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 solvent includes the following glycol ether (ester) solvents: butyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, methoxy butyl acetate, methyl methoxy butyl acetate, ethyl-3. -Ethoxypropionate, propire Nglycol monomethyl ether propionate, glycol ether ester-based solvent of dimethyl carbonate); polymerizable compounds, for example, [epoxy prepolymer (eg, bisphenol type, novolak type, biphenyl type, biphenyl aralkyl type, arylalkylene type, tetrapheni). Roll ethane type, naphthalene type, anthracene type, phenoxy type, dicyclopentadiene type, norbornen type, adamantan type, fluorene type, glycidyl methacrylate copolymer type, etc.); Acrylate prepolymers (eg, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylic acid, etc.); or aliphatic systems such as hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, tetramethylxylylene diisocyanate, etc. Butyl, butyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylic acid, nonanediol diacrylate, phenoxyethyl acrylate, bisphenol A-alkylene oxide adduct (Meta) acrylates, epoxy (meth) acrylates (bisphenol A type epoxy (meth) acrylates, novolak type epoxy (meth) acrylates, etc.); polyester (meth) acrylates (eg, aliphatic polyester type (meth) acrylates, aromatic polyesters) Type (meth) acrylate, etc.); Urethane (meth) acrylate (polyester type urethane (meth) acrylate, polyether type urethane (meth) acrylate, etc.); Silicone (meth) acrylate, cyanoacrylate mono (meth) acrylate, etc.] and Oligomers of these polymerizable compounds; fatty acids such as oleic acid, palmitic acid, and stearic acid; animal and vegetable oils such as olive oil, jojoba oil, and castor oil; silicone oils, fluorine-based inert liquids, process oils, and the like. In the present specification, the non-aromatic hydrocarbon solvent and the aromatic hydrocarbon solvent are collectively referred to as a hydrocarbon solvent.

The non-aqueous solvent preferably contains a hydrocarbon solvent or a glycol ether solvent, and among these, when the modifying group is (a) a hydrocarbon group and (b) a silicone chain, it is carbonized. Hydrogen-based solvents, silicone oils or glycol ether-based solvents (including glycol ether ester-based solvents) are preferable, and (c) in the case of alkylene oxide chains, hydrocarbon-based solvents, alcohol-based solvents, ether-based solvents, ester-based solvents, glycols. Aether-based solvent (including glycol ether ester-based solvent), fatty acid, animal / vegetable oil, silicone oil, fluorine-based inert liquid, process oil, etc. are preferable, and (c) in the case of an alkylene oxide chain, a hydrocarbon-based solvent or glycol ether A system solvent (including a glycol ether ester solvent) is more preferable, and a glycol ether solvent (including a glycol ether ester solvent) is further preferable.
In the case of acid-type anion-modified cellulose fibers, a highly polar solvent is preferable.

The content of the non-aqueous solvent in the composition of the present invention depends on the presence or absence of the inorganic compound, but is generally preferably 15% by mass or more, more preferably 20% by mass or more, and preferably 50% by mass or more. It is preferably 75% by mass or more, more preferably 85% by mass or more, while preferably 99.5% by mass or less, more preferably 99% by mass or less, still more preferably 98% by mass or less, and 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, a 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 dry powder.

Further, in the composition of the present invention, the content of the modified cellulose fiber (not including a modifying group or the like) is preferably 100 parts by mass with respect to 100 parts by mass of the non-aqueous solvent from the viewpoint of suppressing a decrease in viscosity even at a high temperature. It is 0.01 part by mass or more, more preferably 0.05 part by mass or more, further preferably 0.1 part by mass or more, and from the same viewpoint, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, still more preferable. Is 5 parts by mass or less, 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, still more preferably 0. It is 1 part by mass or more and 5 parts by mass or less.

In the composition of the present invention, the content of water 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, still more preferably 0.1% by mass. % Or less, and may be substantially 0% by mass. The water content includes the amount of water brought in from a non-aqueous solvent.

[Inorganic compounds]
To the extent that the effects of the present invention are not impaired, the composition of the present invention comprises metal oxides such as titanium oxide, zinc oxide, aluminum oxide and zirconium oxide; gold, silver, copper, iron, tin, lead, zinc, aluminum and the like. Metal powders; inorganic salts such as calcium carbonate, aluminum hydroxide, ammonium bromide; ceramics, zeolite, carbon black, fullerene, carbon nanotubes, carbon fibers, graphene, silicon carbide, boron nitride, aluminum hydroxide, silica, talc, clay Inorganic compounds exemplified for inorganic solids such as may be contained.
The shape of the inorganic compound is not particularly limited, but powder, granular, fibrous, flake, pellet, lump, and paste are preferable from the viewpoint of handleability.

The content of the inorganic compound in the composition of the present invention varies depending on the intended use and is not particularly limited, but from the viewpoint of the dispersion stability of the inorganic compound at a high temperature of 50 ° C. or higher and the expression of the effect of adding the inorganic compound. With respect to 100 parts by mass of the modified cellulose fiber, preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, still more preferably 1 part by mass or more, still more preferably 2 parts by mass or more, still more preferably 3 parts by mass. More than parts, more preferably 10 parts by mass or more, still more preferably 100 parts by mass or more, while, from the viewpoint of exhibiting the effect of the present invention, preferably 1,000,000 parts by mass or less, more preferably 500,000 parts by mass. Parts or less, more preferably 300,000 parts by mass or less, still more preferably 100,000 parts by mass or less, still more preferably 50,000 parts by mass or less, still more preferably 30,000 parts by mass or less, still more preferably 10,000 parts by mass. It is less than a part.
Therefore, in the composition of the present invention, the mass ratio of the inorganic compound / modified cellulose fiber is preferably 0.1/100 or more and 10000/1 or less, more preferably, from the viewpoint of dispersing the inorganic compound in a non-aqueous solvent. It is 1/100 or more and 1000/1 or less, more preferably 1/10 or more and 300/1 or less, and further preferably 1/1 or more and 100/1 or less.

The content of the inorganic compound in the composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 10% by mass or more, while preferably 99% by mass or less. It is preferably 95% by mass or less, more preferably 90% by mass or less, more preferably 85% by mass or less, and further preferably 80% by mass or less.
In the composition, the mass ratio of the inorganic compound / non-aqueous solvent is preferably 1/100 or more, more preferably 1/10 or more, still more preferably 1/1 or more, from the viewpoint of dispersing the inorganic compound in the non-aqueous solvent. From the viewpoint of dispersion stability in a non-aqueous solvent at 50 ° C. or higher, it is preferably 500/1 or less, more preferably 300/1 or less, still more preferably 100/1 or less.

[Other ingredients]
Other components such as plasticizers, crystal nucleating agents, fillers (inorganic fillers, organic fillers), hydrolysis inhibitors, flame retardants, antioxidants, hydrocarbons, as long as the effects of the present invention are not impaired. Waxes and anionic surfactants such as gelatin, UV absorbers, antistatic agents, antifogging agents, light stabilizers, pigments, antifungal agents, antibacterial agents, foaming agents, surfactants; starches, alginic acid, etc. Polysaccharides; natural proteins such as gelatin, gelatin, casein; tannins; fragrances; flow regulators; leveling agents; conductive agents; UV dispersants; deodorants and the like may be contained in the composition of the present invention. No. Furthermore, other polymer materials and other compositions can be added as long as the effects of the present invention are not impaired. The other component may be the above-mentioned inorganic compound.

[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 or the like.
For example, each of the above-mentioned components is kneaded using a known kneader such as a closed kneader, a single-screw extruder, a roll mill, or an open-roll kneader, or by a solvent casting method, or. It can be carried out by shearing with a shearing device such as a high shearing machine.

[Characteristics of thickener composition]
In general, the viscosity of a liquid object tends to decrease as the temperature increases, but the composition of the present invention is characterized in that the tendency is smaller. 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 preferable from the viewpoint of suppressing the decrease in viscosity even at high temperatures. Is 0.6 or more, more preferably 0.7 or more, still more preferably 0.8 or more, still more preferably 0.9 or more, and preferably 5 or less, still more preferably, from the viewpoint of reducing the temperature dependence. Is 3 or less, more preferably 2 or less, still more preferably 1.5 or less. Further, the value of [viscosity at 125 ° C.] / [viscosity at 25 ° C.] (viscosity ratio at 125 ° C./25 ° C.) of the composition of the present invention is preferably 0. 6 or more, more preferably 0.7 or more, still more preferably 0.8 or more, still more preferably 0.9 or more, and from the viewpoint of reducing the temperature dependence, preferably 5 or less, still more preferably 3 or less. , More preferably 2 or less, still more preferably 1.5 or less.

The viscosity (mPa · s) of the composition of the present invention at 25 ° C. is preferably 100 or more, more preferably 500 or more, still more preferably 500 or more, from the viewpoint of handling the composition, provided ^{that the shear rate is 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, still more preferably 200,000 or less, still more preferably 100,000 or less, still more preferably 30,000 or less. Is.

The viscosity (mPa · s) of the composition of the present invention at 80 ° C. is preferably 100 or more, more preferably 500 or more, still more preferably 500 or more, from the viewpoint of handling the composition, provided ^{that the shear rate is 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, still more preferably 200,000 or less, still more preferably 100,000 or less, still more preferably 30,000 or less. Is.

The viscosity (mPa · s) of the composition of the present invention at 125 ° C. is preferably 100 or more, more preferably 500 or more, still more preferably 500 or more, from the viewpoint of handling the composition, provided ^{that the shear rate is 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, still more preferably 200,000 or less, still more preferably 100,000 or less, still more preferably 30,000 or less. Is.
The thickener composition of the present invention has fluidity as described above, so that workability can be improved.

The method for measuring the viscosity in the present specification can be carried out by the method described in Examples described later using a rheometer.

[Use of thickener composition]
The thickener composition of the present invention can be used in various products without particular limitation. Specific examples of products to which the thickener composition of the present invention can be applied include foods and drinks, cosmetics, quasi-drugs, pharmaceuticals, daily necessities, feeds, miscellaneous goods, pesticides and chemical industry products. More specifically, in the fields of home appliance parts, electronic materials (electronics), packaging containers, aerospace, civil engineering, automobiles, automobiles, etc., resin molding materials, electrical insulation materials, paints, inks, coating agents, adhesives, etc. , Repair materials, adhesives, lubricants, sealing materials, heat insulating materials, sound absorbing materials, artificial leather materials, electronic materials, semiconductor materials, tires, automobile parts, fiber composite materials and the like. Of these, preferred are for electronic materials, optical materials or structural materials.

The blending amount of the thickener composition blended in these products is not particularly limited, but is preferably 0.01 parts by mass or more, more preferably 0.01 parts by mass, based on 100 parts by mass of the product (or the total amount of each component constituting the product). It is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, while preferably 1000 parts by mass or less, more preferably 800 parts by mass or less, still more preferably 500 parts by mass or less.

<Use of thickener composition>
The thickener composition of the present invention contains the modified cellulose fiber and a non-aqueous solvent, and is intended for use at 50 ° C. or higher, preferably 60 ° C. or higher, more preferably 80 ° C. or higher. The upper limit of the usable temperature is preferably 300 ° C., more preferably 280 ° C., still more preferably 250 ° C., still more preferably 200 ° C. from the viewpoint of developing thickening.
Further, the thickener composition of the present invention is preferably used in a temperature range of 50 ° C. or higher, more preferably 100 ° C. or higher, preferably 250 ° C. or lower, while maintaining thickening. Is preferable.
Here, the temperature range of 50 ° C. or higher is, for example, 50 ° C. to 100 ° C. (50 ° C. temperature range), 40 ° C. to 150 ° C. (110 ° C. temperature range), 70 ° C. to 200 ° C. (130 ° C. temperature range). Is.

As used herein, the use of a thickener composition at a specified temperature (or temperature range) means adding the thickening agent composition at a specified temperature (or temperature range) to an object to be thickened. After adding the thickener composition to the object to be thickened, the temperature may be adjusted to a specified temperature (or temperature range).
Since the thickener composition of the present invention is used at 50 ° C. or higher, a part or all of the non-aqueous solvent may volatilize, but it can be used without any problem. Further, depending on the application, there is a mode in which the solvent component is completely evaporated and solidified by further heating after maintaining the viscosity up to a certain temperature. Even in such a mode, the thickening of the present invention is performed. It can be said that the use of the agent composition was suitably achieved. In the use of the thickener composition, it is preferable that the thickener composition further contains the above-mentioned inorganic compound.
Specific embodiments used over a temperature range of 50 ° C. or higher include, for example, a lubricant, grease oil, and the like.
Specific embodiments of use over a temperature range of 50 ° C. or higher to remove a non-aqueous solvent as a result are, for example, paints and inks.

<Viscosity control agent for non-aqueous solvent>
The viscosity control agent of the present invention contains the modified cellulose fiber. The viscosity control agent of the present invention is for a non-aqueous solvent, 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 a decrease in viscosity at a high temperature of 50 ° C. or higher. , A high temperature viscosity control agent. 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 preferably 300 ° C. or lower, more preferably 280 ° C. or higher, still more preferable. Is used at 200 ° C. or lower, more preferably 150 ° C. or lower. Examples of the non-aqueous solvent include those mentioned above.

In the viscosity control agent of the present invention, the content of the modified cellulose fiber (not including modifying groups) is preferably 0. From the viewpoint of controlling the viscosity of the non-aqueous solvent with respect to 100 parts by mass of the non-aqueous solvent. It is 01 parts by mass or more, more preferably 0.05 parts by mass or more, further preferably 0.1 part by mass or more, and from the same viewpoint, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 5. It is blended in parts by mass or less. That is, the content of the modified cellulose fiber (not including modifying groups) is preferably 0.01 part by mass or more and 20 parts by mass or less, more preferably 0.05 part by mass with respect to 100 parts by mass of the non-aqueous solvent. 10 parts by mass or less, more preferably 0.1 parts by mass or more and 5 parts by mass or less.

[Inorganic compounds]
The viscosity control agent of the present invention may contain an inorganic compound that can be used in the above-mentioned thickener composition as long as the effect of the present invention is not impaired. The shape of the inorganic compound is not particularly limited, but powder, granular, fibrous, flake, pellet, lump, and paste are preferable from the viewpoint of handleability.

The amount of the inorganic compound with respect to the modified cellulose fiber in the viscosity control agent of the present invention is as described in the above-mentioned thickener composition, and the preferable range is the same.
The viscosity control agent of the present invention uses a non-aqueous solvent as described in the above-mentioned properties of the thickener composition, having a viscosity of 25 ° C., 80 ° C., 120 ° C., a viscosity ratio of 80 ° C./25 ° C., and a viscosity ratio of 80 ° C./25 ° C. The viscosity ratio of 120 ° C./25 ° C. can be controlled to a preferable value.

<How to apply inorganic compounds>
In the present invention, a composition containing one or more modified cellulose fibers selected from the group consisting of the following (1) and (2), a non-aqueous solvent and an inorganic compound is heated to 100 ° C. or higher. A method for applying an inorganic compound, which comprises a step of removing a non-aqueous solvent.
(1) It has an I-type crystal structure in which a modifying group is bonded to a cellulose fiber, and the modifying group is (a) a hydrocarbon group, (b) a silicone chain, and (c) an alkylene oxide chain. Those containing one or more selected from the group consisting of (2) Acid-type anionic-modified cellulose fibers having an I-type crystal structure Non-aqueous solvents and inorganic compounds are as described above.

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.
Since the composition is suppressed from decreasing in viscosity even at a high temperature of 50 ° C. or higher, it can be applied by suppressing the diffusion of the inorganic compound. Examples of the object to be applied include a metal surface, a plastic surface, paper and the like, and can be used, for example, for paints and inks. Preferred compounds, preferred contents, preferred content ratios, etc. of each component of the composition in the coating method are as described in the above-mentioned composition.

With respect to the above-described embodiments, the present invention further discloses the following methods for applying a thickener composition, a thickener composition, a viscosity control agent, and an inorganic compound.
<1> A thickener composition containing a modified cellulose fiber and a non-aqueous solvent and used at 50 ° C. or higher.
The modified cellulose fiber is one or more selected from the group consisting of the following (1) and (2), and is a thickener composition.
(1) It has an I-type crystal structure in which a modifying group is bonded to a cellulose fiber, and the modifying group is (a) a hydrocarbon group, (b) a silicone chain, and (c) an alkylene oxide chain. Those containing one or more selected from the group consisting of (2) Acid-type anion-modified cellulose fibers having an I-type crystal structure

<2> The composition according to <1> above, wherein the viscosity ratio at 80 ° C./25 ° C. is 0.6 or more and 5 or less.
<3> The composition according to <1> or <2>, wherein the viscosity ratio at 80 ° C./25 ° C. is 0.7 or more and 3 or less.
<4> The composition according to any one of <1> to <3>, wherein the viscosity ratio at 125 ° C./25 ° C. is 0.6 or more and 5 or less.
<5> The composition according to any one of <1> to <4>, wherein the viscosity ratio at 125 ° C./25 ° C. is 0.7 or more and 3 or less.
<6> The composition according to any one of <1> to <5>, wherein the cellulose fiber in (1) is an anion-modified cellulose fiber.
<7> The composition according to any one of <1> to <6> above, wherein the modifying group is bonded to the anionic group of the anionic-modified cellulose fiber via an ionic bond and / or a covalent bond.
<8> The non-aqueous solvent contains a hydrocarbon solvent, an alcohol solvent, an ether solvent, an ester solvent, a glycol ether solvent (including a glycol ether ester solvent), a fatty acid, an animal / vegetable oil, or a silicone oil. , The composition according to any one of <1> to <7>.
<9> The composition according to any one of <1> to <8> above, wherein the non-aqueous solvent contains a hydrocarbon solvent or a glycol ether solvent.
<10> When the modified cellulose fiber contains (a) a hydrocarbon group or (b) a silicone chain, the non-aqueous solvent is a hydrocarbon solvent, a silicone oil or a glycol ether solvent. The composition according to any one of <9>.
<11> When the modified cellulose fiber contains (c) an alkylene oxide chain, the non-aqueous solvent is a hydrocarbon solvent or a glycol ether solvent (including a glycol ether ester solvent). The composition according to any one of <10>.
<12> When the modified cellulose fiber contains (c) an alkylene oxide chain, the non-aqueous solvent is a glycol ether solvent (including a glycol ether ester solvent), any of the above <1> to <11>. The composition according to one.
<13> In one or more (co) polymerization sections in which the alkylene oxide chain is selected from the group consisting of an ethylene oxide (EO) polymerization section, a propylene oxide (PO) polymerization section, and a (EO / PO) copolymer section. The composition according to any one of the above <1> to <12>.
<14> The composition according to any one of <1> to <13>, wherein the average fiber diameter of the modified cellulose fiber is 1 nm or more and 300 nm or less, preferably 2 nm or more and 200 nm or less.
<15> The composition according to any one of <1> to <14>, wherein the average fiber length of the modified cellulose fiber is 100 nm or more and 10,000 nm or less, preferably 200 nm or more and 5000 nm or less.
<16> The composition according to any one of <1> to <15>, which further comprises an inorganic compound.
<17> The mass ratio of the inorganic compound / modified cellulose fiber is 1/100 or more and 500/1 or less, preferably 1/10 or more and 300/1 or less, and more preferably 1/1 or more and 100/1 or less. The composition according to <16>.
<18> The content of the inorganic compound in the composition is preferably 0.1% by mass or more and 90% by mass or less, more preferably 1% by mass or more and 85% by mass or less, and further preferably 10% by mass or more and 80% by mass or less. The composition according to any one of the above <16> or <17>.
<19> The content of the modified cellulose fiber (not including modifying groups) in the composition is preferably 0.01% by mass or more and 50% by mass or less, more preferably 0.05% by mass or more in terms of cellulose. The composition according to any one of <1> to <18>, which is 20% by mass or less, more preferably 0.1% by mass or more and 10% by mass or less.
<20> The content of the modified cellulose fiber (not including modifying groups) in the composition is preferably 0.01 part by mass or more and 20 parts by mass or less, more preferably 20 parts by mass or less, based on 100 parts by mass of the non-aqueous solvent. The composition according to any one of <1> to <19>, wherein the composition is 0.05 parts by mass or more and 10 parts by mass or less, more preferably 0.1 parts by mass or more and 5 parts by mass or less.
<21> The content of the non-aqueous solvent in the composition is 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. The composition according to any one of.
<22> The composition according to any one of <1> to <21>, which is used at 60 ° C. or higher, more preferably 80 ° C. or higher.
<23> The composition according to any one of <1> to <22>, which is used in a temperature range of 50 ° C. or higher, preferably 100 ° C. or higher.
<24> The composition according to any one of <1> to <23>, which is used after removing a non-aqueous solvent.
<25> The composition according to any one of <1> to <24> above, which is for an electronic material, an optical material, or a structural material.
<26> 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) It has an I-type crystal structure in which a modifying group is bonded to a cellulose fiber, and the modifying group is (a) a hydrocarbon group, (b) a silicone chain, and (c) an alkylene oxide chain. Those containing one or more selected from the group consisting of (2) Acid-type anion-modified cellulose fibers having an I-type crystal structure
<27> The use according to <26> above, which is used at 60 ° C. or higher.
<28> The use according to the above <26> or <27>, which is used at 80 ° C. or higher.
<29> The use according to any one of <26> to <28> above, which is used in a temperature range of 50 ° C. or higher.
<30> The use according to any one of <26> to <29> above, which is used in a temperature range of 100 ° C. or higher.
<31> The use according to any one of <26> to <30> above, which removes a non-aqueous solvent.
<32> The use according to any one of <26> to <31> above, wherein the thickener composition has a viscosity ratio of 80 ° C./25 ° C. of 0.6 or more and 5 or less.
<33> The use according to any one of <26> to <32> above, wherein the viscosity ratio of the thickener composition at 80 ° C./25 ° C. is 0.7 or more and 3 or less.
<34> The use according to any one of <26> to <33> above, wherein the thickener composition has a viscosity ratio of 125 ° C./25 ° C. of 0.6 or more and 5 or less.
<35> The composition according to any one of <26> to <34>, wherein the thickener composition has a viscosity ratio of 125 ° C./25 ° C. of 0.7 or more and 3 or less.
<36> The use according to any one of <26> to <35>, wherein the cellulose fiber in (1) is an anion-modified cellulose fiber.
<37> The use according to any one of <26> to <36> above, wherein the modifying group is bonded to the anionic group of the anionic-modified cellulose fiber via an ionic bond and / or a covalent bond.
<38> The non-aqueous solvent contains a hydrocarbon solvent, an alcohol solvent, an ether solvent, an ester solvent, a glycol ether solvent (including a glycol ether ester solvent), a fatty acid, an animal / vegetable oil, or a silicone oil. , The use according to any one of <26> to <37> above.
<39> The use according to any one of <26> to <38> above, wherein the non-aqueous solvent contains a hydrocarbon solvent or a glycol ether solvent.
<40> When the modified cellulose fiber contains (a) a hydrocarbon group or (b) a silicone chain, the non-aqueous solvent is a hydrocarbon solvent, a silicone oil or a glycol ether solvent. Use described in any one of <39>.
<41> When the modified cellulose fiber contains (c) an alkylene oxide chain, the non-aqueous solvent is a hydrocarbon solvent or a glycol ether solvent (including a glycol ether ester solvent). Use described in any one of <40>.
<42> When the modified cellulose fiber contains (c) an alkylene oxide chain, the non-aqueous solvent is a glycol ether solvent (including a glycol ether ester solvent), any of the above <26> to <41>. Use as described in one.
<43> In one or more (co) polymerization sections in which the alkylene oxide chain is selected from the group consisting of an ethylene oxide (EO) polymerization section, a propylene oxide (PO) polymerization section, and a (EO / PO) copolymer section. The use according to any one of the above <26> to <42>.
<44> The use according to any one of <26> to <43>, wherein the average fiber diameter of the modified cellulose fiber is 1 nm or more and 300 nm or less, preferably 2 nm or more and 200 nm or less.
<45> The use according to any one of <26> to <44>, wherein the average fiber length of the modified cellulose fiber is 100 nm or more and 10,000 nm or less, preferably 200 nm or more and 5000 nm or less.
<46> The use according to any one of <26> to <45> above, wherein the thickener composition further contains an inorganic compound.
<47> The mass ratio of the inorganic compound / modified cellulose fiber in the thickener composition is 0.1/100 or more and 10000/1 or less, preferably 1/100 or more and 1000/1 or less, and more preferably 1/10 or more. The use according to any one of the above <26> to <46>, which is 300/1 or less, more preferably 1/1 or more and 100/1 or less.
<48> The content of the inorganic compound in the composition is preferably 0.1% by mass or more and 90% by mass or less, more preferably 1% by mass or more and 85% by mass or less, and further preferably 10% by mass or more and 80% by mass or less. The use according to any one of the above <26> to <47>.
<49> The content of the modified cellulose fiber (excluding modifying groups) in the composition is preferably 0.01% by mass or more and 50% by mass or less, more preferably 0.05% by mass or more in terms of cellulose. The use according to any one of the above <26> to <48>, which is 20% by mass or less, more preferably 0.1% by mass or more and 10% by mass or less.
<50> The content of the modified cellulose fiber (not including modifying groups) in the composition is preferably 0.01 part by mass or more and 20 parts by mass or less, more preferably 20 parts by mass or less, based on 100 parts by mass of the non-aqueous solvent. The use according to any one of <26> to <49> above, which is 0.05 part by mass or more and 10 parts by mass or less, more preferably 0.1 part by mass or more and 5 parts by mass or less.
<51> The content of the non-aqueous solvent in the composition is 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. Use described in any one of.
<52> The use according to any one of <26> to <51> above, wherein the thickener composition is a composition for an electronic material, an optical material, or a structural material.
<53> A viscosity control agent for a non-aqueous solvent containing one or more modified cellulose fibers selected from the group consisting of the following (1) and (2).
(1) It has an I-type crystal structure in which a modifying group is bonded to a cellulose fiber, and the modifying group is (a) a hydrocarbon group, (b) a silicone chain, and (c) an alkylene oxide chain. Those containing one or more selected from the group consisting of (2) Acid-type anion-modified cellulose fibers having an I-type crystal structure
<54> The viscosity control agent according to <53>, which further contains an inorganic compound.
<55> The viscosity control agent according to <53> or <54>, which is used at 50 ° C. or higher.
<56> The viscosity control agent according to any one of <53> to <55>, which is used at 60 ° C. or higher.
<57> The viscosity control agent according to any one of <53> to <56>, which is used at 80 ° C. or higher.
<58> The viscosity control agent according to any one of <53> to <57>, which is used in a temperature range of 50 ° C. or higher.
<59> The viscosity control agent according to any one of <53> to <58>, which is used in a temperature range of 100 ° C. or higher.
<60> The viscosity control agent according to any one of <53> to <59>, wherein the viscosity ratio at 80 ° C./25 ° C. is 0.6 or more and 5 or less.
<61> The viscosity control agent according to any one of <53> to <60>, wherein the viscosity ratio at 80 ° C./25 ° C. is 0.7 or more and 3 or less.
<62> The viscosity control agent according to any one of <53> to <61>, wherein the viscosity ratio at 125 ° C./25 ° C. is 0.6 or more and 5 or less.
<63> The viscosity control agent according to any one of <53> to <62>, wherein the viscosity ratio at 125 ° C./25 ° C. is 0.7 or more and 3 or less.
<64> A composition containing one or more modified cellulose fibers selected from the group consisting of the following (1) and (2), a non-aqueous solvent and an inorganic compound is heated to 100 ° C. or higher to be non-processed. A method for applying an inorganic compound, which comprises a step of removing an aqueous solvent.
(1) It has an I-type crystal structure in which a modifying group is bonded to a cellulose fiber, and the modifying group is (a) a hydrocarbon group, (b) a silicone chain, and (c) an alkylene oxide chain. Those containing one or more selected from the group consisting of (2) Acid-type anion-modified cellulose fibers having an I-type crystal structure
<65> The coating method according to <64>, wherein the coating method is preferably heated to 150 ° C. or higher, more preferably 200 ° C. or higher.
<66> The content of the inorganic compound in the composition is preferably 0.1% by mass or more and 90% by mass or less, more preferably 1% by mass or more and 85% by mass or less, and further preferably 10% by mass or more and 80% by mass or less. The coating method according to the above <64> or <65>.
<67> The content of the modified cellulose fiber (not including modifying groups) in the composition is preferably 0.01% by mass or more and 50% by mass or less, more preferably 0.05% by mass or more in terms of cellulose. The coating method according to any one of <64> to <66>, wherein the coating method is 20% by mass or less, more preferably 0.1% by mass or more and 10% by mass or less.
<68> The content of the modified cellulose fiber (not including modifying groups) in the composition is preferably 0.01 part by mass or more and 20 parts by mass or less, more preferably 20 parts by mass or less, based on 100 parts by mass of the non-aqueous solvent. The coating method according to any one of <64> to <67>, wherein the coating method is 0.05 parts by mass or more and 10 parts by mass or less, more preferably 0.1 parts by mass or more and 5 parts by mass or less.
<69> The content of the non-aqueous solvent in the composition is 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. The coating method according to any one of the above.

Hereinafter, the present invention will be specifically described with reference to Examples and the like. It should be noted that the following examples are merely examples of the present invention and do not mean any limitation. The "normal pressure" indicates 101.3 kPa, and the "normal temperature" indicates 25 ° C.

[Average fiber diameter, average fiber length and average aspect ratio of miniaturized anion-modified cellulose fiber and modified cellulose fiber]
If the measurement target is a finely divided anion-modified cellulose fiber, add water, or if the measurement target is a modified cellulose fiber, add the same solvent as that used when preparing the thickener composition, and add the content thereof. Prepare a dispersion of 0.0005% by mass. If the solvent is squalane or TGME, IPA is used. Atomic force microscope (AFM) (Nanoscope II Tappingmode AFM, manufactured by Digital instrument, Nanoscope II Tappingmode AFM; probe manufactured by Nanosensors, Point Probe (AFM) Using NCH)), the fiber height (difference in height between the presence and absence of fibers) of the cellulose fibers in the observation sample is measured. At that time, in a microscope image in which the cellulose fibers can be confirmed, 100 or more cellulose fibers are extracted, and the average fiber diameter is calculated from the fiber heights thereof. The average fiber length is calculated from the distance in the fiber direction. The average aspect ratio is calculated from the average fiber length / average fiber diameter. The height analyzed in the image by AFM can be regarded as the fiber diameter.

Only in Example 10, it was difficult to confirm the modified cellulose fiber by the measurement using the above AFM. Therefore, only in Example 10, the obtained thickener composition was diluted with IPA to 0.02% by mass, and one drop of the solution sonicated for 5 minutes was dropped onto mica. After air-drying, observe the sample gold-spattered with MSP-1S (manufactured by Vacuum Device Co., Ltd.) using an electron microscope VE-8800 (manufactured by KEYENCE) under the measurement conditions of an acceleration voltage of 5 kV and a spot diameter of 8. The average fiber diameter, average fiber length and average aspect ratio of the modified cellulose fibers were determined by the same method as described above.

[Average fiber diameter and average fiber length of raw material cellulose fiber and anion-modified cellulose fiber]
Deionized water is added to the cellulose fibers to be measured to prepare a dispersion having a content of 0.01% by mass. Using a wet dispersion type image analysis particle size distribution meter (manufactured by Jasco International, trade name: IF-3200), the dispersion is used for front lens: 2x, telecentric zoom lens: 1x, image resolution: 0.835 μm / pixel. , Syringe inner diameter: 6515 μm, spacer thickness: 500 μm, image recognition mode: ghost, threshold: 8, analytical sample volume: 1 mL, sampling: 15%. 100 or more cellulose fibers are measured, and the average ISO fiber diameter thereof is taken as the average fiber diameter, and the average ISO fiber length is calculated as the average fiber length.

[Anionic group content of anionic-modified cellulose fibers and modified cellulose fibers]
Take the cellulose fiber to be measured with a dry mass of 0.5 g in a beaker, add deionized water or a mixed solvent of methanol / water = 2/1 (volume ratio) to make a total of 55 mL, and add 5 mL of 0.01 M sodium chloride aqueous solution to this. To prepare a dispersion. The dispersion is stirred until the cellulose fibers to be measured are sufficiently dispersed. Add 0.1 M hydrochloric acid to this dispersion to adjust the pH to 2.5 to 3, and use an automatic titrator (manufactured by Toa DKK, trade name "AUT-701") to add a 0.05 M aqueous sodium hydroxide solution. Then, the solution is added dropwise to the dispersion under the condition of a waiting time of 60 seconds, and the electric conductivity and pH values are measured every minute. Continue the measurement until the pH reaches about 11, and obtain a conductivity curve. From this conductivity curve, the quantification of sodium hydroxide titration is obtained, and the anionic group content of the cellulose fiber to be measured is calculated by the following formula.
Anionic group content (mmol / g) = [Sodium hydroxide aqueous solution droplet quantification (mL) × Sodium hydroxide aqueous solution concentration (0.05 M)] / [Mass of cellulose fiber to be measured (0.5 g)]

[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.
On the other hand, separately from this, in a beaker, 100 g of an aqueous dispersion of the oxidized cellulose fiber to be measured (solid content content 1.0% by mass), 100 g of an acetate buffer (pH 4.8), 2-methyl-2-butene. 0.33 g and 0.45 g of sodium chlorite are added and stirred at 25 ° C. for 16 hours to oxidize the aldehyde group remaining on the oxidized cellulose fiber. After completion of the reaction, the cellulose fibers are washed with deionized water to obtain cellulose fibers obtained by oxidizing an aldehyde group. The carboxy group content of the dried product obtained by freeze-drying treatment is measured by the above-mentioned method for measuring the anionic group content, and the "carboxy group content of the oxidized cellulose fiber" is calculated. Subsequently, the aldehyde group content of the oxidized cellulose fiber to be measured is calculated by the formula 1.

Alaldehyde group content (mmol / g) = (carboxy group content of oxidized cellulose fiber)-(carboxy group content of oxidized cellulose fiber to be measured) ... Equation 1

[Solid content in gel or dispersion]
Measure using a halogen moisture meter (manufactured by Shimadzu Corporation; trade name "MOC-120H"). Measurement is performed every 30 seconds at a constant temperature of 150 ° C. for 1 g of the sample, and the value at which the mass loss is 0.1% or less of the initial amount of the sample is defined as the solid content. If it is difficult to analyze the solid content concentration by the above analysis method because an organic solvent having a high boiling point is used, a known alternative method such as a phenol sulfuric acid method may be used separately.

[Amount of binding of modifying group and introduction rate of modified cellulose fiber]
The binding amount of the modifying group is obtained by the following IR measurement method, and the binding amount and the introduction rate are calculated by the following formula. Specifically, the IR measurement is performed by measuring the infrared absorption spectrum of the dried modified cellulose fiber by the ATR method using an infrared absorption spectroscope (IR) (Nicolet 6700 manufactured by Thermo Fisher Scientific Co., Ltd.). , The amount of binding of the modifying group and the introduction rate are calculated by the formulas A and B. The following shows the case where the anionic group is a carboxy group, that is, the case of an oxidized cellulose fiber. The following " ^{peak intensity of 1720 cm -1} " is the peak intensity derived from the carbonyl group. In the case of an anionic group other than the carboxy group, the wavenumber value may be appropriately changed to calculate the bond amount and introduction rate of the modifying group.

<Formula A-1 (in the case of ionic bond)>
Bonding amount of modifying group (mmol / g) = a × (bc) ÷ b
a: Carboxy group content of cellulose oxide fiber (mmol / g)
b: the peak intensity of the oxidized cellulose fibers 1720cm ^-1 c: <(For amide bond) Formula A-2> reforming peak intensity of 1720 cm ^-1 of the cellulose fibers
Modulating group binding amount (mmol / g) = de
d: Carboxy group content of cellulose oxide fiber (mmol / g)
e: Carboxy group content of modified cellulose fiber (mmol / g)
<Equation B>
Introductory rate of modifying group (mol%) = 100 × f / g
f: Bonding amount of modifying group (mmol / g)
g: Carboxy group content of cellulose oxide fiber (mmol / g)

[Confirmation of crystal structure in modified cellulose fiber]
The crystal structure of the modified cellulose fiber is confirmed by measuring under the following conditions using an X-ray diffractometer (MiniFlexII manufactured by Rigaku Co., Ltd.).
The measurement conditions are X-ray source: Cu / Kα-radiation, tube voltage: 30 kv, tube current: 15 mA, measurement range: diffraction angle 2 θ = 5 to 45 °, and X-ray scan speed: 10 ° / min. As a sample for measurement, the cellulose fiber to be measured is compressed into pellets having an ^{area of 320 mm 2 × thickness of 1 mm.} Further, the crystallinity of the cellulose type I crystal structure is calculated by calculating the obtained X-ray diffraction intensity based on the following formula C.

<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, and I _18.5 is the amorphous portion (diffraction angle 2θ = 18.5). °) Diffraction intensity]

On the other hand, when the crystallinity obtained by the above formula C is 35% or less, from the viewpoint of improving the calculation accuracy, P199-200 of "Wood Science Experiment Manual" (edited by Japan Wood Society; published in April 2000). It is preferable to calculate based on the following formula D according to the description of.
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.

<Equation D>
Cellulose type I crystallinity (%) = [ _Ac / ( _Ac + A _a )] × 100
[In the equation, _Ac is a lattice plane (002 plane) (diffraction angle 2θ = 22.6 °), (011 plane) (diffraction angle 2θ = 15.1 °) and (0-11 plane) in X-ray diffraction. sum of the peak areas of (the diffraction angle 2θ = 16.2 °), _{a a} represents a peak area of an amorphous portion (angle of diffraction 2θ = 18.5 °), the X-ray diffraction chart each peak area is obtained Obtained by fitting with a Gaussian function]

[Cellulose fiber in modified cellulose fiber (converted amount)]
The amount of cellulose (converted amount) in the modified cellulose fiber is the amount of cellulose in the modified cellulose fiber excluding the modifying group. In the modified cellulose fiber in the present invention, the formula amount of the modifying group may be considerably larger (for example, than the molecular weight of glucose). When is appropriate, the amount of cellulose constituting the modified cellulose fiber (converted amount) is displayed instead of the amount of the modified cellulose fiber.
The cellulose fiber (converted amount) in the modified cellulose fiber is measured by the following method.

(1) When one kind of "modifying compound" is added The amount of cellulose fibers (converted amount) is calculated by the following formula E.
<Formula E>
Cellulose fiber amount (converted 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 there are two or more types of "modifying compounds" to be added The amount of cellulose fibers in consideration of the molar ratio of each compound (that is, the molar ratio when the total molar amount of the added compounds is 1) Calculate (converted amount).

[Preparation of anion-modified cellulose fiber 1]
Preparation Example 1
Softwood bleached kraft pulp (manufactured by West Freather, trade name: Hinton) was used as the raw material of natural cellulose fiber. As the TEMPO, a commercially available product (ALDRICH, Free radical, 98% by mass) was used. Commercially available products were used as sodium hypochlorite, sodium bromide and sodium hydroxide.

First, 10 g of the bleached kraft pulp fiber and 990 g of deionized water were weighed in a 2 L PP beaker equipped with a mechanical stirrer and a stirring blade, and the mixture was 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 mass% sodium hypochlorite aqueous solution were added to 10 g of the pulp fiber in this order. Using a pH stat titration with an automatic titrator (manufactured by DKK-TOA Corporation, trade name: AUT-701), a 0.5 M sodium hydroxide aqueous solution was added dropwise to maintain the pH at 10.5. After the reaction was carried out at a stirring speed of 100 rpm at 25 ° C. for 120 minutes, the dropping of the aqueous sodium hydroxide solution was stopped, and a suspension of anionic-modified cellulose fibers (that is, oxidized cellulose fibers) in which the anionic group was a carboxy group was prepared. Obtained.

After adding 0.01 M hydrochloric acid to the obtained suspension of anionic-modified cellulose fibers to adjust the pH to 2, filter by measuring the conductivity using a compact electric conductivity meter (LAQUAtwin EC-33B, manufactured by HORIBA, Ltd.). Cellulose fibers were thoroughly washed with deionized water until the liquid became 200 μs / cm or less, and then dehydrated to obtain anion-modified cellulose fibers. The carboxy group content of the anion-modified cellulose fiber was 1.50 mmol / g, and the aldehyde group content was 0.23 mmol / g.

Preparation Example 2 (Production of Micronized Anion-Modified Cellulose Fiber)
Deionized water was added to the anion-modified cellulose fiber finally obtained in Preparation Example 1 to prepare 100 g of a suspension (solid content content: 2.0% by mass). A 0.5 M aqueous sodium hydroxide solution was added to adjust the pH to 8, and then deionized water was added to bring the total amount to 200 g. This suspension was subjected to a micronization treatment at 150 MPa three times using a high-pressure homogenizer (manufactured by Yoshida Machinery Co., Ltd., trade name: NanoVeta L-ES) three times, and a miniaturized anion-modified cellulose fiber dispersion liquid (solid content content 1. 0% by mass) was obtained. The counter ion of the carboxy group of this miniaturized anion-modified cellulose fiber was sodium ion.

Preparation Example 3 (Production of Micronized Anion-Modified Cellulose Fiber with Reduction Treatment of Aldehyde Group)
182 g of the finely divided anion-modified cellulose fiber dispersion (solid content content 1.0% by mass) obtained in Preparation Example 2 was weighed, and deionized water was added to make a total of 400 g. 1.2 mL of 0.1 M aqueous sodium hydroxide solution and 120 mg of sodium borohydride were added thereto, and the mixture was stirred at 25 ° C. for 4 hours. Next, 9 mL of 1M hydrochloric acid was added for protonation. After completion of the reaction, the cake was filtered and washed with deionized water 6 times to remove salts and hydrochloric acid, and the aldehyde group was reduced. The finely divided anion-modified cellulose fiber dispersion liquid (solid content content 0. 9% by mass) was obtained. The obtained cellulose fiber had a carboxy group content of 1.50 mmol / g and an aldehyde group content of 0.02 mmol / g. The carboxy group of this miniaturized anion-modified cellulose fiber is a free acid type (COOH) and is abbreviated as "TCNF (acid type)". The average fiber diameter of the finely divided anion-modified cellulose fibers was 3.3 nm, and the average fiber length was 600 nm.

[Preparation of anion-modified cellulose fiber 2]
Preparation Example 4
After sufficiently stirring 10 g of coniferous bleached kraft pulp (manufactured by West Freder Co., Ltd., trade name: Hinton) as natural cellulose with 990 g of ion-exchanged water, TEMPO (manufactured by ALDRICH, Free radical, 98) per 10 g of the pulp. (% by mass) 0.13 g, 1.3 g of sodium bromide, and 27 g of a 10.5 mass% sodium hypochlorite aqueous solution (10.5 mass% aqueous solution) were added in this order. Using a pH stat titration with an automatic titrator (AUT-701, manufactured by DKK-TOA CORPORATION), a 0.5 M aqueous sodium hydroxide solution was added dropwise to maintain the pH at 10.5. After the reaction was carried out at a stirring speed of 200 rpm for 120 minutes (20 ° C.), the dropping of sodium hydroxide was stopped, and a suspension of anionic-modified cellulose fibers (that is, oxidized cellulose fibers) in which the anionic group was a carboxy group was prepared. Obtained.

0.01 M hydrochloric acid was added to the obtained suspension of anion-modified cellulose fibers to adjust the pH to 2, and then the conductivity was measured using a compact electric conductivity meter (LAQUAtwin EC-33B, manufactured by HORIBA, Ltd.). The anion-modified cellulose fibers were thoroughly washed with ion-exchanged water until the filtrate became 200 μs / cm or less, and then dehydrated to obtain cake-shaped anion-modified cellulose fibers. The obtained 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 carboxy group content of 1.5 mmol / g. This anion-modified cellulose fiber was TCNF (acid type).

[Preparation of anion-modified cellulose fibers 3]
Preparation Example 5 (Preparation of Shortened Anion-Modified Cellulose Fiber)
The anion-modified cellulose fiber obtained in Preparation Example 4 was charged with an absolute dry mass of 1.8 g, and ion-exchanged water was added until the mass of the contents became 36 g. The mixture was then treated at 95 ° C. for 3 hours with stirring to give an aqueous suspension of the shortened anion-modified cellulose fibers. The obtained anion-modified cellulose fibers 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).

[Preparation of anion-modified cellulose fibers 4]
Preparation Example 6
After sufficiently stirring 8 g of coniferous bleached kraft pulp (manufactured by West Freder Co., Ltd., trade name: Hinton) as natural cellulose with 760 g of ion-exchanged water, TEMPO (manufactured by ALDRICH Co., Ltd., Free radical, 98) is added to the pulp 8 g. (% by mass) 0.09 g, 1.0 g of sodium bromide, and 21 g of a 5.0 mass% sodium hypochlorite aqueous solution (3.8 mmol / g with respect to 1 g of pulp) were added in this order. Using a pH stat titration with an automatic titrator (AUT-701, manufactured by DKK-TOA CORPORATION), a 0.5 M aqueous sodium hydroxide solution was added dropwise to maintain the pH at 10.5. After the reaction was carried out at a stirring speed of 200 rpm for 120 minutes (20 ° C.), the dropping of sodium hydroxide was stopped, and a suspension of anionic-modified cellulose fibers (that is, oxidized cellulose fibers) in which the anionic group was a carboxy group was prepared. Obtained.

After adding 0.01 M hydrochloric acid to the obtained suspension of anionic-modified cellulose fibers to adjust the pH to 2, a compact electric conductivity meter (LAQUAtwin EC-33B, manufactured by HORIBA, Ltd.) using ion-exchanged water. The anion-modified cellulose fibers were sufficiently washed until the electric conductivity of the filtrate was measured to 200 μs / cm or less, and then dehydration treatment was performed to obtain cake-shaped anion-modified cellulose fibers. The carboxy group content of the obtained anion-modified cellulose fiber was 1.3 mmol / g. This anion-modified cellulose fiber was TCNF (acid type).

[Preparation of thickener composition]
Example 1
The micronized anion-modified cellulose fiber dispersion obtained in Preparation Example 3 was washed 3 times with isopropyl alcohol (IPA) and then washed 3 times with Squalane to replace the solvent. The obtained gel was placed in a beaker at 66.7 g (solid content: 0.9% by mass) and 1.53 g of amino-modified silicone (corresponding to 1 equivalent with respect to the carboxy group of the anion-modified cellulose fiber) and mixed. Squalane was added to the total amount to 120 g. This mixture is stirred with a mechanical stirrer for 5 minutes at room temperature, and then treated with a high-pressure homogenizer (manufactured by Yoshida Machinery Co., Ltd., trade name: NanoVeta L-ES) at 150 MPa for 10 passes to make anionic-modified cellulose fibers amino-modified. A squalane dispersion of modified cellulose fibers in which silicone was linked via ionic bonds was obtained. This dispersion was used as a thickener composition.

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

Example 3
The anion-modified cellulose fiber dispersion obtained in Preparation Example 4 was washed 3 times with 1-methoxy-2-propanol (PGME) and subjected to solvent substitution. The obtained gel was placed in a beaker in 7.0 g (solid content 14.6% by mass) and 3.1 g of EOPO amine (corresponding to 1 equivalent with respect to the carboxy group of the anion-modified cellulose fiber) and mixed. 33.0 g of PGME was added to the total to 43 g. This solution is stirred with a mechanical stirrer at room temperature for 1 hour, and then treated with a high-pressure homogenizer (manufactured by Yoshida Machinery Co., Ltd., trade name: NanoVeta L-ES) at 150 MPa for 5 passes to give EOPO amine to anionic-modified cellulose fibers. Obtained a 1-methoxy-2-propanol dispersion of modified cellulose fibers linked via ionic bonds. This dispersion was used as a thickener composition.

Example 4
Methyl ethyl ketone (MEK) was used in place of the PGME of Example 3, and the cells were washed three times to replace the solvent. The obtained gel was placed in a beaker in 5.3 g (solid content content: 3.77% by mass) and 0.086 g of oleylamine (corresponding to 1 equivalent with respect to the carboxy group of the anion-modified cellulose fiber) and mixed therein. 20.0 g of MEK and 40.0 g of squalane were added to make a total of 65 g. This solution was stirred with a mechanical stirrer at room temperature for 1 hour, and then treated with a high-pressure homogenizer (manufactured by Yoshida Machinery Co., Ltd., trade name: NanoVeta L-ES) at 150 MPa for 5 passes. Solvents other than squalane were removed by drying the dispersion at 80 ° C. under reduced pressure to obtain 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.

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.

Example 6
The anion-modified cellulose fiber dispersion obtained in Preparation Example 5 was washed with triethylene glycol monobutyl ether (manufactured by Tokyo Chemical Industry Co., Ltd., abbreviated as "TGME") three times to replace the solvent. 11.2 g of the obtained gel (solid content content 13.4% by mass) and 2.0 g of a tetrabutylammonium hydroxide aqueous solution having a concentration of 25% by mass (corresponding to 1 equivalent with respect to the carboxy group of the anion-modified cellulose fiber). The mixture was placed in a beaker and mixed, and 16.8 g of triethylene glycol monobutyl ether was added thereto to make a total of 30 g. This solution is stirred with a mechanical stirrer at room temperature for 1 hour, and then treated with a high-pressure homogenizer (manufactured by Yoshida Machinery Co., Ltd., trade name: NanoVeta L-ES) at 150 MPa for 5 passes to give tetrabutyl to anionic-modified cellulose fibers. A triethylene glycol monobutyl ether dispersion of modified cellulose fibers in which ammonium was linked via an ionic bond was obtained. This dispersion was used as a thickener composition.

Example 7
The modifying compound used in Example 6 was mixed with 1.0 g of a tetrabutylammonium hydroxide aqueous solution having a concentration of 25% by mass (corresponding to 0.5 equivalent with respect to the carboxy group of the anion-modified cellulose fiber) and 2.0 g of EOPO amine (corresponding to 0.5 equivalent with respect to the carboxy group of the anion-modified cellulose fiber). By performing the same operation as in Example 6 except that the amount was changed to 0.5 equivalent with respect to the carboxy group of the anion-modified cellulose fiber, tetrabutylammonium and EOPOamine were ionically bonded to the anion-modified cellulose fiber. A triethylene glycol monobutyl ether dispersion of modified cellulose fibers linked via the above was obtained. This dispersion was used as a thickener composition.

Example 8
By performing the same operation as in Example 7 except that the modifying compound used in Example 7 was changed to EOPO amine (corresponding to 1 equivalent with respect to the carboxy group of the anion-modified cellulose fiber), the anion-modified cellulose was performed. A TGME dispersion of modified cellulose fibers in which EOPO amines were linked to the fibers via ionic bonds was obtained. This dispersion was used as a thickening composition.

Example 9
A TGME dispersion of modified cellulose fibers was obtained in the same manner as in Example 3 except that the PGME of the solvent used in Example 3 was replaced with TGME. This dispersion was used as a thickening composition. The concentration of the modified cellulose fiber (that is, the solid content) in the thickening composition was set to the value shown in Table 1-1.

Example 10
1.38 g (solid content content 18.5% by mass) of the cake-shaped anion-modified cellulose fiber obtained in Preparation Example 6 was put into a beaker, and 50 g of ion-exchanged water and 0.66 g of EOPO amine (anion-modified) were added thereto. (Equivalent to 1 equivalent to the carboxy group of the cellulose fiber) was added and mixed to make a total of 52 g. This solution was stirred with a mechanical stirrer at room temperature for 1 hour, and then treated with a high-pressure homogenizer (manufactured by Yoshida Machinery Co., Ltd., trade name: NanoVeta L-ES) at 100 MPa for 1 pass. Then, 50 g of TGME was added, and the mixture was further stirred at 100 MPa for 1 pass treatment. Solvents other than TGME were removed by drying this dispersion at 80 ° C. under reduced pressure to obtain a TGME dispersion of modified cellulose fibers in which EOPOamine was linked to anion-modified cellulose fibers via ionic bonds. This dispersion was used as a thickener composition.

The modifying compounds used in the above examples and the like are as follows.
Amino-modified silicone (manufactured by Toray Dow Corning Co., Ltd., BY16-209)
EOPO Amine (Made by Huntsman, USA, Jeffamine M2070, PO / EO (molar ratio) = 10/31)
Oleylamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
25% by mass tetrabutylammonium hydroxide solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
Amino-modified silicone has a silicone chain as a modifying group, EOPOamine has an alkylene oxide chain ((EO / PO) copolymer) as a modifying group, and oleylamine and tetrabutylammonium hydroxide have a hydrocarbon group as a modifying group. Provide to the fiber.

[Preparation of Small Molecule Thickener Composition]
Comparative Example 1
To a vial, add 0.05 g (0.5% by mass) of lithium 12-hydroxystearate (manufactured by Katsuta Kako Co., Ltd.) as a thickener to 10 g of squalane and heat in a block heater heated to 205 ° C. -The thickener was dissolved by stirring. This was allowed to cool at room temperature to obtain a small molecule thickener composition of Comparative Example 1.

Comparative Example 2
Fatty acid Amide S (manufactured by Kao Corporation) is added to a vial as a thickener by adding 1.0 g (5% by mass) to 20 g of TGME, and the thickener is heated and stirred in a block heater heated to 90 ° C. Was dissolved. This was allowed to cool at room temperature to obtain a small molecule thickening composition of Comparative Example 2.

Comparative Example 3
A 2% by mass aqueous dispersion of unmodified cellulose fibers (Sugino Machine Limited, BiNFi-s, WFo-10002 (average fiber diameter 10 to 50 nm)) was washed once with 1-methoxy-2-propanol (PGME). After that, it was washed with methyl ethyl ketone (MEK) three times to replace the solvent. 3.3 g (solid content content 4.6% by mass), 5 g of PGME and 30 g of MEK were added to the beaker of the obtained mixture, and 40.0 g of squalane was further added to make a total of 78 g. This solution was stirred with a mechanical stirrer for 1 hour and then treated with a high-pressure homogenizer (manufactured by Yoshida Machinery Co., Ltd., trade name: NanoVeta L-ES) at 150 MPa for 5 passes to obtain an unmodified cellulose fiber dispersion.

PGME / MEK was removed from the dispersion using an evaporator (80 ° C., 2 hours) to obtain a squalane dispersion containing unmodified cellulose fibers. In the step of removing PGME / MEK, the unmodified cellulose fibers aggregated and separated into a liquid and an aggregate. Therefore, evaluation such as viscosity measurement could not be performed.

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 in Comparative Example 3. The obtained mixture was added to a beaker in an amount of 7.6 g (solid content: 2.7% by mass) and 40.0 g of DMF to make a total of 48 g. This solution is stirred with a mechanical stirrer for 1 hour and then treated with a high-pressure homogenizer (manufactured by Yoshida Machinery Co., Ltd., trade name: NanoVeta L-ES) at 150 MPa for 5 passes to obtain a DMF dispersion of unmodified cellulose fibers. rice field. Although it was possible to measure the viscosity of this dispersion at 25 ° C, it was not possible to measure the viscosity at 80 ° C because the liquid and agglomerates were separated.

Comparative Example 5
After sufficiently stirring 20 g of the cake-like anion-modified cellulose fiber (solid content content 26.1% by mass) obtained in Preparation Example 4 with 250 g of ion-exchanged water, a compact pH meter (Co., Ltd.) In the pH measurement of the filtrate by HORIBA, Ltd. (LAQUATWIN-PH-11B), an aqueous sodium hydroxide solution was added until the pH reached 7.0 to obtain anion-modified cellulose fibers having Na-substituted carboxy group terminals. The obtained Na-substituted anionic-modified cellulose fiber aqueous dispersion was washed with DMF three times to perform solvent substitution.

5.0 g (solid content content: 3.0% by mass) and 25.0 g of DMF were added to the beaker to make a total of 30 g of the obtained composition. This solution is stirred with a mechanical stirrer for 1 hour, and then treated with a high-pressure homogenizer (manufactured by Yoshida Machinery Co., Ltd., trade name: NanoVeta L-ES) at 150 MPa for 5 passes to obtain a DMF dispersion of Na-type anion-modified cellulose fibers. Obtained. Although it was possible to measure the viscosity of this dispersion at 25 ° C, it was not possible to measure the viscosity at 80 ° C because the liquid and agglomerates were separated.

[Rheometer evaluation of thickener composition]
The viscosity of the thickener composition was evaluated by measuring the viscosity using a rheometer (Physica MCR300, manufactured by Anton Paar). The measuring jig uses a cone type jig CP50-1 (rotation axis compliance is 4.5 x ^10-7 m / N), and the measurement conditions are the shear rate of 0.001 to ^{1000 s -1 for} the first time and 1000 to 1000 for the second time. Measurements were made under the conditions of 0.001s ^-1 and 0.001 to 1000s ^{-1 for the third time, and the viscosity at each temperature at a shear rate of 1.0s -1} was compared at the time of the third measurement from the viewpoint of viscosity stability. bottom.
As a reference example, the viscosity of each non-aqueous solvent itself was also measured by the same method.

The composition and results of each example are shown in Table 1-1, Table 1-2, Table 2-1 and Table 2-2.

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

Example 11
2.5 g of the TGME dispersion prepared in Example 8 and 10 g of the inorganic powder were added to the vial, and the mixture was stirred with a spatula for 2 minutes. Then, the mixture was stirred at 2200 rpm for 10 minutes using Awatori Rentaro (ARE-310, manufactured by Shinky Co., Ltd.). Then, the paste was stirred with a spatula to prepare an inorganic powder-containing paste.
The prepared inorganic powder-containing paste was added dropwise (25 ° C.) on a slide glass using a micropipette. The slide glass was placed on a hot plate heated to 120 ° C. and 200 ° C. and heated for 1 minute. Then, the diameter of the spread of the inorganic powder of each paste was measured by observation with an optical microscope, and the area ratio of the inorganic powder-containing paste before and after heating was evaluated. At the time of measurement at 200 ° C., TGME was almost completely removed by volatilization. The results are shown in Table 4.

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

Reference example 6
An inorganic powder-containing paste was prepared in the same manner as in Example 11 except that the TGME dispersion used in Example 11 was changed to TGME. Then, the same evaluation as in Example 11 was performed. The results are shown in Table 4.

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

From Tables 1 to 2, it was found that in Examples 1 to 4 and 8 to 10, the decrease in viscosity at 80 ° C. was suppressed as compared with the viscosity at 25 ° C. From FIGS. 1 and 2, it was found that the composition of the example of the present application exhibited a stable thickening effect in a wide temperature range as compared with the composition of the comparative example.
The same effect was confirmed in the modified cellulose fibers in which the fibers were shortened (Examples 5 to 7). From these results, it was found that the thickener composition of the present invention is a thickener composition that can be used at a temperature exceeding 50 ° C.
From Table 4, it was found that Example 11 containing the inorganic compound did not reduce the viscosity even at a high temperature because of the high-temperature thickening of the non-aqueous solvent, that is, the inorganic compound did not spread.
From these results, it can be seen that the composition of the present invention is useful as a composition for applications involving processing at 50 ° C. or higher, for example, for electronic materials, optical materials, or structural materials.

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 automobiles.

Claims (23)

1. A thickener composition containing modified cellulose fibers and a non-aqueous solvent and used at 50 ° C. or higher.
   The modified cellulose fiber is one or more selected from the group consisting of the following (1) and (2), and is a thickener composition.
   (1) It has an I-type crystal structure in which a modifying group is bonded to a cellulose fiber, and the modifying group is (a) a hydrocarbon group, (b) a silicone chain, and (c) an alkylene oxide chain. Those containing one or more selected from the group consisting of (2) Acid-type anion-modified cellulose fibers having an I-type crystal structure
2. The thickener composition according to claim 1, wherein the viscosity ratio at 80 ° C./25 ° C. is 0.6 or more.
3. The thickener composition according to claim 1 or 2, wherein the cellulose fiber in the above (1) is an anion-modified cellulose fiber.
4. The thickener composition according to claim 3, wherein the modifying group is bonded to the anionic group of the anionic-modified cellulose fiber via an ionic bond and / or a covalent bond.
5. Claimed that the alkylene oxide chain is one or more (co) polymerized parts selected from the group consisting of an ethylene oxide (EO) polymerized part, a propylene oxide (PO) polymerized part, and a (EO / PO) copolymerized part. Item 3. The thickener composition according to any one of Items 1 to 4.
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 for electronic materials, optical materials, or structural materials.
10. The thickener composition according to any one of claims 1 to 9, further comprising an inorganic compound.
11. A viscosity control agent for a non-aqueous solvent containing one or more modified cellulose fibers selected from the group consisting of the following (1) and (2).
    (1) It has an I-type crystal structure in which a modifying group is bonded to a cellulose fiber, and the modifying group is (a) a hydrocarbon group, (b) a silicone chain, and (c) an alkylene oxide chain. Those containing one or more selected from the group consisting of (2) Acid-type anion-modified cellulose fibers having an I-type crystal structure
12. The viscosity control agent according to claim 11, further comprising an inorganic compound.
13. The viscosity control agent according to claim 11 or 12, which is used at 50 ° C. or higher.
14. The viscosity control agent according to any one of claims 11 to 13, wherein the viscosity ratio at 80 ° C./25 ° C. is 0.6 or more.
15. The viscosity control agent according to any one of claims 11 to 14, wherein the viscosity ratio at 120 ° C./25 ° C. is 0.6 or more.
16. 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) It has an I-type crystal structure in which a modifying group is bonded to a cellulose fiber, and the modifying group is (a) a hydrocarbon group, (b) a silicone chain, and (c) an alkylene oxide chain. Those containing one or more selected from the group consisting of (2) Acid-type anion-modified cellulose fibers having an I-type crystal structure
17. The use according to claim 16, wherein the viscosity ratio at 80 ° C./25 ° C. is 0.6 or more.
18. The use according to claim 16 or 17, wherein the viscosity ratio at 120 ° C./25 ° C. is 0.6 or more.
19. The use according to any one of claims 16 to 18, which is used in a temperature range of 50 ° C. or higher.
20. The use according to any one of claims 16 to 19, which is used in a temperature range of 100 ° C. or higher.
21. The use according to any one of claims 16 to 20, which removes a non-aqueous solvent.
22. The use according to any one of claims 16 to 21, wherein the thickener composition further contains an inorganic compound.
23. A composition containing one or more modified cellulose fibers selected from the group consisting of the following (1) and (2), a non-aqueous solvent and an inorganic compound is heated to 100 ° C. or higher to obtain a non-aqueous solvent. A method of applying an inorganic compound, which comprises a step of removing.
    (1) It has an I-type crystal structure in which a modifying group is bonded to a cellulose fiber, and the modifying group is (a) a hydrocarbon group, (b) a silicone chain, and (c) an alkylene oxide chain. Those containing one or more selected from the group consisting of (2) Acid-type anion-modified cellulose fibers having an I-type crystal structure

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