TW202202569A - Tackifier composition - Google Patents

Abstract

The present invention relates to a tackifier composition, which contains modified cellulose fibers and a non-aqueous solvent and is used at a temperature of 50°C or higher, wherein the modified cellulose fibers are selected from the following (1) and ( 2) One or more of the group formed. (1) A type I crystal structure formed by bonding a modifying group to a cellulose fiber, and the modifying group contains a group selected from (a) a hydrocarbon group, (b) a polysiloxane chain, and (c) an alkylene oxide chain One or more of the formed group; (2) Acid-type anion-modified cellulose fibers with I-type crystal structure. The viscosity-increasing agent composition containing a non-aqueous solvent of the present invention can also suppress a decrease in viscosity at a high temperature of 50° C. or higher.

Description

Tackifier composition

The present invention relates to a tackifier composition, a viscosity control agent for a non-aqueous solvent, use of the tackifier composition, and a coating method of an inorganic compound.

In recent years, attention has been paid to a technology with less load on the environment, and in this technical background, a material using cellulose fibers, which are naturally and abundantly present as a biomass material, has attracted attention. For example, Patent Document 1 discloses a fine cellulose fiber composite dispersion containing a fine cellulose fiber composite in which an amine is ionically bonded to an anionic group of an anionic modified cellulose fiber containing an anionic group body, dispersant, and organic liquid compounds. In addition, Patent Document 2 discloses a method for producing a gel-like composition comprising: after dispersing cellulose having a cellulose I-type crystal structure in water, converting the hydroxyl group of the cellulose into a substituent having a carboxyl group steps; the step of replacing the water used as the dispersion medium of the above-mentioned cellulose with an organic solvent; the step of hydrophobizing the cellulose after the above-mentioned dispersing medium is replaced; The step of dispersing a gel-like composition of cellulose nanofibers in a solvent is characterized in that the above-mentioned cellulose hydrophobization is carried out by neutralization reaction using polyetheramine.

Patent Document 1 describes the dispersibility of cellulose fibers to 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. In these documents, there is no description about the change of viscosity properties at high temperature. prior art literature Patent Literature

Patent Document 1: Japanese Patent Laid-Open No. 2019-119867 Patent Document 2: Japanese Patent Laid-Open No. 2017-19896

The present invention relates to the following [1] to [7]. [1] A tackifier composition containing modified cellulose fibers and a non-aqueous solvent and used at a temperature of 50° C. or higher, The said modified cellulose fiber is 1 or more types chosen from the group which consists of following (1) and (2). (1) A type I crystal structure formed by bonding a modifying group to a cellulose fiber, and the modifying group contains a group selected from (a) a hydrocarbon group, (b) a polysiloxane chain, and (c) an alkylene oxide chain 1 or more of the group formed (2) Acid-type anion-modified cellulose fibers with I-type crystal structure [2] The tackifier composition according to the above [1], which is used for electronic materials, optical materials or structural materials. [3] The tackifier composition according to the above [1] or [2], further comprising an inorganic compound. [4] A viscosity control agent for a non-aqueous solvent, comprising at least one modified cellulose fiber selected from the group consisting of the following (1) and (2). (1) A type I crystal structure formed by bonding a modifying group to a cellulose fiber, and the modifying group contains a group selected from (a) a hydrocarbon group, (b) a polysiloxane chain, and (c) an alkylene oxide chain 1 or more of the group formed (2) Acid-type anion-modified cellulose fibers with I-type crystal structure [5] The viscosity control agent according to the above [4], further comprising an inorganic compound. [6] Use of a tackifier composition containing at least one modified fiber selected from the group consisting of the following (1) and (2) at a temperature of 50° C. or higher Fiber and non-aqueous solvents. (1) A type I crystal structure formed by bonding a modifying group to a cellulose fiber, and the modifying group contains a group selected from (a) a hydrocarbon group, (b) a polysiloxane chain, and (c) an alkylene oxide chain 1 or more of the group formed (2) Acid-type anion-modified cellulose fibers with I-type crystal structure [7] A method for coating an inorganic compound, comprising: a modified cellulose fiber, a non-aqueous solvent, and an inorganic compound as one or more selected from the group consisting of the following (1) and (2) The step of removing the non-aqueous solvent by heating the composition to 100°C or higher. (1) A type I crystal structure formed by bonding a modifying group to a cellulose fiber, and the modifying group contains a group selected from (a) a hydrocarbon group, (b) a polysiloxane chain, and (c) an alkylene oxide chain 1 or more of the group formed (2) Acid-type anion-modified cellulose fibers with I-type crystal structure

The present invention relates to a tackifier composition suitable for a non-aqueous solvent used at a temperature of 50° C. or higher because the viscosity reduction can be suppressed even at high temperature.

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

Although the detailed mechanism of the tackifier composition of the present invention is not clear, it is presumed as follows: the cellulose fibers introduced with the hydrophobic modified group are uniformly dispersed in the non-aqueous solvent and form a relaxed network structure, thereby allowing the It shows stickiness maintenance effect.

<Tackifier composition> The tackifier composition of the present invention contains modified cellulose fibers and a non-aqueous solvent, and is used at a temperature of 50°C or higher.

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

(1) A type I crystal structure formed by bonding a modifying group to a cellulose fiber, and the modifying group contains a group selected from (a) a hydrocarbon group, (b) a polysiloxane chain, and (c) an alkylene oxide chain One or more of the group formed. (2) Acid-type anion-modified cellulose fibers with an I-type crystal structure. In addition, in this specification, the modified cellulose fibers of the above (1) are referred to as "modified cellulose fibers (1)", and the modified cellulose fibers of the above (2) are referred to as "modified cellulose fibers (1)" when it is necessary to distinguish them. The fibers are called "modified cellulose fibers (2)".

Modified Cellulose Fiber(1) The modified cellulose fibers (1) are obtained by bonding a modifying group to the cellulose fibers. The cellulose fiber is preferably anion-modified cellulose fiber from the viewpoint of the easiness of bonding of modifying groups.

(Anionic-modified cellulose fibers) Anionic-modified cellulose fibers are those having an anionic group in the molecule, for example, one or more groups selected from the group consisting of a carboxyl group, a ()phosphorous acid group, and a sulfonic acid group. Cellulose fibers. The introduction of anionic groups into cellulose fibers can be achieved by the following method. From the viewpoints of availability and effect, anionically modified cellulose fibers having a carboxyl group as an anionic group are preferred, and the group at the C6 position (-CH ₂ OH) constituting the glucose unit of the cellulose fibers is more preferred. Anionically modified cellulose fibers (referred to as "oxidized cellulose fibers") selectively converted to carboxyl groups. Furthermore, the counter ion (counter ion) of the anionic group is preferably a proton.

The anionic group content in the anionically modified cellulose fiber is preferably 0.1 mmol/g or more, more preferably 0.4 mmol/g or more, and still more preferably 0.6 mmol/g, from the viewpoint of stably introducing the modifying group. g or more, more preferably 0.7 mmol/g or more, still more preferably 0.8 mmol/g or more. Also, from the viewpoint of improving workability, 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, and further Preferably it is 2.0 mmol/g or less, More preferably, it is 1.9 mmol/g or less. In addition, the "anionic group content" means the total amount of anionic groups in glucose constituting the cellulose fiber, and specifically, it was measured by the method described in the following examples.

Although the preferred ranges of the average fiber diameter and average fiber length of the anionically modified cellulose fibers are also affected by the order of the production steps, they are preferably equal to those of the raw cellulose fibers.

The term "modifying group bonded to an anionic group of the anionically modified cellulose fiber" means that the modified group is bonded to an anionic group, preferably a carboxyl group, which the anionically modified cellulose fiber has. An ionic bond and/or a covalent bond can be mentioned as a bonding form of a modifying group and an anionic group. As a covalent bond, an amide bond, an ester bond, and a urethane bond are mentioned, for example; Preferably, an amide bond is mentioned.

(modifying group) As a modification group, (a) hydrocarbon group, (b) polysiloxane chain, and (c) alkylene oxide chain are mentioned. These modifying groups may be bound (introduced) to cellulose fibers alone or in combination of two or more.

(a) Hydrocarbon group The hydrocarbon group may, for example, be a monovalent hydrocarbon group such as a chain saturated hydrocarbon group, a chain unsaturated hydrocarbon group, a cyclic saturated hydrocarbon group, and an aromatic hydrocarbon group.

The number of carbon atoms in the hydrocarbon group is 1 or more, preferably 3, 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 simply referred to as high temperature). Above, 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 the following substituents, or 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 include propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, and isobutyl group. , pentyl, third pentyl, isopentyl, hexyl, isohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, tridecyl, tetraethyl, Tetrabutyl, tetrapropyl, tetradecyl, octadecyl, behenyl, octadecyl, etc.

The chain unsaturated hydrocarbon group is preferably one having 3 or more carbon atoms and 30 or less carbon atoms, and specific examples thereof include propenyl, butenyl, isobutenyl, isopentenyl, pentenyl, and hexenyl. , heptenyl, octenyl, nonenyl, decenyl, dodecenyl, tridecenyl, tetradecenyl, octadecenyl.

The cyclic saturated hydrocarbon group is preferably one having 3 to 20 carbon atoms, and specific examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, Cyclononyl, cyclodecyl, cyclododecyl, cyclotridecyl, cyclotetradecyl, cyclooctadecyl, etc.

As an aromatic hydrocarbon group, an aryl group, an aralkyl group, etc. are mentioned, for example. As the aryl group and the aralkyl group, the aromatic ring itself may be substituted, or it may be unsubstituted. As a heterocyclic aromatic hydrocarbon group, an imidazolyl group is mentioned.

The total carbon number of the aryl group is preferably 6 or more and 24 or less. Specific examples of the aryl group include, for example, phenyl, naphthyl, anthracenyl, phenanthryl, biphenyl, triphenyl, and bitriphenyl. group, and the group after these groups are substituted with a substituent.

The total carbon number of the aralkyl group is preferably 7 or more and 24 or less. Specific examples of the aralkyl group include benzyl, phenethyl, phenylpropyl, phenylpentyl, phenylhexyl, Phenylheptyl, phenyloctyl, and aromatic groups of these groups are substituted with substituents, and the like. The total carbon number of the imidazolyl group is preferably 3 or more and 24 or less. Specific examples of the imidazolyl group include, for example, imidazolyl, methylimidazolyl, ethylimidazolyl, propylimidazolyl, and 2-phenylimidazole. group, benzimidazolyl group, and the group after these groups are substituted by substituents, etc.

(b) polysiloxane chain The so-called polysiloxane chain uses a siloxane bond as one of the valent groups of the main chain, and may be further accompanied by an alkylene group. The polysiloxane chain may further have the following substituents.

(c) Alkylene oxide chain The alkylene oxide chain refers to the structure of a (co)polymer containing ethylene oxide (EO) or propylene oxide (PO), and is preferably selected from the structure of a polymer containing EO (EO polymerization part), a polymer containing One or more of the group consisting of the structure of the polymer of PO (PO polymerization part) and the structure ((EO/PO) copolymerization part) of the copolymer containing EO and PO randomly or in block form (Co)polymerization section. The alkylene oxide chain may further have the following substituents.

As the alkylene oxide chain, for example, the following formula can be exemplified:

[hua 1]

(In the formula, R ¹ represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a -CH ₂ CH(CH ₃ )NH ₂ group; EO and PO exist randomly or in blocks, and a represents EO The average added mole is 0 or a positive number, and b represents a 0 or a positive number of the average added mole of PO; where a and b are both 0 except for the case) represented by a valence base.

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

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

Specific examples of the hydrocarbon group in which R ¹ in the above formula is 1 or more and 6 or less carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, 3-butyl base, isobutyl, pentyl, third pentyl, isopentyl, hexyl and isohexyl, etc.

The formula weight (molecular weight) of the alkylene oxide chain is preferably 500 or more, more preferably 1,000 or more, and from the same viewpoint, preferably 10,000 or less, more preferably 7,000 or less. The formula weight of the alkylene oxide chain can be calculated and obtained from the average added mole number at the time of producing the following amine compound having an alkylene oxide chain.

The PO content (mol%) in the (EO/PO) copolymerization part is preferably 1 mol% or more, more preferably 5 mol% or more, from the viewpoint of suppressing viscosity reduction even at high temperatures, and the same From a viewpoint, it is preferably 100 mol % or less, more preferably 95 mol % or less, and still more preferably 90 mol % or less. The content rate of PO in the (EO/PO) copolymerization part can be calculated and calculated|required from the average added mole number at the time of manufacture of the amine compound which has the following alkylene oxide chain.

(d) other substituents In addition, the modifying group may further have a substituent. As a substituent, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a 2nd butoxy group, a 3rd butoxy group, and a pentyloxy group may, for example, be mentioned. , isopentyloxy, hexyloxy and other alkoxy groups with 1 to 6 carbon atoms; methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxy An alkoxy-carbonyl group whose carbon number is 1 to 6 in an alkoxy group such as carbonyl, second butoxycarbonyl, third butoxycarbonyl, pentyloxycarbonyl, and isopentyloxycarbonyl; fluorine atom, chlorine atom, Halogen atoms such as bromine atom and iodine atom; Acetyl, propionyl and other acyl groups with 1 to 6 carbon atoms; aralkyl groups; aralkyloxy groups; alkylamine groups with 1 to 6 carbon atoms; Dialkylamine group with carbon number of 1 to 6; hydroxyl group.

[Manufacturing method of modified cellulose fiber (1)] The modified cellulose fiber (1) can be produced, for example, by introducing an anionic group into the cellulose fiber of the raw material to produce an anionically modified cellulose fiber (step 1); then, bonding the modifying group to the anionically modified cellulose fiber Anionic groups of cellulose fibers (step 2).

(step 1) Cellulose fiber as raw material The cellulose fiber used as the raw material of the anion-modified cellulose fiber is preferably natural cellulose in terms of the environment, for example, wood pulp such as conifer pulp, hardwood pulp, etc.; cotton pulp such as cotton linters and cotton linters Paper pulp; non-wood pulp such as straw pulp and bagasse pulp; bacterial cellulose, etc.; these can be used alone or in combination of two or more.

The average fiber diameter of the cellulose fibers of the raw material is not particularly limited, but from the viewpoints of workability and cost, it is preferably 5 μm or more, more preferably 7 μm or more, and from the same viewpoint, preferably 500 μm or less , more preferably 300 μm or less. The average fiber diameter of the cellulose fibers of the raw material was determined by the method described in the following examples.

In addition, the average fiber length of the cellulose fibers of the raw material is not particularly limited, but from the viewpoints of availability and cost, it is preferably 5 μm or more, more preferably 25 μm or more, and from the same viewpoint, preferably 5,000 μm or less, more preferably 3,000 μm or less. The average fiber length of the raw cellulose fibers can be measured according to the method described in the following examples.

Approach (1) Introducing a carboxyl group as an anionic group into a cellulose fiber As a method of introducing carboxyl groups into cellulose fibers, for example: a method of oxidizing hydroxyl groups of cellulose fibers and converting them into carboxyl groups; or introducing an acid anhydride selected from compounds having carboxyl groups, compounds having carboxyl groups, and the like. A method for reacting at least one of the group consisting of derivatives with hydroxyl groups of cellulose fibers.

As a method of oxidizing the hydroxyl groups of cellulose fibers, for example, the method described in Japanese Patent Laid-Open No. 2015-143336 or Japanese Patent Laid-Open No. 2015-143337, that is, 2, 2, 6, 6-Tetramethyl-1-piperidine-N-oxygen radical (TEMPO) is used as a catalyst to react an oxidizing agent such as sodium hypochlorite and a bromide such as sodium bromide with the raw cellulose fibers. Using TEMPO as a catalyst to oxidize cellulose fibers, the C6 group of glucose in the structural unit of cellulose fibers can be selectively converted into carboxyl groups to obtain the above oxidized cellulose fibers.

The compound having a carboxyl group for introducing a carboxyl group into the cellulose fiber is not particularly limited, and specifically, halogenated acetic acid may be mentioned. As halogenated acetic acid, chloroacetic acid etc. are mentioned.

The acid anhydride of a compound having a carboxyl group for introducing a carboxyl group into cellulose fibers and derivatives thereof are not particularly limited, and examples thereof include maleic anhydride, succinic anhydride, phthalic anhydride, adipic anhydride, and the like. The acid anhydride of the dicarboxylic acid compound or the imidate of the acid anhydride of the compound having a carboxyl group, and the derivative of the acid anhydride of the compound having a carboxyl group. These compounds may also be substituted with hydrophobic groups.

(2) Introducing a sulfonic acid group or a ()phosphorous acid group as an anionic group into a cellulose fiber As a method of introducing a sulfonic acid group into the cellulose fiber, a method of adding sulfuric acid to the cellulose fiber and heating it, etc. may be mentioned.

As a method of introducing a ()phosphorous acid group into a cellulose fiber, a method of mixing a powder or an aqueous solution of ()phosphorous acid or a ()phosphorous acid derivative into a dry state or a wet state of the cellulose fiber; A method of adding an aqueous solution of ()phosphorous acid or a ()phosphorous acid derivative to a dispersion of cellulose fibers, etc. In the case of adopting these methods, dehydration treatment, heat treatment, etc. are usually performed after mixing or adding a powder or aqueous solution of ()phosphorous acid or a ()phosphorous acid derivative.

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

(1) Introduced via ionic bond In the case of introducing the modifying group via ionic bond, the anion-modified cellulose fiber and the compound for modification may be mixed, whereby the anion-modified cellulose fiber contained in the An ionic bond is formed between the anionic group and the amine group of the compound for modification. Specifically, when oxidized cellulose fibers are used as the anionically modified cellulose fibers and a primary amine having the above-mentioned modifying groups is used as the compound for modification, the above-mentioned modifying groups can be introduced into the constituent fibers via ionic bonds as shown in the following formula The carboxyl group at the C6 position of the glucose of the cellulose fiber (in the formula, ^C6 is the carbon atom at the 6 position of the glucose constituting the cellulose fiber, and R is a modification group).

[hua 2]

compound for modification As the modification compound used in this aspect, any desired modification group can be introduced, and preferably, amine compounds, phosphonium compounds, or guanidine-containing compounds having the above-mentioned hydrocarbon groups, alkylene oxide chains or polysiloxane chains are exemplified. base compounds, etc.

Amine compounds 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 polysiloxane chain as a modifying group, and the hydrocarbon group or the like is introduced into the anionically modified cellulose fiber through an ionic bond to become a modified cellulose fiber. Modified base.

As the amine compound, any of a primary amine, a secondary amine, a tertiary amine, and a quaternary ammonium compound may be used. Preferred examples of the anion component of the quaternary ammonium compound include halogen ions such as chloride ions and bromide ions, hydrogen sulfate ions, perchloric acid ions, tetrafluoroborate ions, and hexafluorophosphoric acid from the viewpoint of reactivity. radical ion, trifluoromethanesulfonic acid ion, hydroxyl ion.

Amine compounds with hydrocarbon groups Specific examples of the amine compound having a hydrocarbon group include primary to tertiary amines such as ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, butylamine, dibutylamine, hexylamine, 2- Ethylhexylamine, dihexylamine, trihexylamine, octylamine, dioctylamine, trioctylamine, dodecylamine, di-dodecylamine, stearylamine, distearylamine, monoethanolamine, diethanolamine , triethanolamine, oleylamine, aniline, octadecylamine, dimethyl behenamine, benzylamine, naphthylamine, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl yl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-(3-aminopropyl)imidazole, etc. As a quaternary ammonium compound, for example, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetraethylammonium chloride, tetrapropylammonium hydroxide (TPAH), hydroxide Tetrabutylammonium (TBAH), Tetrabutylammonium Chloride, Lauryl Trimethyl Ammonium Chloride, Dilauryl Dimethyl Chloride, Stearyl Trimethyl Ammonium Chloride, Distearyl Dimethyl Chloride Methylammonium, cetyltrimethylammonium chloride, alkylbenzyldimethylammonium chloride.

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

Amine compounds with alkylene oxide chains The alkylene oxide chain in the amine compound and the nitrogen atom of the amine compound are preferably directly bonded or bonded via a linking group. The linking group is preferably a hydrocarbon group, and an alkylene group having preferably 1 or more and 6 or less, more preferably 1 or more and 3 or less carbon atoms may be mentioned. As the alkylene group, for example, ethylidene and propylidene are preferable.

As an amine which has an alkylene oxide chain, the compound represented by following formula (i) is mentioned, for example.

[hua 3]

R ¹ , a and b in the formula (i) are the same as R ¹ , a and b in the formula representing an example of the above alkylene oxide chain.

The amine compound having an alkylene oxide chain can be prepared according to a known method. For example, a desired amount of ethylene oxide and propylene oxide may be added to propylene glycol alkyl ether, and then the hydroxyl end may be aminated. The alkyl ether may optionally be cleaved with an acid, thereby making the terminal a hydrogen atom. For these production methods, refer to Japanese Patent Laid-Open No. 3-181448, and the details of the amine compound are described in, for example, Japanese Patent No. 6105139.

As the amine compound having an alkylene oxide chain, for example, commercially available products can be preferably used. Specific examples include Jeffamine M-2070, Jeffamine M-2005, Jeffamine M-2095, Jeffamine M-1000, Jeffamine M-600, Surfoamine B200, Surfoamine L100, Surfoamine L200, Surfoamine L207, Surfoamine L300, Surfoamine B-100, XTJ-501, XTJ-506, XTJ-507, XTJ-508, M3000, Jeffamine ED-900, Jeffamine ED -2003, Jeffamine D-2000, Jeffamine D-4000, XTJ-510, Jeffamine T-3000, 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, etc. These can be used individually or in combination of 2 or more types.

Amine compounds with polysiloxane chains The amine compound may, for example, have a structure in which an amine group is bonded to a skeleton of a polysiloxane chain through an alkylene group or the like. In this specification, this amine compound may be called "amine group-modified polysiloxane". The amine group-modified polysiloxane can be prepared by using a commercially available product or according to a known method. Only one type of amino-modified polysiloxane may be used, or two or more types may be used.

As the amine group-modified polysiloxane, in terms of performance, TSF4703 (kinematic viscosity: 1000, amine group equivalent: 1600) and TSF4708 (kinematic viscosity: 1000, amine group equivalent: 2800), SS-3551 (kinematic viscosity: 1000, amine group equivalent: 1600), SF8457C (kinematic viscosity: 1200, amine group equivalent: 1800) manufactured by Dow Corning Toray Silicone (stock), SF8417 (kinematic viscosity: 1200, amine group) Base equivalent: 1700), BY16-209 (Kinematic viscosity: 500, Amine equivalent: 1800), BY16-892 (Kinematic viscosity: 1500, Amine equivalent: 2000), BY16-898 (Kinematic viscosity: 2000, Amine equivalent: 2000) : 2900), FZ-3760 (kinematic viscosity: 220, amine group equivalent: 1600), KF8002 (kinematic viscosity: 1100, amine group equivalent: 1700) manufactured by Shin-Etsu Chemical Co., Ltd., KF867 (kinematic viscosity: 1300, amine group) Base equivalent: 1700), KF-864 (Kinematic viscosity: 1700, Amine equivalent: 3800), BY16-213 (Kinematic viscosity: 55, Amine equivalent: 2700), BY16-853U (Kinematic viscosity: 14, Amine equivalent: 2700) : 450). In ( ), kinematic viscosity indicates the measured value at 25°C (unit: mm ² /s), and the unit of amine group equivalent is g/mol.

Guanidine-containing compounds 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 polysiloxane chain as a modifying group, and the hydrocarbon group or the like is introduced into the anionically modified cellulose fiber through an ionic bond to become a modified fiber. Modifiers in cellulose fibers. As a guanidine group-containing compound, diphenylguanidine, xylylguanidine, 1,2,3-triphenylguanidine, aminoguanidine, and arginine may, for example, be mentioned.

reaction conditions, etc. The amount of the modification compound to be used is preferably 0.01 mol or more of the amine group in the modification compound, more preferably 0.01 mol or more, with respect to 1 mol of the carboxyl group contained in the oxidized cellulose fiber from the viewpoint of reactivity. 0.1 mol or more, more preferably 0.5 mol or more, more preferably 0.7 mol or more, more preferably 1 mol or more, and from the viewpoint of product purity, preferably The amount is 50 mol or less, more preferably 20 mol or less, and still more preferably 10 mol or less. When the compound for modification has a plurality of amine groups, it is used so that the total number of moles of the amino groups becomes the above-mentioned number of moles.

Solvents are preferably used for mixing. As the solvent, it is preferable to select a solvent for dissolving the compound to be used, and examples thereof include methanol, ethanol, isopropanol (IPA), N,N-dimethylformamide (DMF), dimethylmethylene Dust (DMSO), N,N-dimethylacetamide, tetrahydrofuran (THF), acetone, methyl ethyl ketone (MEK), cyclohexanone, ethyl acetate, acetonitrile, dichloromethane, chloroform, toluene, Acetic acid, 1-methoxy-2-propanol (PGME), water, etc.; these can be used alone or in combination of two or more.

From the viewpoint of the reactivity of the compound, the temperature during mixing is preferably 0°C or higher, more preferably 5°C or higher, and still more preferably 10°C or higher. Moreover, from the viewpoint of suppressing the coloration of the modified cellulose fibers, it is preferably 50°C or lower, more preferably 40°C or lower, and still more preferably 30°C or lower. The mixing time can be appropriately set according to the type of the compound and solvent to be used, but from the viewpoint of the reactivity of the compound, it is preferably 0.01 hour or more, more preferably 0.1 hour or more, and from the viewpoint of productivity, it is preferably 48 hours or less, more preferably 24 hours or less.

(2) Introduced via amide bond When the modification group is introduced through an amide bond, the anion-modified cellulose fiber and the modification compound can be mixed in the presence of a known condensing agent, whereby the anion-modified cellulose fiber contained in the anion-modified cellulose fiber can be mixed. An amide bond is formed between the amine group and the amine group of the compound for modification.

Specifically, when oxidized cellulose fibers are used as the anionically modified cellulose fibers and a primary amine having the above-mentioned modifying group is used as the compound for modification, the above-mentioned modifying group can be introduced into the compound via an amide bond as shown in the following formula. The carboxyl group at the C6 position of the glucose constituting the cellulose fiber (in the formula, ^C6 is the carbon atom at the 6 position of the glucose constituting the cellulose fiber, and R is a modification group).

[hua 4]

compound for modification As the compound for modification used in this aspect, any desired modifying group may be introduced, and preferably, an amine compound having the above-mentioned hydrocarbon group, alkylene oxide chain or polysiloxane chain is exemplified.

Amine compounds 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 polysiloxane chain as a modifying group, and the hydrocarbon group or the like is introduced into the anionically modified cellulose fiber through an amide bond to become a modified cellulose fiber. the modifier base.

As an amine compound, a primary amine and a secondary amine are mentioned. Specific examples of the amine compound include the amine compound having a hydrocarbon group, the amine compound having an alkylene oxide chain, and the amine compound having a polysiloxane chain, which are exemplified in the above-mentioned "(1) Aspect of introduction via ionic bond" Middle primary amine and secondary amine.

Reaction conditions The amount of the modification compound to be used is preferably 0.05 mol or more, and more preferably 0.1 mol or more, with respect to 1 mol of the carboxyl group contained in the oxidized cellulose fiber from the viewpoint of reactivity. , and more preferably 0.2 mol or more, more 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 mol or less, more preferably 10 mol or less. When the compound for modification has a plurality of amine groups, it is used so that the total number of moles of the amino groups becomes the above-mentioned number of moles.

The condensing agent is not particularly limited, and examples thereof include those described in Peptide Synthesis (Maruzen Co., Ltd.) P116 of the Synthetic Chemical Series, or those described in Tetrahedron, 57, 1551 (2001), and examples thereof include 4-(4,6-dimethicone). Methoxy-1,3,5-tri((2-yl)-4-methylmorpholine hydrochloride (hereinafter, sometimes referred to as "DMT-MM") and the like. Moreover, the reaction may be performed only by heat treatment without using a condensing agent.

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

The reaction time and reaction temperature in the amidation reaction can be appropriately selected according to the type of the compound and solvent to be used, but from the viewpoint of the reaction rate, it is preferably 1 to 24 hours, more preferably 10 to 20 hours. Moreover, from the viewpoint of reactivity, the reaction temperature is preferably 0°C or higher, more preferably 5°C or higher, and still more preferably 10°C or higher. Moreover, 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 step) Cellulose fibers are micronized at any stage of the manufacturing method of the modified cellulose fibers (eg, before step 1, before step 2, and after step 2), whereby micro-scale cellulose fibers can be micronized into nano-scale. By reducing the average fiber diameter to nanometer size, the dispersibility in the resin is improved, which is preferable.

For the miniaturization treatment, a known miniaturization treatment method can be used. For example, in the case of obtaining modified cellulose fibers with an average fiber diameter of nanometer size, a treatment method using an attritor such as a particle attritor or a treatment method using a high-pressure homogenizer in a medium may be performed.

Examples of the medium include alcohols having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, such as water, methanol, ethanol, propanol, and 1-methoxy-2-propanol (PGME); acetone, methyl alcohol, etc. Ketones with 3 to 6 carbon atoms such as methyl ethyl ketone and methyl isobutyl ketone; ketones with 2 to 4 carbon atoms such as ethyl acetate and butyl acetate; saturated or unsaturated hydrocarbons with 1 to 6 carbon atoms; benzene Aromatic hydrocarbons such as , toluene; halogenated hydrocarbons such as chlorinated methane and chloroform; lower alkyl ethers with 2 to 5 carbon atoms; N,N-dimethylformamide (DMF), N,N-dimethylacetamide Polar solvents such as amine, dimethyl sulfoxide, etc. These can be used individually or in mixture of 2 or more types. The amount of the medium used is as long as the effective amount that can disperse the modified cellulose fibers. Compared with the modified cellulose fibers, it is more preferable to use 1 mass times or more, more preferably 2 mass times or more, and It is 500 mass times or less, more preferably 200 mass times or less.

As an apparatus used for the miniaturization treatment, in addition to a high-pressure homogenizer, a known disperser can be preferably used. For example, disintegration, beaters, low pressure homogenizers, grinders, particle attritors, choppers, ball mills, jet mills, short shaft extruders, 2 shaft extruders, ultrasonic mixers, domestic juicing mixers can be used machine etc. In addition, the solid content content of the modified cellulose fibers in the refining treatment is preferably 50% by mass or less.

(Short fiber treatment) In any stage of the production method of the modified cellulose fibers (1), the cellulose fibers may be further subjected to a short fiberization treatment, that is, a treatment of shortening the fiber length. The short fiberizing treatment can be achieved by subjecting the target cellulose fibers to one or more treatment methods selected from the group consisting of alkali treatment, acid treatment, heat treatment, ultraviolet treatment, electron beam treatment, mechanical treatment, and enzyme treatment.

Modified Cellulose Fiber(2) The modified cellulose fibers (2) are acid-type anion-modified cellulose fibers having a specific average fiber diameter. The acid-type anion-modified cellulose fiber refers to the one in which the opposite ion of the anionic group is a proton in the "anion-modified cellulose fiber" in the description of the modified cellulose fiber (1), preferably as oxidized cellulose The opposite ion of fiber and carboxyl group is proton.

The preferred range of the content of anionic groups in the modified cellulose fibers (2) is the same as the preferred range of the content of anionic groups in "anionic modified cellulose fibers" in the description of the modified cellulose fibers (1) . The modified cellulose fiber (2) can be produced by going through step 1 in "the production method of the modified cellulose fiber (1)" and then the above-mentioned "miniaturization step". The short fiberization treatment of the cellulose fibers can also be performed at any stage of the production method of the modified cellulose fibers (2).

[Properties of Modified Cellulose Fibers] The main properties of the modified cellulose fibers in the present invention are as follows.

(average fiber diameter, average fiber length) The modified cellulose fibers are preferably those subjected to a micronization process to become nano-sized. The average fiber diameter of the modified cellulose fibers in this case is preferably 1 nm or more, more preferably 2 nm or more, from the viewpoints of workability, availability, cost, and suppression of viscosity reduction even at high temperatures. From the viewpoint of properties and solvent dispersibility, it is preferably 300 nm or less, more preferably 200 nm or less, still more preferably 150 nm or less, and still more preferably 120 nm or less. The average fiber diameter of the modified cellulose fibers subjected to the miniaturization treatment was obtained by the method described in the following examples.

The average fiber length of the modified cellulose fibers is preferably 100 nm or more, more preferably 200 nm or more, from the viewpoints of workability, availability, cost, and suppression of viscosity reduction even at high temperatures. From the viewpoint that the viscosity ratio of °C/25°C is close to 1, it is preferably 10000 nm or less, and more preferably 5000 nm or less. The average fiber length of the modified cellulose fibers was determined by the method described in the following examples.

(average aspect ratio) In the present invention, the modified cellulose fibers can also be subjected to short fiberization treatment. The average aspect ratio of the modified cellulose fibers is not particularly limited, but from the viewpoint of exhibiting the effect as a thickener, it is preferably 5 or more, more preferably 10 or more, still more preferably 20 or more, and another On the other hand, from the viewpoint of availability and workability, it is preferably 300 or less, more preferably 200 or less, and still more preferably 100 or less. The average aspect ratio of the modified cellulose fibers was determined by the method described in the following examples. By using modified cellulose fibers with a small average aspect ratio, the viscosity ratio at 80°C/25°C can be made close to 1, thereby improving workability.

(The amount of bonding and the introduction rate of the modified group) From the viewpoints of dispersibility and suppression of viscosity reduction even at high temperatures, the bonding amount of the modifying groups in the modified cellulose fibers is preferably 0.01 mmol/g or more, more preferably 0.1 mmol/g or more, and from the same viewpoints. In other words, 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 as modifying groups are simultaneously introduced into the modified cellulose fibers, the bonding amount of the modifying groups is preferably within the above-mentioned range.

From the viewpoints of dispersibility and suppression of viscosity reduction at high temperatures, the introduction rate of the modifying group in the modified cellulose fibers is preferably 10 mol% or more, the higher the better, and 100 mol% more preferred. When any two or more kinds of modifying groups as modifying groups are introduced at the same time, the total introduction rate is within a range not exceeding 100 mol % of the upper limit, preferably within the above-mentioned range.

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

(Crystal structure) The modified cellulose fibers preferably have a cellulose I-type crystal structure from the viewpoint of suppressing the decrease in viscosity even at high temperatures, and from the viewpoint of the strength of the molded body of the resin composition, the crystals of the modified cellulose fibers are preferred. The chemical degree is preferably 10% or more, more preferably 15% or more, and still more preferably 20% or more. Moreover, from the viewpoint of availability of raw materials, it is preferably 90% or less, more preferably 85% or less, still more preferably 80% or less, and still more preferably 75% or less. Furthermore, in this specification, the degree of crystallinity of cellulose fibers is the degree of crystallinity of cellulose type I calculated from the diffraction intensity value obtained by the X-ray diffraction method, and can be based on the following examples. method to measure. In addition, the so-called cellulose I type refers to the crystal form of natural cellulose, and the so-called cellulose I type crystallinity refers to the ratio of the amount of crystalline domains in the entire cellulose fiber. The presence or absence of the cellulose I-type crystal structure was determined by the presence of a peak at 2θ=22.6° in X-ray diffraction measurement.

The content of the modified cellulose fibers in the composition of the present invention is, in terms of cellulose (excluding modifying groups, etc.), preferably from the viewpoint of imparting viscosity increase to the composition and suppressing a decrease in viscosity even at high temperatures 0.01 mass % or more, more preferably 0.05 mass % or more, still more preferably 0.1 mass % or more, on the other hand, from the viewpoint of the handling of the composition, preferably 50 mass % or less, more preferably 30 mass % Hereinafter, it is more preferably 20 mass % or less, more preferably 15 mass % or less, more preferably 10 mass % or less, and still more preferably 5 mass % or less. Hereinafter, the amount of modified cellulose fibers is a cellulose conversion value that does not include modification groups.

[Non-aqueous solvent] Regarding the non-aqueous solvent, from the viewpoint of using the tackifier composition of the present invention at a temperature of 50°C or higher, the melting point is preferably 100°C or lower, more preferably 50°C or lower, and still more preferably 20°C or lower, 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 used.

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

Specifically, alcohol-based solvents such as methanol, n- and isopropanol, 3-butanol, 1-butanol, 1-hexanol, hexanal, and glycerin; acetone, methyl ethyl ketone (MEK), etc. , methyl isobutyl ketone (MIBK), cyclohexanone, methyl cyclohexyl ketone, diisobutyl ketone, diacetone alcohol, isophorone and other ketone solvents; diethyl ether, tetrahydrofuran (THF), diethyl ether Ether-based solvents such as methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, polycarboxylic acid esters (such as phthalate, succinate, adipate, etc.), aliphatic polybasic such as glycerin Ester solvents such as fatty acid esters of alcohols; N,N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), ethylene carbonate, N,N-dimethylacetamide (DMAc) ), N-methylpyrrolidone and other highly polar solvents; chlorinated methane (methylene chloride), dichloromethane, chloroform, trichloroethylene, perchloroethylene, chlorobenzene and other halogen-based solvents; hexane, petroleum ether, liquid Non-aromatic hydrocarbon-based solvents such as paraffin, squalane, and squalene; aromatic hydrocarbon-based solvents such as benzene, toluene, and xylene; nitrile-based solvents such as acetonitrile; tertiary butyl glycol, methyl diethylene glycol, Ethyl diethylene glycol, butyl diethylene glycol, 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, tri, poly) ethylene glycol dimethyl (diethyl) ether, (mono, di, tri, poly) ) glycol ether-based solvents such as ethylene glycol monobutyl ether, polyethylene glycol, methoxy polyethylene glycol, polyoxyethylene bisphenol A, and polyoxypropylene bisphenol A (the glycol ether-based solvents include the following glycols Ether (ester) solvent: butyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, methoxybutyl acetate, methyl acetate Methoxybutyl ester, ethyl-3-ethoxy propionate, propylene glycol monomethyl ether propionate, glycol ether ester solvent of dimethyl carbonate); polymerizable compounds such as [epoxy prepolymer ( For example, bisphenol type, novolac type, biphenyl type, biphenyl aralkyl type, aryl alkylene type, tetraphenol ethane type, naphthalene type, anthracene type, phenoxy type, dicyclopentadiene type, norene type, adamantane type, pycnogenol type, glycidyl methacrylate copolymer system, etc.); isocyanates (such as toluene diisocyanate, diphenylmethane diisocyanate and other aromatic systems or hexamethylene diisocyanate, benzene Aliphatic systems such as dimethyl diisocyanate, isophorone diisocyanate, tetramethylxylylene diisocyanate, etc.); acrylic prepolymers (such as methyl acrylate, methyl methacrylate, ethyl acrylate, methyl acrylate, etc.) Ethyl acrylate, butyl acrylate, butyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, nonanediol diacrylate, Phenoxyethyl acrylate, (meth)acrylate of bisphenol A-alkylene oxide adduct, (meth)acrylate epoxy ester (bisphenol A type (meth)acrylate epoxy ester, novolak type (meth)acrylate epoxy ester, etc.); polyester (meth)acrylate (e.g. Aliphatic polyester (meth)acrylate, aromatic polyester (meth)acrylate, etc.); (meth)acrylate urethane (polyester (meth)acrylate urethane) , polyether (meth)acrylate urethane, etc.); polysiloxane (meth)acrylate, mono(meth)acrylate of cyanoacrylate, etc.] and oligomers of these polymerizable compounds etc.; fatty acids such as oleic acid, palmitic acid, stearic acid; olive oil, jojoba oil, castor oil and other animal/vegetable oils; polysiloxane oil, fluorine-based inert liquid, processing oil, etc. In this specification, the non-aromatic hydrocarbon-based solvent and the aromatic hydrocarbon-based solvent are collectively referred to as a hydrocarbon-based solvent.

The non-aqueous solvent preferably contains a hydrocarbon-based solvent or a glycol ether-based solvent, and among these, when the above-mentioned modifying group is (a) a hydrocarbon group and (b) a polysiloxane chain, a hydrocarbon is preferable solvent, polysiloxane oil or glycol ether solvent (including glycol ether ester solvent), in the case of (c) alkylene oxide chain, preferably hydrocarbon solvent, alcohol solvent, ether solvent, Ester-based solvents, glycol ether-based solvents (including glycol ether-based solvents), fatty acids, animal/vegetable oils, polysiloxane oils, fluorine-based inert liquids, processing oils, etc., in the case of (c) alkylene oxide chains In this case, a hydrocarbon-based solvent or a glycol ether-based solvent (including a glycol ether ester-based solvent) is more preferable, and a glycol ether-based solvent (including a glycol ether ester-based solvent) is more preferable. Moreover, in the case of an acid-type anion-modified cellulose fiber, 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 usually preferably 15% by mass or more, more preferably 20% by mass or more, preferably 50% by mass or more, more preferably 75% by mass above, more preferably 85 mass % or more, on the other hand, preferably 99.5 mass % or less, more preferably 99 mass % or less, still more preferably 98 mass % or less, more preferably 15 mass % or more and 99.5 mass % Below, it is more preferable that it is 20 mass % or more and 99 mass % or less. Furthermore, a part or all of the non-aqueous solvent may be removed from the composition of the present invention as needed. Therefore, the composition of the present invention may be in the state of a solution or dispersion, or may be in the state of a powder after drying.

Moreover, in the composition of the present invention, the content of the modified cellulose fibers (excluding modifying groups, etc.) is preferably 0.01 mass parts per 100 mass parts of the non-aqueous solvent, from the viewpoint of suppressing the viscosity decrease even at high temperature. parts by mass or more, more preferably not less than 0.05 parts by mass, still more preferably not less than 0.1 parts by mass, and from the same viewpoint, preferably not more than 20 parts by mass, more preferably not more than 10 parts by mass, still more preferably not more than 5 parts by mass , with respect to 100 parts by mass of the non-aqueous solvent, preferably 0.01 parts by mass or more and 20 parts by mass or less, more preferably 0.05 parts by mass or more and 10 parts by mass or less, and still more preferably 0.1 parts 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, and still more preferably 0.1% by mass or less , and may be substantially 0 mass %. The water content includes the entrained amount of water from the non-aqueous solvent.

[inorganic compound] The composition of the present invention may also contain metal oxides such as titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, etc.; gold, silver, copper, iron, tin, lead, zinc, aluminum, etc. Metal powders such as calcium carbonate, aluminum hydroxide, ammonium bromide and other inorganic salts; ceramics, zeolite, carbon black, fullerenes, carbon nanotubes, carbon fibers, graphene, silicon carbide, boron nitride, aluminum nitride , inorganic compounds exemplified by inorganic solids such as silica, talc, and clay. The shape of the inorganic compound is not particularly limited, but from the viewpoint of workability, powder, granular, fibrous, flake, granular, block, and paste are preferred.

The content of the inorganic compound in the composition of the present invention varies depending on the application and is not particularly limited. From the viewpoint of the dispersion stability of the inorganic compound at a high temperature of 50°C or higher and the performance of the addition effect of the inorganic compound , relative to 100 parts by mass of the modified cellulose fibers, preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, more preferably 2 parts by mass or more, and still more preferably 3 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 100 parts by mass or more, on the other hand, from the viewpoint of the effect of the present invention, preferably 1,000,000 parts by mass or less, more preferably 500,000 parts by mass Parts by mass 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 or less. Therefore, in the composition of the present invention, from the viewpoint of dispersing the inorganic compound in the non-aqueous solvent, the mass ratio of the inorganic compound/modified cellulose fiber is preferably 0.1/100 or more and 10,000/1 or less, more preferably 1 /100 or more and 1000/1 or less, more preferably 1/10 or more and 300/1 or less, still more preferably 1/1 or more and 100/1 or less.

In addition, in the composition, the content of the inorganic compound is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 10% by mass or more, and on the other hand, preferably 99% by mass or less, more preferably 95 mass % or less, more preferably 90 mass % or less, more preferably 85 mass % or less, still more preferably 80 mass % or less. In the composition, from the viewpoint of dispersing the inorganic compound in the non-aqueous solvent, the mass ratio of the inorganic compound/non-aqueous solvent is preferably 1/100 or more, more preferably 1/10 or more, and still more preferably 1/1 Above, from the viewpoint of dispersion stability in a non-aqueous solvent at 50° C. or higher, preferably 500/1 or less, more preferably 300/1 or less, and 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, as hydrocarbon-based waxes, within the range that does not impair the effect of the present invention Lubricants, ultraviolet absorbers, antistatic agents, antifogging agents, light stabilizers, pigments, rust inhibitors, antibacterial agents, foaming agents, surfactants, etc. Polysaccharides; natural proteins such as gelatin, gum, and casein; tannins; fragrances; flow regulators; leveling agents; Furthermore, in the range which does not impair the effect of this invention, another polymer material or other composition may be added. In addition, other components may be the above-mentioned inorganic compounds.

[Manufacturing method of tackifier composition] The thickener composition of this invention can be manufactured by mixing the said modified cellulose fiber, the said non-aqueous solvent, etc., for example. For example, each of the above-mentioned components can be kneaded by using a known kneader such as a closed kneader, a uniaxial or biaxial extruder, a roll mill, an open roll kneader, or by a solvent casting method or by using It is performed by shearing with a shearing device such as a high shearing machine.

[Properties of the tackifier composition] In general, liquids have a tendency to decrease in viscosity at higher temperatures, and the composition of the present invention is characterized by a relatively small tendency. Specifically, the value of [viscosity at 80°C]/[viscosity at 25°C] (viscosity ratio at 80°C/25°C) of the composition of the present invention is preferably from the viewpoint of suppressing viscosity reduction even at high temperatures 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, more preferably 3 or less, furthermore 2 or less is preferable, and 1.5 or less is more preferable. Furthermore, 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 from the viewpoint of suppressing viscosity reduction even at high temperatures , 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, more preferably 3 or less, and still more preferably 2 or less, more preferably 1.5 or less.

The viscosity (mPa·s) at 25°C of the composition of the present invention is preferably 100 or more, more preferably 500 or more, from the viewpoint of the handling of the composition under the condition of a shear rate of 1.0 s ⁻¹ . More preferably, it is 1,000 or more, and on the other hand, from the viewpoint of workability as a tackifier composition, it is preferably 500,000 or less, more preferably 300,000 or less, still more preferably 200,000 or less, and still more preferably 100,000 or less, more preferably 30,000 or less.

The viscosity (mPa·s) at 80°C of the composition of the present invention is preferably 100 or more, more preferably 500 or more, from the viewpoint of the handling of the composition, under the condition of a shear rate of 1.0 s ⁻¹ . More preferably, it is 1,000 or more, and on the other hand, from the viewpoint of workability as a tackifier composition, it is preferably 500,000 or less, more preferably 300,000 or less, still more preferably 200,000 or less, and still more preferably 100,000 or less, more preferably 30,000 or less.

The viscosity (mPa·s) at 125°C of the composition of the present invention is preferably 100 or more, more preferably 500 or more, from the viewpoint of the handling of the composition under the condition of a shear rate of 1.0 s ⁻¹ . More preferably, it is 1,000 or more, and on the other hand, from the viewpoint of workability as a tackifier composition, it is preferably 500,000 or less, more preferably 300,000 or less, still more preferably 200,000 or less, and still more preferably 100,000 or less, more preferably 30,000 or less. The tackifier composition of the present invention has fluidity as described above, thereby improving workability.

In addition, the measurement method of the viscosity in this specification can be performed by the method described in the following Example using a rheometer.

[Use of tackifier composition] The tackifier composition of the present invention can be used for various products without particular limitation. Specific examples of products to which the thickener composition of the present invention can be applied include food and beverages, cosmetics, quasi-drugs, pharmaceuticals, daily necessities, feeds, miscellaneous goods, agricultural chemicals, and chemical industrial products. More specifically, in the fields of home appliance parts, electronic materials (electronic equipment), packaging containers, aerospace, civil engineering, automobiles, and vehicle applications, for example, resin molding materials, electrical insulating materials, paints, and inks are exemplified. , coating agents, adhesives, repair materials, adhesives, lubricants, sealing materials, heat insulation materials, sound-absorbing materials, artificial leather materials, electronic materials, semiconductor materials, tires, auto parts, fiber composite materials, etc. Preferred among these are for electronic materials, optical materials or structural materials.

The amount of the tackifier composition prepared in these products is not particularly limited, and relative to 100 parts by mass of the product (or the total amount of the components constituting the product), preferably 0.01 part by mass or more, more preferably 0.05 part by mass The mass part or more is more preferably 0.1 mass part or more, and on the other hand, 1000 mass parts or less is preferable, 800 mass parts or less is more preferable, and 500 mass parts or less is further more preferable.

<Use of tackifier composition> The tackifier composition of the present invention contains the above-mentioned modified cellulose fibers and a non-aqueous solvent, and is used at a temperature of 50°C or higher, preferably 60°C or higher, and 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 viscosity increasing performance. In addition, the tackifier composition of the present invention is preferably used in a temperature range of preferably 50°C or higher, more preferably 100°C or higher, and preferably 250°C or lower. Instructions. The so-called temperature range above 50°C, for example, is 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) .

In this specification, the use of the tackifier composition at a specified temperature (or temperature range) can be exemplified as follows: adding the tackifier composition at a specified temperature (or temperature range) to the object to be thickened; or After adding the tackifier composition to the object to be thickened, it is adjusted to a predetermined temperature (or temperature range). Since the tackifier composition of the present invention is used at a temperature of 50° C. or higher, some or all of the non-aqueous solvent may be volatilized, but it can be used without problems. In addition, depending on the application, there is also a form in which the viscosity is maintained at a temperature as high as a certain temperature, and then the solvent component is completely evaporated by heating and then solidified. In this form, the viscosity increase of the present invention can also be preferably achieved. use of the composition. In the use of the tackifier composition, the aforementioned tackifier composition preferably further contains the aforementioned inorganic compound. As a specific form used over a temperature range of 50°C or higher, for example, it is a lubricant or lubricating oil. As a specific embodiment that is used over a temperature range of 50° C. or higher, and as a result, the non-aqueous solvent is removed, for example, it is a paint or an ink.

<Viscosity control agent for non-aqueous solvents> The viscosity control agent of the present invention contains the above-mentioned modified cellulose fibers. The viscosity control agent of the present invention is used for a non-aqueous solvent, and it is a high temperature viscosity control agent that can control the viscosity of a non-aqueous solvent by applying the viscosity control agent to a non-aqueous solvent, for example, suppressing the viscosity decrease at a high temperature of 50°C or higher . As described above, the viscosity control agent of the present invention is used at a temperature of preferably 50°C or higher, preferably 60°C or higher, more preferably 80°C or higher, and on the other hand, preferably 300°C or lower, more preferably It is used at a temperature of 280°C, more preferably 200°C or lower, and still more preferably 150°C or lower. As the non-aqueous solvent, the above-mentioned ones may, for example, be mentioned.

From the viewpoint of controlling the viscosity of the non-aqueous solvent with respect to 100 parts by mass of the non-aqueous solvent, the content of the modified cellulose fibers (excluding modification groups, etc.) of the viscosity control agent of the present invention is preferably 0.01 part by mass or more, and more It is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and from the same viewpoint, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less. That is, the content of the modified cellulose fibers (excluding modifying groups, etc.) is preferably 0.01 parts by mass or more and 20 parts by mass or less, more preferably 0.05 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the non-aqueous solvent. , and more preferably 0.1 parts by mass or more and 5 parts by mass or less.

[inorganic compound] The viscosity control agent of the present invention may also contain inorganic compounds that can be used in the above-mentioned tackifier composition within a range that does not impair the effects of the present invention. The shape of the inorganic compound is not particularly limited, but from the viewpoint of workability, powder, granular, fibrous, flake, granular, block, and paste are preferred.

The amount of the inorganic compound in the viscosity control agent of the present invention relative to the modified cellulose fibers is as described in the above-mentioned viscosity-increasing agent composition, and the preferred range is the same. The viscosity control agent of the present invention can control the non-aqueous solvent to the viscosity of 25°C, 80°C, 120°C, the viscosity ratio of 80°C/25°C, and the viscosity ratio of 120°C/25°C, as described in the properties of the above-mentioned tackifier composition. The preferred value of the viscosity ratio in ℃.

<Coating method of inorganic compound> The present invention has the method of heating a composition containing at least one modified cellulose fiber selected from the group consisting of the following (1) and (2), a non-aqueous solvent and an inorganic compound to 100° C. or higher The coating method of the inorganic compound in the step of removing the non-aqueous solvent. (1) A type I crystal structure formed by bonding a modifying group to a cellulose fiber, and the modifying group contains a group selected from (a) a hydrocarbon group, (b) a polysiloxane chain, and (c) an alkylene oxide chain 1 or more of the group formed (2) Acid-type anion-modified cellulose fibers with I-type crystal structure The non-aqueous solvent and the inorganic compound are as described above.

The heating temperature varies depending on the non-aqueous solvent used, but is preferably 150°C or higher, more preferably 200°C or higher. Preferably, the non-aqueous solvent is almost completely removed. The composition also inhibits viscosity reduction at higher temperatures above 50°C, so that the diffusion and coating of inorganic compounds can be inhibited. As an object to be coated, a metal surface, a plastic surface, paper, etc. can be mentioned, for example, it can be used for paint or ink. The preferred compound, preferred content, preferred content ratio, etc. of each component of the composition in the coating method are as described in the above-mentioned composition.

Regarding the above-mentioned embodiment, the present invention further discloses the following tackifier composition, use of the tackifier composition, viscosity control agent, and coating method of the inorganic compound. <1> A tackifier composition containing modified cellulose fibers and a non-aqueous solvent and used at a temperature of 50°C or higher, The said modified cellulose fiber is 1 or more types chosen from the group which consists of following (1) and (2). (1) A type I crystal structure formed by bonding a modifying group to a cellulose fiber, and the modifying group contains a group selected from (a) a hydrocarbon group, (b) a polysiloxane chain, and (c) an alkylene oxide chain 1 or more of the group formed (2) Acid-type anion-modified cellulose fibers with I-type crystal structure

<2> The composition according to the above <1>, wherein the viscosity ratio at 80°C/25°C is 0.6 or more and 5 or less. <3> The composition according to the above <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 the above <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 the above <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 the above <1> to <5>, wherein the cellulose fibers in the above (1) are anionically modified cellulose fibers. <7> The composition of any one of the above <1> to <6>, wherein the modifying group is bonded to the anionic group of the anionically modified cellulose fiber via an ionic bond and/or a covalent bond. <8> The composition according to any one of the above <1> to <7>, wherein the non-aqueous solvent contains a hydrocarbon-based solvent, an alcohol-based solvent, an ether-based solvent, an ester-based solvent, and a glycol ether-based solvent (excluding two alcohol ether ester solvent), fatty acid, animal/vegetable oil or polysiloxane oil. <9> The composition according to any one of the above <1> to <8>, wherein the non-aqueous solvent contains a hydrocarbon-based solvent or a glycol ether-based solvent. <10> The composition according to any one of the above <1> to <9>, wherein when the modified cellulose fiber contains (a) a hydrocarbon group or (b) a polysiloxane chain, the non-aqueous solvent is a hydrocarbon-based solvent Solvent, silicone oil or glycol ether solvent. <11> The composition according to any one of the above <1> to <10>, wherein when the modified cellulose fiber contains (c) an alkylene oxide chain, the non-aqueous solvent is a hydrocarbon-based solvent or a glycol ether solvent (excluding glycol ether ester solvent). <12> The composition according to any one of the above <1> to <11>, wherein when the modified cellulose fiber contains (c) an alkylene oxide chain, the non-aqueous solvent is a glycol ether-based solvent (not a Contains glycol ether ester solvent). <13> The composition according to any one of the above <1> to <12>, wherein the alkylene oxide chain is selected from the group consisting of ethylene oxide (EO) polymerization part, propylene oxide (PO) polymerization part, and (EO) /PO) One or more (co)polymerization parts in the group consisting of the copolymerization parts. <14> The composition according to any one of the above <1> to <13>, wherein the average fiber diameter of the modified cellulose fibers 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 the above <1> to <14>, wherein the average fiber length of the modified cellulose fibers is 100 nm or more and 10000 nm or less, preferably 200 nm or more and 5000 nm or less. <16> The composition according to any one of the above-mentioned <1> to <15>, which further contains an inorganic compound. <17> The composition of the above <16>, wherein 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 it is 1/1 or more and 100/1 or less. <18> The composition according to the above <16> or <17>, wherein 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 more preferably 10% by mass or more and 80% by mass or less. <19> The composition according to any one of the above <1> to <18>, wherein the content of the modified cellulose fibers (excluding modification groups, etc.) in the composition is preferably 0.01 mass in terms of cellulose % or more and 50 mass % or less, more preferably 0.05 mass % or more and 20 mass % or less, still more preferably 0.1 mass % or more and 10 mass % or less. <20> The composition according to any one of the above <1> to <19>, wherein the content of the modified cellulose fibers (excluding modification groups, etc.) in the composition is preferably 100 parts by mass of the non-aqueous solvent It is 0.01 mass part or more and 20 mass parts or less, More preferably, it is 0.05 mass part or more and 10 mass parts or less, More preferably, it is 0.1 mass part or more and 5 mass parts or less. <21> The composition according to any one of the above <1> to <20>, wherein 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. <22> The composition according to any one of the above <1> to <21>, which is used at a temperature of 60°C or higher, more preferably 80°C or higher. <23> The composition according to any one of the above <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 the above-mentioned <1> to <23>, which is used after removing the non-aqueous solvent. <25> The composition according to any one of the above-mentioned <1> to <24>, which is used for an electronic material, an optical material or a structural material. <26> Use of a tackifier composition for use at a temperature of 50°C or higher, the tackifier composition containing one selected from the group consisting of the following (1) and (2) The above modified cellulose fibers and non-aqueous solvent. (1) A type I crystal structure formed by bonding a modifying group to a cellulose fiber, and the modifying group contains a group selected from (a) a hydrocarbon group, (b) a polysiloxane chain, and (c) an alkylene oxide chain 1 or more of the group formed (2) Acid-type anion-modified cellulose fibers with I-type crystal structure <27> The use according to the above <26>, which is used at a temperature of 60°C or higher. <28> The use according to the above-mentioned <26> or <27>, which is used at a temperature of 80°C or higher. <29> The use according to any one of the above <26> to <28>, which is used in a temperature range of 50°C or higher. <30> The use according to any one of the above <26> to <29>, which is used in a temperature range of 100°C or higher. <31> The use according to any one of the above-mentioned <26> to <30>, which removes a non-aqueous solvent. <32> The use according to any one of the above <26> to <31>, wherein the viscosity ratio at 80°C/25°C of the tackifier composition is 0.6 or more and 5 or less. <33> The use according to any one of the above <26> to <32>, wherein the viscosity ratio at 80°C/25°C of the tackifier composition is 0.7 or more and 3 or less. <34> The use according to any one of the above <26> to <33>, wherein the viscosity ratio at 125°C/25°C of the tackifier composition is 0.6 or more and 5 or less. <35> The composition according to any one of the above <26> to <34>, wherein the viscosity ratio at 125°C/25°C of the tackifier composition is 0.7 or more and 3 or less. <36> The use according to any one of the above <26> to <35>, wherein the cellulose fibers in the above (1) are anionically modified cellulose fibers. <37> The use according to any one of the above <26> to <36>, wherein the modifying group is bonded to the anionic group of the anionically modified cellulose fiber via an ionic bond and/or a covalent bond. <38> The use according to any one of the above <26> to <37>, wherein the non-aqueous solvent contains a hydrocarbon-based solvent, an alcohol-based solvent, an ether-based solvent, an ester-based solvent, and a glycol ether-based solvent (excluding glycols) ether ester solvents), fatty acids, animal/vegetable oils, or silicone oils. <39> The use according to any one of the above <26> to <38>, wherein the non-aqueous solvent contains a hydrocarbon-based solvent or a glycol ether-based solvent. <40> The use according to any one of the above <26> to <39>, wherein when the modified cellulose fiber contains (a) a hydrocarbon group or (b) a polysiloxane chain, the non-aqueous solvent is a hydrocarbon-based solvent , polysiloxane oil or glycol ether solvent. <41> The use according to any one of the above <26> to <40>, wherein when the modified cellulose fiber contains (c) an alkylene oxide chain, the non-aqueous solvent is a hydrocarbon-based solvent or a glycol ether-based solvent Solvent (including glycol ether ester solvent). <42> The use according to any one of the above <26> to <41>, wherein when the modified cellulose fiber contains (c) an alkylene oxide chain, the non-aqueous solvent is a glycol ether-based solvent (including two alcohol ether ester solvent). <43> The use according to any one of the above <26> to <42>, wherein the alkylene oxide chain is selected from the group consisting of ethylene oxide (EO) polymerization part, propylene oxide (PO) polymerization part, and (EO/ PO) One or more (co)polymerization parts in the group consisting of copolymerization parts. <44> The use according to any one of the above <26> to <43>, wherein the average fiber diameter of the modified cellulose fibers 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 the above <26> to <44>, wherein the average fiber length of the modified cellulose fibers is 100 nm or more and 10000 nm or less, preferably 200 nm or more and 5000 nm or less. <46> The use according to any one of the above <26> to <45>, wherein the tackifier composition further contains an inorganic compound. <47> The use according to any one of the above <26> to <46>, wherein the mass ratio of the inorganic compound/modified cellulose fiber in the tackifier composition is 0.1/100 or more and 10000/1 or less, more It is preferably 1/100 or more and 1000/1 or less, more preferably 1/10 or more and 300/1 or less, and still more preferably 1/1 or more and 100/1 or less. <48> The use according to any one of the above <26> to <47>, wherein the content of the inorganic compound in the composition is preferably 0.1 mass % or more and 90 mass % or less, more preferably 1 mass % or more and 85 mass % The mass % or less is more preferably 10 mass % or more and 80 mass % or less. <49> The use according to any one of the above <26> to <48>, wherein in the composition, the content of the modified cellulose fibers (excluding modifying groups, etc.) is preferably 0.01% by mass in terms of cellulose It is more than 50 mass %, More preferably, it is 0.05 mass % or more and 20 mass % or less, More preferably, it is 0.1 mass % or more and 10 mass % or less. <50> The use according to any one of the above <26> to <49>, wherein in the composition, the content of the modified cellulose fibers (excluding modification groups, etc.) is preferably 100 parts by mass of the non-aqueous solvent. 0.01 mass part or more and 20 mass parts or less, More preferably, it is 0.05 mass part or more and 10 mass parts or less, More preferably, it is 0.1 mass part or more and 5 mass parts or less. <51> The use according to any one of the above <26> to <50>, wherein 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. <52> The use according to any one of the above <26> to <51>, wherein the tackifier composition is a composition for electronic materials, optical materials or structural materials. <53> A viscosity control agent for a non-aqueous solvent, comprising at least one modified cellulose fiber selected from the group consisting of the following (1) and (2). (1) A type I crystal structure formed by bonding a modifying group to a cellulose fiber, and the modifying group contains a group selected from (a) a hydrocarbon group, (b) a polysiloxane chain, and (c) an alkylene oxide chain 1 or more of the group formed (2) Acid-type anion-modified cellulose fibers with I-type crystal structure <54> The viscosity control agent of said <53> which further contains an inorganic compound. <55> The viscosity control agent of the above-mentioned <53> or <54>, which is used at a temperature of 50°C or higher. <56> The viscosity control agent according to any one of the above <53> to <55>, which is used at a temperature of 60°C or higher. <57> The viscosity control agent according to any one of the above <53> to <56>, which is used at a temperature of 80°C or higher. <58> The viscosity control agent according to any one of the above <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 the above <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 the above <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 the above <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 the above <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 the above <53> to <62>, wherein the viscosity ratio at 125°C/25°C is 0.7 or more and 3 or less. <64> A method for coating an inorganic compound, comprising: a modified cellulose fiber, a non-aqueous solvent, and an inorganic compound as one or more selected from the group consisting of the following (1) and (2). The step of removing the non-aqueous solvent by heating the composition to 100°C or higher. (1) A type I crystal structure formed by bonding a modifying group to a cellulose fiber, and the modifying group contains a group selected from (a) a hydrocarbon group, (b) a polysiloxane chain, and (c) an alkylene oxide chain 1 or more of the group formed (2) Acid-type anion-modified cellulose fibers with I-type crystal structure <65> The coating method according to the above <64>, which is preferably heated to 150°C or higher, more preferably 200°C or higher. <66> The coating method according to the above-mentioned <64> or <65>, wherein the content of the inorganic compound in the composition is preferably 0.1 mass % or more and 90 mass % or less, more preferably 1 mass % or more and 85 mass % Hereinafter, it is more preferably 10 mass % or more and 80 mass % or less. <67> The coating method according to any one of the above <64> to <66>, wherein in the composition, the content of the modified cellulose fibers (excluding modification groups, etc.) is calculated in terms of cellulose, preferably 0.01 The mass % or more and 50 mass % or less, more preferably 0.05 mass % or more and 20 mass % or less, and still more preferably 0.1 mass % or more and 10 mass % or less. <68> The coating method according to any one of the above <64> to <67>, wherein in the composition, the content of the modified cellulose fibers (excluding modification groups, etc.) is more than 100 parts by mass of the non-aqueous solvent. 0.01 mass part or more and 20 mass parts or less are preferable, 0.05 mass part or more and 10 mass parts or less are more preferable, and 0.1 mass part or more and 5 mass parts or less are still more preferable. <69> The coating method according to any one of the above <64> to <68>, wherein 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 More than 99 mass % or less. [Example]

Hereinafter, an Example etc. are shown and this invention is demonstrated concretely. In addition, the following examples are merely illustrative of the present invention, and do not mean any limitation. In addition, the so-called "normal pressure" means 101.3 kPa, and the so-called "normal temperature" means 25°C.

[Average fiber diameter, average fiber length and average aspect ratio of micronized anionically modified cellulose fibers and modified cellulose fibers] When the measurement object is the micronized anion-modified cellulose fiber, water is added, or when the measurement object is the modified cellulose fiber, the same solvent as the solvent used in the preparation of the tackifier composition is added to prepare it. A dispersion liquid with a content of 0.0005 mass %. Furthermore, IPA is used when the solvent is squalane or TGME. An atomic force microscope (AFM) (manufactured by Digital Instruments, Nanoscope II Tappingmode AFM, manufactured by Nanosensors, Inc., used as a probe; Point Probe (NCH)) to measure the fiber height of the cellulose fibers in the observed sample (the difference in height between the part where the fiber exists and the part where the fiber does not exist). At this time, 100 or more cellulose fibers were extracted from the microscope image in which the cellulose fibers were confirmed, and the average fiber diameter was calculated from the fiber heights thereof. The average fiber length was calculated from the distance in the fiber direction. The average aspect ratio is calculated from the average fiber length/average fiber diameter. The height for analysis in images obtained by AFM can be considered as fiber diameter.

Only in Example 10, it was not easy to confirm the modified cellulose fibers by the measurement using the above-mentioned AFM. Therefore, only in Example 10, the solution obtained by diluting the obtained tackifier composition to 0.02 mass % with IPA and performing ultrasonic treatment for 5 minutes was added dropwise to mica by one drop. After natural drying, using an electron microscope VE-8800 (manufactured by KEYENCE Corporation), under the measurement conditions of an accelerating voltage of 5 kV and a spot diameter of 8 After observation, the average fiber diameter, average fiber length and average aspect ratio of the modified cellulose fibers were obtained by the same method as above.

[Average fiber diameter and average fiber length of raw cellulose fibers and anionically modified cellulose fibers] Deionized water was added to the cellulose fibers to be measured to prepare a dispersion liquid having a content of 0.01% by mass. The dispersion liquid was measured under the following conditions: Front lens: 2x, Telecentric zoom lens: 1x , Image resolution: 0.835 μm/pixel, syringe inner diameter: 6515 μm, spacer thickness: 500 μm, image recognition mode: ghosting, threshold: 8, analysis sample volume: 1 mL, sampling: 15%. 100 or more cellulose fibers were measured, the average ISO (International Organization for Standardization) fiber diameter of these fibers was taken as the average fiber diameter, and the average ISO fiber length was calculated as the average fiber length.

[Anionic group content of anionically modified cellulose fibers and modified cellulose fibers] Take the dry mass of 0.5 g of cellulose fiber to be measured and put it in a beaker, add deionized water or a mixed solvent of methanol/water = 2/1 (volume ratio) to make the whole 55 mL, and add 0.01 M chloride to it. A dispersion liquid was prepared by adding 5 mL of sodium aqueous solution. The dispersion liquid is stirred until the cellulose fibers to be measured are sufficiently dispersed. To this dispersion liquid, 0.1 M hydrochloric acid was added to adjust the pH to 2.5 to 3. Using an automatic titrator (manufactured by Toa DKK, trade name "AUT-701"), a 0.05 M aqueous sodium hydroxide solution was added for a waiting time of 60 seconds. It was added dropwise to the dispersion under the same conditions, and the conductivity and pH value were measured every 1 minute. The measurement was continued until the pH value reached about 11, and a conductivity curve was obtained. The titration of sodium hydroxide was obtained from this conductivity curve, and the anionic group content of the cellulose fiber to be measured was calculated by the following formula. Anionic group content (mmol/g) = [titration amount of sodium hydroxide aqueous solution (mL) × sodium hydroxide aqueous solution concentration (0.05 M)]/[mass of cellulose fibers to be measured (0.5 g)]

[Aldehyde group content of oxidized cellulose fibers] The carboxyl group content of the oxidized cellulose fiber to be measured was measured by the above-mentioned measuring method of anionic group content. On the other hand, 100 g of an aqueous dispersion of oxidized cellulose fibers to be measured (solid content: 1.0 mass %), 100 g of an acetic acid buffer (pH 4.8), 2-methyl-2- 0.33 g of butene and 0.45 g of sodium chlorite were stirred at 25° C. for 16 hours to oxidize the aldehyde groups remaining in the oxidized cellulose fibers. After the reaction is completed, the cellulose fibers are washed with deionized water to obtain the cellulose fibers after the oxidation treatment of the aldehyde groups. The carboxyl group content of the dried product obtained by freeze-drying was measured by the above-mentioned measuring method of anionic group content, and the "carboxy group content of oxidized cellulose fiber after oxidation treatment" was calculated. Next, the aldehyde group content of the oxidized cellulose fiber to be measured was calculated using the formula 1.

Aldehyde group content (mmol/g) = (Carboxyl group content of oxidized cellulose fibers after oxidation treatment) - (Carboxyl group content of oxidized cellulose fibers to be measured)・・・Formula 1

[Solid content in gel or dispersion] The measurement was performed using a halogen moisture meter (manufactured by Shimadzu Corporation; trade name "MOC-120H"). For 1 g of the sample, the measurement was performed every 30 seconds at a constant temperature of 150°C, and the value at which the mass was reduced to 0.1% or less of the initial amount of the sample was taken as the solid content content. Furthermore, when it is difficult to analyze the solid content concentration by the above-mentioned analytical method due to the use of a high-boiling organic solvent, a known alternative method such as the phenol-sulfuric acid method may be used separately.

[Binding Amount and Introduction Rate of Modified Groups in Modified Cellulose Fiber] The binding amount of the modifying group was determined by the following IR (Infrared) measurement method, and the binding amount and introduction rate were calculated by the following formula Rate. Specifically, the IR measurement was performed using an infrared absorption spectrometer (IR) (Nicolet 6700, manufactured by Thermo Fisher Scientific) and an ATR (attenuated total reflectance method, attenuated total reflection) method to measure the infrared ray of the dried modified cellulose fibers. The absorption spectrum was used, and the bonding amount and the introduction rate of the modified group were calculated by formulas A and B. Hereinafter, the case where the anionic group is a carboxyl group, that is, the case where the oxidized cellulose fiber is shown will be shown. The following "peak intensity at 1720 cm ^-1 " is derived from the peak intensity of carbonyl groups. Furthermore, in the case of an anionic group other than a carboxyl group, the value of the wave number may be appropriately changed, and the bonding amount and the introduction rate of the modifying group may be calculated.

<Formula A-1 (in the case of an ionic bond)> Bonding amount of the modifying group (mmol/g)=a×(b-c)÷ba: Carboxyl group content of oxidized cellulose fibers (mmol/g) b: oxidized fibers The peak intensity c of cellulose fibers at 1720 cm ^-1 : the peak intensity of modified cellulose fibers at 1720 cm ^-1 <Formula A-2 (in the case of amide bonds)> Bonding amount of the modified group (mmol/g )=d-ed: content of carboxyl groups in oxidized cellulose fibers (mmol/g) e: content of carboxyl groups in modified cellulose fibers (mmol/g) <Formula B> Modification group introduction rate (mol%)=100×f /gf: Bonding amount of modified groups (mmol/g) g: Carboxyl group content of oxidized cellulose fibers (mmol/g)

[Confirmation of Crystal Structure in Modified Cellulose Fiber] The crystal structure of the modified cellulose fiber was confirmed by measuring under the following conditions using an X-ray diffractometer (manufactured by Rigaku Corporation, MiniFlex II). The measurement conditions were set as X-ray source: Cu/Kα-radiation, tube voltage: 30 kv, tube current: 15 mA, measurement range: diffraction angle 2θ=5-45°, X-ray scanning speed: 10°/min. As a sample for measurement, the cellulose fiber to be measured was compressed into pellets having an area of 320 mm ² × a thickness of 1 mm. In addition, the degree of crystallinity of the cellulose I-type crystal structure is obtained by calculating the X-ray diffraction intensity based on the following formula C.

<Formula C> Cellulose I-type crystallinity (%)=[(I _22.6 -I _18.5 )/I _22.6 ]×100 [In the formula, I _22.6 represents the lattice plane (002 plane) in X-ray diffraction ( Diffraction intensity of diffraction angle 2θ=22.6°), I _18.5 represents the diffraction intensity of amorphous part (diffraction angle 2θ=18.5°)]

On the other hand, when the degree of crystallinity obtained by the above formula C is 35% or less, it is preferable to follow the "Guidelines for Experiments in Wood Science" (edited by the Japan Society of Wood; 2000) from the viewpoint of improving the calculation accuracy. It is calculated based on the following formula D according to the description of P199-200 of the April issue). Therefore, when the crystallinity degree obtained by the said Formula C is 35% or less, the value calculated based on the following Formula D can be used as a crystallinity degree.

<Formula D> Cellulose I-type crystallinity (%) = [A _c /(A _c +A _a )] × 100 [wherein, A _c represents the lattice plane (002 plane) (diffraction plane) in X-ray diffraction The sum of the peak areas of the diffraction angle 2θ=22.6°), (011 plane) (diffraction angle 2θ=15.1°) and (0-11 plane) (diffraction angle 2θ=16.2°), A _a represents the amorphous part ( The peak area of the diffraction angle 2θ=18.5°), each peak area is obtained by fitting the obtained X-ray diffraction pattern with a Gaussian function]

[Cellulose fiber in modified cellulose fiber (converted amount)] The so-called cellulose amount (converted amount) in the modified cellulose fiber refers to the amount of cellulose other than the modifying group in the modified cellulose fiber. In the modified cellulose fibers of the present invention, the formula amount of the modifying group may reach a certain level (for example, greater than the molecular weight of glucose). Therefore, in this specification, it is more stable to explain after excluding the difference in the formula amount of the modifying group. In this case, it is not represented by the amount of modified cellulose fibers but by the amount of cellulose (converted amount) constituting the modified cellulose fibers. The cellulose fiber (converted amount) in the modified cellulose fiber was measured by the following method.

When only one "modification compound" is added The amount of cellulose fibers (converted amount) was calculated by the following formula E. <Formula E> Amount of cellulose fiber (converted amount) (g) = mass of modified cellulose fiber (g)/[1 + molecular weight of compound for modification (g/mol) × bonding amount of modification group (mmol/g) × 0.001] (2) When two or more kinds of "modification compounds" are added The cellulose fiber amount (converted amount) was calculated in consideration of the molar ratio of each compound (that is, the molar ratio when the total molar amount of the added compounds was set to 1).

[Preparation of Anionic Modified Cellulose Fiber 1] Preparation Example 1 Bleached kraft pulp of conifers (manufactured by West Fraser, trade name: Hinton) was used as the natural cellulose fiber of the raw material. As TEMPO, a commercial item (manufactured by ALDRICH, Free radical, 98% by mass) was used. Commercially available products were used as sodium hypochlorite, sodium bromide, and sodium hydroxide.

First, weigh 10 g of the above bleached kraft pulp fibers and 990 g of deionized water, put them in a 2 L beaker made of PP (Polypropylene) equipped with a mechanical stirrer and stirring wings, and stir at 25°C and 100 rpm for 30 minutes. minute. 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 sequentially added to 10 g of the pulp fibers. Using an automatic titrator (manufactured by Toa DKK, trade name: AUT-701), titration was performed using a constant pH (pH-Stat), and the pH value was maintained at 10.5 after adding a 0.5 M aqueous sodium hydroxide solution. After the reaction was carried out at 25°C for 120 minutes at a stirring speed of 100 rpm, the dropwise addition of the aqueous sodium hydroxide solution was stopped to obtain a suspension of anionic modified cellulose fibers with carboxyl groups as anionic groups (ie oxidized cellulose fibers).

After adding 0.01 M hydrochloric acid to the obtained suspension of anion-modified cellulose fibers to make pH = 2, the cellulose fibers were sufficiently washed with deionized water until by using a miniaturized conductivity meter (Horiba). The conductivity of the filtrate was measured to be 200 μs/cm or less by LAQUAtwin EC-33B), and then dehydration treatment was performed to obtain an anion-modified cellulose fiber. In addition, the carboxyl 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 (Manufacture of Micronized Anion Modified Cellulose Fiber) To the anionically modified cellulose fiber finally obtained in Preparation Example 1, deionized water was added 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 this to adjust to pH=8, and then deionized water was added to make the total 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: Nanoovater L-ES) to obtain a micronized anion-modified cellulose fiber dispersion (solid content content). 1.0 mass %). The opposite ion of the carboxyl group of the micronized anion-modified cellulose fiber is sodium ion.

Preparation Example 3 (Production of Micronized Anion-Modified Cellulose Fibers Obtained by Reduction of Aldehyde Groups) 182 g of the micronized anion-modified cellulose fiber dispersion liquid (solid content content 1.0 mass %) obtained in Preparation Example 2 was weighed, and deionized water was added to make a total of 400 g. To this, 1.2 mL of a 0.1 M aqueous sodium hydroxide solution and 120 mg of sodium borohydride were added, followed by stirring at 25°C for 4 hours. Next, 9 mL of 1 M hydrochloric acid was added for protonation. After the reaction was completed, filtration was carried out, and the obtained filter cake was washed 6 times with deionized water to remove salt and hydrochloric acid to obtain a micronized anion-modified cellulose fiber dispersion liquid (solid content content 0.9) whose aldehyde group was reduced by treatment. quality%). The carboxyl group content of the obtained cellulose fibers was 1.50 mmol/g, and the aldehyde group content was 0.02 mmol/g. The carboxyl group possessed by the micronized anion-modified cellulose fiber is in the free acid form (COOH), which is abbreviated as "TCNF (acid form)". The average fiber diameter of the micronized anionically 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 10 g of bleached kraft pulp (manufactured by West Fraser Co., Ltd., trade name: Hinton), which is a natural cellulose, was sufficiently stirred with 990 g of ion-exchanged water, TEMPO (manufactured by ALDRICH Co., Ltd., Free radical, 98 mass %) 0.13 g, sodium bromide 1.3 g, 10.5 mass % sodium hypochlorite aqueous solution (10.5 mass % aqueous solution) 27 g. Using an automatic titrator (manufactured by Toa DKK Co., Ltd., AUT-701), a 0.5 M aqueous sodium hydroxide solution was added dropwise using constant pH titration, and the pH was maintained at 10.5. After the reaction was carried out at a stirring speed of 200 rpm for 120 minutes (20° C.), the dropwise addition of sodium hydroxide was stopped to obtain a suspension of anionically modified cellulose fibers with carboxyl groups as anionic groups (ie, oxidized cellulose fibers).

After adding 0.01 M hydrochloric acid to the obtained suspension of anion-modified cellulose fibers to adjust the pH to 2, the anion-modified cellulose fibers were sufficiently washed with ion-exchanged water until they were miniaturized and electrically conductive. The filtrate was subjected to dehydration treatment until the filtrate became 200 μs/cm or less by measuring the conductivity of a rate meter (manufactured by Horiba, Ltd., LAQUAtwin EC-33B) to obtain a cake-like anion-modified cellulose fiber. The obtained anionically modified cellulose fibers had an average fiber length of 594 μm, an average fiber diameter of 2.7 μm, an aspect ratio of 220, and a carboxyl group content of 1.5 mmol/g. The anionically modified cellulose fibers are TCNF (acid form).

[Preparation of Anion Modified Cellulose Fiber 3] Preparation Example 5 (Preparation of Short Fiber Anion Modified Cellulose Fiber) The anion-modified cellulose fiber obtained in Preparation Example 4 was added in an absolute dry mass of 1.8 g, and ion-exchanged water was added until the mass of the content became 36 g. Next, while stirring, the mixture was treated at 95° C. for 3 hours to obtain an aqueous suspension of short-fibered anion-modified cellulose fibers. The obtained anionically 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 carboxyl group content of 1.5 mmol/g. The anionically modified cellulose fibers are TCNF (acid form).

[Preparation of anionically modified cellulose fibers 4] Preparation Example 6 After fully stirring 8 g of conifer bleached kraft pulp (manufactured by West Fraser, trade name: Hinton), which is a natural cellulose, with 760 g of ion-exchanged water, TEMPO (manufactured by Aldrich Co., Ltd., Free radical, 98 mass %) 0.09 g, sodium bromide 1.0 g, 5.0 mass % sodium hypochlorite aqueous solution 21 g (3.8 mmol/g with respect to 1 g of pulp). Using an automatic titrator (manufactured by East Asia DKK Co., Ltd., AUT-701), a 0.5 M aqueous sodium hydroxide solution was added dropwise using constant pH titration, and the pH value was kept at 10.5. After the reaction was carried out at a stirring speed of 200 rpm for 120 minutes (20° C.), the dropwise addition of sodium hydroxide was stopped to obtain a suspension of anionic modified cellulose fibers with carboxyl groups as anionic groups (ie, oxidized cellulose fibers).

After adding 0.01 M hydrochloric acid to the obtained suspension of anion-modified cellulose fibers to adjust the pH to 2, the anion-modified cellulose fibers were sufficiently washed with ion-exchanged water until they became conductive by miniaturization. The conductivity of the filtrate was measured to be 200 μs/cm or less by a rate meter (manufactured by Horiba, Ltd., LAQUAtwin EC-33B), and then dehydration was performed to obtain a cake-like anion-modified cellulose fiber. The carboxyl group content of the obtained anionically modified cellulose fibers was 1.3 mmol/g. The anionically modified cellulose fibers are TCNF (acid form).

[Preparation of tackifier composition] Example 1 The micronized anion-modified cellulose fiber dispersion liquid obtained in Preparation Example 3 was washed three times with isopropyl alcohol (IPA), and then washed three times with squalane to perform solvent replacement. 66.7 g of the obtained gel (solid content: 0.9 mass %) and 1.53 g of amine group-modified polysiloxane (equivalent to 1 equivalent with respect to the carboxyl groups of the anion-modified cellulose fibers) were added to a beaker. It was mixed, and squalane was added thereto to make a total of 120 g. The mixture was stirred at room temperature for 5 minutes with a mechanical stirrer, and then treated with a high pressure homogenizer (manufactured by Yoshida Machinery Co., Ltd., trade name: Nanovater L-ES) at 150 MPa for 10 passes, thereby obtaining amine group modification. A squalane dispersion of modified cellulose fibers in which polysiloxane is linked to anionically modified cellulose fibers through ionic bonds. This dispersion liquid was used as a tackifier composition.

Example 2 A modified fiber was obtained in the same manner as in Example 1, except that IPA in Example 1 was replaced by acetone, squalane was replaced by toluene, and amine group-modified polysiloxane was replaced by monoamine EOPO amine Toluene dispersion of cellulose fibers. This dispersion liquid was used as a tackifier composition.

Example 3 The anion-modified cellulose fiber dispersion liquid obtained in Preparation Example 4 was washed three times with 1-methoxy-2-propanol (PGME) and replaced with a solvent. 7.0 g of the obtained gel (solid content: 14.6 mass %) and 3.1 g of EOPO amine (equivalent to 1 equivalent with respect to the carboxyl group of the anionically modified cellulose fiber) were added to a beaker and mixed, and PGME was added thereto. 33.0 g for a total of 43 g. After stirring the solution at room temperature with a mechanical stirrer for 1 hour, it was treated with a high-pressure homogenizer (manufactured by Yoshida Machine Co., Ltd., trade name: Nanovater L-ES) at 150 MPa for 5 passes, thereby obtaining EOPO amine via ions. 1-Methoxy-2-propanol dispersion of modified cellulose fibers bonded to anionically modified cellulose fibers. This dispersion liquid was used as a tackifier composition.

Example 4 Methyl ethyl ketone (MEK) was used instead of PGME of Example 3, and the solvent was replaced by washing three times. 5.3 g of the obtained gel (solid content content: 3.77% by mass) and 0.086 g of oleylamine (equivalent to 1 equivalent with respect to the carboxyl groups of the anionically modified cellulose fibers) were added to a beaker and mixed, and MEK was added thereto. 20.0 g and 40.0 g of squalane make a total of 65 g. This solution was stirred at room temperature for 1 hour with a mechanical stirrer, and then treated with a high-pressure homogenizer (manufactured by Yoshida Machine Co., Ltd., trade name: Nanovater L-ES) at 150 MPa for 5 passes. The dispersion liquid was dried under reduced pressure at 80° C. to remove solvents other than squalane to obtain a squalane dispersion liquid of modified cellulose fibers in which oleylamine was linked to the anionically modified cellulose fibers via ionic bonds. This dispersion liquid was used as a tackifier composition.

Example 5 A DMF dispersion of anionically modified cellulose fibers was obtained in the same manner as in Example 3, except that DMF was used instead of PGME of Example 3, and the compound for modification was not used. This dispersion liquid was used as a tackifier composition.

Example 6 The anion-modified cellulose fiber dispersion liquid obtained in Preparation Example 5 was washed three times with triethylene glycol monobutyl ether (manufactured by Tokyo Chemical Industry Co., Ltd., abbreviated as "TGME") to perform solvent replacement. 11.2 g of the obtained gel (solid content content: 13.4 mass %) and 2.0 g of an aqueous solution of tetrabutylammonium hydroxide having a concentration of 25 mass % (equivalent to 1 equivalent with respect to the carboxyl groups of the anionically modified cellulose fibers) were added to the solution. The beaker was mixed, and 16.8 g of triethylene glycol monobutyl ether was added thereto to make a total of 30 g. This solution was stirred at room temperature for 1 hour with a mechanical stirrer, and then treated with a high-pressure homogenizer (manufactured by Yoshida Machine Co., Ltd., trade name: Nanovater L-ES) at 150 MPa for 5 passes to obtain tetrabutylammonium A dispersion of modified cellulose fibers in triethylene glycol monobutyl ether linked to anionically modified cellulose fibers via ionic bonds. This dispersion liquid was used as a tackifier composition.

Example 7 The modification compounds used in Example 6 were changed to 1.0 g of an aqueous solution of tetrabutylammonium hydroxide having a concentration of 25% by mass (equivalent to 0.5 equivalent to the carboxyl group of the anion-modified cellulose fiber) and 2.0 g of EOPO amine (relative to the carboxyl group of the anion-modified cellulose fiber). Except that the carboxyl group of the anion-modified cellulose fiber is equivalent to 0.5 equivalent), the same operation as in Example 6 was carried out, thereby obtaining tetrabutylammonium and EOPO amine linked to the anion-modified cellulose fiber through ionic bonds. Modified cellulose fiber triethylene glycol monobutyl ether dispersion. This dispersion liquid was used as a tackifier composition.

Example 8 EOPO amine was obtained by carrying out the same operation as in Example 7, except that the modification compound used in Example 7 was changed to EOPO amine (equivalent to 1 equivalent with respect to the carboxyl group of the anionically modified cellulose fiber). TGME dispersion of modified cellulose fibers linked to anionically modified cellulose fibers via ionic bonds. This dispersion liquid was used as a tackifying composition.

Example 9 A TGME dispersion of modified cellulose fibers was obtained in the same manner as in Example 3, except that PGME of the solvent used in Example 3 was replaced with TGME. This dispersion liquid was used as a tackifying composition. In addition, the density|concentration (namely, solid content) of the modified cellulose fiber in a tackifying composition was set as the value described in Table 1-1.

Example 10 1.38 g (solid content content: 18.5 mass %) of the cake-like anion-modified cellulose fibers obtained in Preparation Example 6 was put into a beaker, and 50 g of ion-exchanged water and 0.66 g of EOPO amine (relative to The carboxyl group of the anion-modified cellulose fiber is equivalent to 1 equivalent) and mixed so that the total amount becomes 52 g. This solution was stirred at room temperature for 1 hour with a mechanical stirrer, and then treated with a high-pressure homogenizer (manufactured by Yoshida Machine Co., Ltd., trade name: Nanovater L-ES) at 100 MPa for one pass. Then, 50 g of TGME was added and stirred, and then 1-forming treatment was further performed at 100 MPa. The dispersion liquid was dried under reduced pressure at 80° C. to remove solvents other than TGME to obtain a TGME dispersion liquid of modified cellulose fibers in which the EOPO amine was ionically linked to the anionically modified cellulose fibers. This dispersion liquid was used as a tackifier composition.

The compounds for modification used in the above examples and the like are as follows. Amino-modified polysiloxane (manufactured by Toray Dow Corning Co., Ltd., BY16-209) EOPO amine (manufactured by Huntsman, USA, Jeffamine M2070, PO/EO (mol 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 polysiloxane will be used as the modified polysiloxane chain, EOPO amine will be used as the modified alkylene oxide chain ((EO/PO) copolymer), oleylamine and tetrabutylammonium hydroxide will be used as the modification The hydrocarbon groups of the radicals are respectively provided to the cellulose fibers.

[Production of low molecular weight thickener composition] Comparative Example 1 0.05 g (0.5 mass %) of lithium 12-hydroxystearate (manufactured by Katsuta Chemical Co., Ltd.) as a tackifier relative to 10 g of squalane was added to a small glass bottle, and heated to 205 Only heating and stirring in the block heater at ℃, so as to dissolve the tackifier. Let it cool at room temperature. The low molecular weight thickener composition of Comparative Example 1 was obtained.

Comparative Example 2 1.0 g (5 mass %) of fatty acid amide S (manufactured by Kao Co., Ltd.) as a tackifier with respect to 20 g of TGME was added to a small glass bottle, and was heated to 90°C in a block heater. Heating and stirring are performed to dissolve the thickener. This was left to cool at room temperature to obtain the low-molecular-weight viscosity-increasing composition of Comparative Example 2.

Comparative Example 3 2 mass % of unmodified cellulose fibers (manufactured by SUGINO MACHINE, BiNFi-s, WFo-10002 (average fiber diameter 10-50 nm)) were dispersed in water with 1-methoxy-2-propanol (PGME) After the body was washed once, it was washed three times with methyl ethyl ketone (MEK) for solvent replacement. 3.3 g of the obtained mixture (solid content content: 4.6 mass %), 5 g of PGME, and 30 g of MEK were put into a beaker, and 40.0 g of squalane was further added to make a total of 78 g. After stirring the solution with a mechanical stirrer for 1 hour, it was treated with a high-pressure homogenizer (manufactured by Yoshida Machinery Co., Ltd., trade name: Nanovater L-ES) at 150 MPa for 5 passes to obtain a dispersion of unmodified cellulose fibers. liquid.

About this dispersion liquid, PGME/MEK was removed using an evaporator (80 degreeC, 2 hours), and the squalane dispersion liquid containing unmodified cellulose fibers was obtained. In the step of removing PGME/MEK, the unmodified cellulose fibers coagulate and separate into liquid and coagulate. 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 in place of PGME/MEK in Comparative Example 3. 7.6 g of the obtained mixture (solid content content: 2.7 mass %) and 40.0 g of DMF were added to a beaker to make a total of 48 g. After stirring the solution with a mechanical stirrer for 1 hour, it was treated with a high-pressure homogenizer (manufactured by Yoshida Machinery Co., Ltd., trade name: Nanovater L-ES) at 150 MPa for 5 passes to obtain DMF dispersion of unmodified cellulose fibers. liquid. Although the viscosity measurement of this dispersion liquid at 25 degreeC was possible, it was separated into a liquid and an aggregate at 80 degreeC, and the viscosity measurement could not be performed.

Comparative Example 5 20 g of cake-like anion-modified cellulose fibers (solid content content: 26.1% by mass) obtained in Preparation Example 4 were thoroughly stirred in 250 g of ion-exchanged water, and then an aqueous sodium hydroxide solution was added until The pH value of the filtrate was 7.0 in the pH value measurement of the filtrate by a small pH meter (manufactured by Horiba Manufacturing Co., Ltd., LAQUATWIN-PH-11B) to obtain an anion-modified cellulose fiber whose carboxyl terminal was substituted with Na. The obtained aqueous dispersion of Na-substituted anion-modified cellulose fibers was washed three times with DMF to perform solvent replacement.

5.0 g of the obtained composition (solid content content: 3.0 mass %) and 25.0 g of DMF were added to a beaker to make a total of 30 g. After stirring the solution with a mechanical stirrer for 1 hour, it was treated with a high-pressure homogenizer (manufactured by Yoshida Machinery Co., Ltd., trade name: Nanovater L-ES) at 150 MPa for 5 passes to obtain Na-type anion-modified cellulose. DMF dispersion of fibers. Although the viscosity measurement of this dispersion liquid at 25 degreeC was possible, it was separated into a liquid and an aggregate at 80 degreeC, and the viscosity measurement could not be performed.

[Rheometer Evaluation of Thickener Composition] The viscosity evaluation of the tackifier composition was carried out by using a rheometer (manufactured by Anton Paar, Physica MCR300) to measure the viscosity. The measuring jig uses a conical jig CP50-1 (the compliance of the rotation axis is 4.5×10 ^-7 m/N), and the measurement conditions are that the first shear speed is 0.001 to 1000 s ^-1 , and the second time is 1000 to 0.001 s ^-1 and 0.001 to 1000 s ^-1 for the third measurement. From the viewpoint of viscosity stability, in the third measurement, the shear rate was 1.0 s -1 at each temperature ^. The viscosity at ¹ hour was compared. In addition, as a reference example, the viscosity of each non-aqueous solvent itself was also measured by the same method.

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

[Table 1-1] Table 1-1 Tackifier composition Modified Cellulose Fiber Modified compounds or modifiers non-aqueous solvent Crystal structure Crystallinity (%) type Average fiber diameter (nm) Average fiber length (nm) Average aspect ratio Concentration in the composition (mass %) type Addition amount (equivalent) Import rate* (%) Example 1 Type I 40 TEMPO oxidizes CNF 3 600 200 0.5 Amine modified polysiloxane 1 100 Squalane Example 2 Type I 42 TEMPO oxidizes CNF 3 600 200 0.5 EOPOamine 1 100 Toluene Example 3 Type I 42 TEMPO oxidizes CNF 4 600 150 3 EOPOamine 1 100 PGME Example 4 Type I 40 TEMPO oxidizes CNF 4 600 150 0.5 oleylamine 1 100 Squalane Example 5 Type I 40 TEMPO oxidizes CNF 5 640 128 0.5 H - - DMF Example 6 Type I 43 TEMPO oxidizes CNF 4 350 88 5 TBAH 1 100 TGME Example 7 Type I 43 TEMPO oxidizes CNF 4 350 88 5 EOPOamine/TBAH 0.5/0.5 50/50 TGME Example 8 Type I 43 TEMPO oxidizes CNF 4 350 88 5 EOPOamine 1 100 TGME Example 9 Type I 42 TEMPO oxidizes CNF 4 600 150 1 EOPOamine 1 100 TGME Example 10 Type I 43 TEMPO oxidizes CNF 110 4870 44 0.5 EOPOamine 1 100 TGME *: For COOH groups

[Table 1-2] Table 1-2 Evaluation results Viscosity (mPa s)** Evaluation of Viscosity of Slurry Containing Inorganic Powder Rheological diagram 80℃/25℃ Viscosity Ratio 120℃/25℃ Viscosity Ratio 25℃ 80℃ 120℃ Example 1 1503 911 2,351 - figure 1 0.61 1.56 Example 2 11910 8128 - - - 0.68 - Example 3 8614 8117 - - - 0.94 - Example 4 2252 1985 - - - 0.88 - Example 5 6955 13250 - - - 1.91 - Example 6 467 981 - - - 2.10 - Example 7 874 921 - - - 1.05 - Example 8 9699 8813 15,250 Table 4 figure 2 0.91 1.57 Example 9 9,935 6,295 8,156 - figure 2 0.63 0.82 Example 10 4,933 3,912 4,456 - figure 2 0.79 0.90 **: @ Shear Speed 1.0 s ^-1

[table 2-1] table 2-1 Tackifier composition Modified Cellulose Fiber Modified compounds or modifiers non-aqueous solvent Crystal structure Crystallinity (%) type Average fiber diameter (nm) Average fiber length (nm) Average aspect ratio Concentration in the composition (mass %) type Addition amount (equivalent) Import rate* (%) Comparative Example 1 - - (Lithium 12-hydroxystearate) - - - (0.5) - - - Squalane Comparative Example 2 - - (fatty acid amide S) - - - (5) - - - TGME Comparative Example 3 Type I 58 Unmodified CNF Unable to measure due to agglomeration 0.5 - - - Squalane Comparative Example 4 Type I 58 Unmodified CNF 340 26830 78.9 0.5 - - - DMF Comparative Example 5 Type I 40 TEMPO oxidizes CNF 300 21560 71.9 0.5 Na - - DMF Reference Example 1 - - without - - - - - - - Squalane Reference example 2 - - without - - - - - - - DMF Reference Example 3 - - without - - - - - - - Toluene Reference Example 4 - - without - - - - - - - PGME Reference Example 5 - - without - - - - - - - TGME *: For COOH groups

[Table 2-2] Table 2-2 Evaluation results Viscosity (mPa s)** Evaluation of Viscosity of Slurry Containing Inorganic Powder Rheological diagram 80℃/25℃ Viscosity Ratio 120℃/25℃ Viscosity Ratio 25℃ 80℃ 120℃ Comparative Example 1 200 35 twenty three - figure 1 0.18 0.12 Comparative Example 2 795 2 1 Table 4 - 0.00 0.00 Comparative Example 3 separate separate - - - Unable to calculate - Comparative Example 4 561 separate - - - Unable to calculate - Comparative Example 5 679 separate - - - Unable to calculate - Reference Example 1 30 11 5 - - 0.36 - Reference example 2 0.8 0.4 - - - 0.50 - Reference Example 3 0.5 0.4 - - - 0.80 - Reference Example 4 5 1 - - - 0.10 - Reference Example 5 9 4 3 - - 0.44 - **: @ Shear Speed 1.0 s ^-1

[Rheological graph of the viscosity-increasing composition] The rheological curves of the tackifier compositions in Example 1, Comparative Example 1, and Examples 8 to 10 are shown in FIGS. 1 and 2 . The rheological graphs of FIGS. 1 and 2 were carried out under the measurement conditions of Table 3 using the above-mentioned rheometer and measuring jig.

[table 3] Table 3 Measurement Conditions of Rheogram Number of Steps Deformation speed (1/s) temperature(℃) Measurement interval (s) Heating rate (℃/s) 1 0.01~1000 25 1 - 2 1000~0.01 25 1 - 3 1 25-120 1 0.2 ※Take step 3 as the official measurement and create a rheology chart.

Example 11 2.5 g of the TGME dispersion prepared in Example 8 and 10 g of the inorganic powder were added to a small glass bottle, and stirred with a spatula for 2 minutes. Then, it stirred at 2200 rpm for 10 minutes using the Taro defoaming mixer (ARE-310, the Thinky Co., Ltd. make). Then, it stirred with a spatula, and prepared the slurry containing an inorganic powder. Using a micropipette, 10 μL of the prepared slurry containing inorganic powder was added dropwise to a glass slide (25°C). The slide was placed on a hot plate heated to 120°C and 200°C, and heated for 1 minute. Then, the diffusion diameter of the inorganic powder of each slurry was measured by optical microscope observation, and the evaluation of the area ratio of the slurry containing the inorganic powder before and after heating was performed. Furthermore, when measured at 200°C, TGME was almost completely removed by volatilization. The results are shown in Table 4.

Comparative Example 6 In a small glass bottle, 10 g of inorganic powder was added to 2.5 g of the TGME dispersion liquid (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. After that, it was left to cool and stirred with a spatula, thereby obtaining a slurry containing inorganic powder. Then, the same evaluation as Example 11 was performed. The results are shown in Table 4.

Reference Example 6 An inorganic powder-containing slurry was prepared in the same manner as in Example 11, except that the TGME dispersion liquid used in Example 11 was changed to TGME. Then, the same evaluation as 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 Metal Mining Co., Ltd., part number: wet copper powder 1100Y, average particle size 1.1 μm)

[Table 4] Table 4 Composition of slurry containing inorganic powder Evaluation of the physical properties of the slurry Inorganic powder solvent Tackifier Dropping slurry area at 25°C (mm ² ) Dropping slurry area at 120°C (mm ² ) Dropping slurry area at 200°C (mm ² ) 120℃/25℃ area ratio 200℃/25℃ area ratio quality% quality% quality% Example 11 80 19 Modified CNF in Example 8 1 27.98 28.83 29.02 1.03 1.04 Comparative Example 6 80 19 Fatty acid amide S 1 21.14 42.41 46.91 2.01 2.22 Reference Example 6 80 20 - 0 32.46 37.48 38.69 1.15 1.19

From Tables 1 to 2, in Examples 1 to 4 and 8 to 10, the decrease in viscosity at 80°C was suppressed compared to the viscosity at 25°C. According to Figures 1 and 2, it can be seen that the composition of the embodiment of the present application shows a stable viscosity-increasing effect in a wider temperature range than the composition of the comparative example. The same effect was also confirmed in those in which the modified cellulose fibers were short-fibered (Examples 5 to 7). According to this result, the tackifier composition of the present invention is a tackifier composition that can be used at a temperature exceeding 50°C. According to Table 4, Example 11 containing the inorganic compound has the high-temperature viscosity-increasing property of the non-aqueous solvent, so even at a relatively high temperature, it will not be diluted, that is, the inorganic compound will not diffuse. From these results, it was found that the composition of the present invention is effectively used for applications involving processing at 50° C. or higher, such as compositions for electronic materials, optical materials, or structural materials. [Industrial Availability]

The tackifier composition of the present invention can be used in the fields of home appliance parts, electronic materials (electronic equipment), packaging materials, aerospace, civil engineering, automobiles, and vehicles.

FIG. 1 is a rheology curve diagram of the tackifier compositions in Example 1 and Comparative Example 1. FIG. FIG. 2 is a rheological graph of the tackifier compositions in Examples 8-10.

Claims (23)

A tackifier composition, which contains modified cellulose fibers and a non-aqueous solvent and is used at a temperature of 50°C or higher, The above-mentioned modified cellulose fibers are one or more selected from the group consisting of the following (1) and (2): (1) A type I crystal structure formed by bonding a modifying group to a cellulose fiber, and the modifying group contains a group selected from (a) a hydrocarbon group, (b) a polysiloxane chain, and (c) an alkylene oxide chain 1 or more of the group formed (2) Acid-type anion-modified cellulose fibers with an I-type crystal structure. According to the tackifier composition of claim 1, the viscosity ratio at 80°C/25°C is 0.6 or more. The tackifier composition according to claim 1 or 2, wherein the cellulose fibers in the above (1) are anionically modified cellulose fibers. The tackifier composition of claim 3, wherein the modifying group is bonded to the anionic group of the anionically modified cellulose fiber via an ionic bond and/or a covalent bond. The tackifier composition of any one of claims 1 to 4, wherein the alkylene oxide chain is selected from the group consisting of ethylene oxide (EO) polymerization part, propylene oxide (PO) polymerization part, and (EO/PO) One or more (co)polymerization parts in the group consisting of copolymerization parts. The tackifier composition according to any one of claims 1 to 5, wherein the non-aqueous solvent contains a hydrocarbon-based solvent or a glycol ether-based solvent. The tackifier 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-based solvent. The tackifier composition according to any one of claims 1 to 7, wherein the average fiber diameter of the modified cellulose fibers is 1 nm or more and 300 nm or less. The tackifier composition according to any one of claims 1 to 8, which is used for electronic materials, optical materials or structural materials. The tackifier composition according to any one of claims 1 to 9, which further comprises an inorganic compound. A viscosity control agent for a non-aqueous solvent, comprising at least one modified cellulose fiber selected from the group consisting of the following (1) and (2): (1) A type I crystal structure formed by bonding a modifying group to a cellulose fiber, and the modifying group contains a group selected from (a) a hydrocarbon group, (b) a polysiloxane chain, and (c) an alkylene oxide chain 1 or more of the group formed (2) Acid-type anion-modified cellulose fibers with an I-type crystal structure. The viscosity control agent of claim 11 further comprises an inorganic compound. If the viscosity control agent of claim 11 or 12, it is used at a temperature above 50°C. The viscosity control agent according to any one of claims 11 to 13, whose viscosity ratio at 80°C/25°C is 0.6 or more. The viscosity control agent according to any one of Claims 11 to 14, whose viscosity ratio at 120°C/25°C is 0.6 or more. Use of a tackifier composition for use at a temperature of 50°C or higher, the tackifier composition containing at least one modified form selected from the group consisting of the following (1) and (2) Cellulose fiber and non-aqueous solvent: (1) A type I crystal structure formed by bonding a modifying group to a cellulose fiber, and the modifying group contains a group selected from (a) a hydrocarbon group, (b) a polysiloxane chain, and (c) an alkylene oxide chain 1 or more of the group formed (2) Acid-type anion-modified cellulose fibers with an I-type crystal structure. For the purpose of claim 16, the viscosity ratio at 80°C/25°C is above 0.6. For use in claim 16 or 17, the viscosity ratio at 120°C/25°C is 0.6 or more. According to the use of any one of claims 16 to 18, it is used in a temperature range above 50°C. According to the use of any one of claims 16 to 19, it is used in a temperature range above 100°C. The use according to any one of claims 16 to 20, wherein the non-aqueous solvent is removed. The use according to any one of claims 16 to 21, wherein the above-mentioned tackifier composition further comprises an inorganic compound. A method for coating an inorganic compound, comprising heating a composition containing modified cellulose fibers at least one selected from the group consisting of the following (1) and (2), a non-aqueous solvent, and an inorganic compound The step of removing the non-aqueous solvent to above 100°C: (1) A type I crystal structure formed by bonding a modifying group to a cellulose fiber, and the modifying group contains a group selected from (a) a hydrocarbon group, (b) a polysiloxane chain, and (c) an alkylene oxide chain 1 or more of the group formed (2) Acid-type anion-modified cellulose fibers with an I-type crystal structure.

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